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Electrocatalysis - Science topic

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Questions related to Electrocatalysis
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I want to perform pulse electrolysis, but I am unsure which program I need to run in the electrochemical workstation.
Thanks
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I want to measured the ECSA of a trimetalic alloys to be used for electrocatalysis. Additionally what could be better way to evalute ECSA of oxide materials for electrocatalysis? Further how could I measure ECSA of a metalic or multimetalic alloy supported on a oxide matrix?
Please help me.
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Suggest reviewing the following paper:
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Pt has been remarkable Hydrogen Evolution Reaction electrocatalyst in Acid which perform good even in large scale electrolysers.
While there are plenty of engineered HER catalyst reports most of them fail at reasonably high currents and long term testing. I wonder if there is any catalyst with higher intrinsic activity than Pt?
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Dear Aaditya
Then main important feature of Pt, by which makes it an ideal option, is the fact that Pt is a noble metal. For electrodeposition studies in acidic media, you have no concern about the possible dissolution of Pt. Therefore, you can focus on the mechanism of hydrogen evolution. I think you can also use other noble metals such as Pd, Ag, etc..
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Dear colleagues. I'm studying ORR on carbon materials, including graphene oxide. I'm new in this research direction and have questions: what are the compositions of the most suitable electrolytes for ORR on carbon materials? In many research papers, 0.1M KOH is presented as the most suitable one. But, acidic and neutral solutions could also be good? I need the clear understanding of the rules behind choosing the electrolyte for ORR. Any good papers, clear answers, please, share with me.
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Selecting the most suitable electrolyte for the Oxygen Reduction Reaction (ORR) on carbon materials involves a complex interplay of factors. While 0.1M KOH (potassium hydroxide) is commonly used and has been shown to be effective for some applications, the choice of electrolyte depends on various considerations including electrode materials, operating conditions, and specific goals of the electrochemical system.
Here are some points to consider:
  1. Alkaline Electrolytes (e.g., KOH):Pros: Alkaline electrolytes like KOH are generally considered suitable for ORR on carbon materials. KOH provides high ionic conductivity and can be cost-effective. Cons: However, in some cases, alkaline electrolytes may lead to electrode degradation or limit the stability of certain electrode materials. The presence of hydroxide ions can influence surface chemistry and affect the reaction mechanism.
  2. Acidic Electrolytes (e.g., H2SO4):Pros: Acidic electrolytes can provide high proton concentration, facilitating the ORR process. Some carbon materials might show improved activity in acidic conditions. Cons: However, acidic environments can also lead to corrosion of certain electrode materials. It's crucial to ensure that the chosen materials are stable in the acidic environment.
  3. Neutral Electrolytes: Pros: Neutral solutions avoid extreme pH conditions that can impact material stability. They can be suitable for systems where pH sensitivity is a concern. Cons: Neutral solutions might have lower ion conductivity compared to alkaline or acidic solutions.
The choice of electrolyte should be guided by these factors:
  • Electrode Material: Different carbon materials have varying responses to different electrolytes. Conductivity and stability of the electrode material in the chosen electrolyte play a significant role.
  • Reaction Mechanism: The reaction mechanism of the ORR can vary depending on the pH and electrolyte composition. This can influence reaction kinetics and overall performance.
  • System Requirements: Consider the specific requirements of your system, such as operating conditions (temperature, pressure), energy efficiency, and the overall electrochemical setup.
  • Corrosion: Some electrolytes might lead to electrode corrosion, limiting the durability of the system. Compatibility with electrode materials is crucial.
  • Literature and Experimentation: Reviewing literature on ORR studies for carbon materials can provide insights into the success of various electrolytes. Additionally, conducting experiments with different electrolytes under controlled conditions can help determine the optimal choice.
  • Application: The intended application of the electrochemical system is important. For example, fuel cells, metal-air batteries, and electrochemical sensors might have varying electrolyte requirements.
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I am planning on transitioning towards Power-to-X with a focus on water splitting and CO2 to fuel applications. However, there is still a lot that I need to learn before I can start working on the subject. Can you please recommend some good resources to start understanding these techniques from the very basics?
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Start with: Electrochemical Methods: Fundamentals and Applications, by Allen Bard and Larry Faulkner. Available on Amazon.
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I am doing electrocatalysis, OER. I did Chronoamperometry, and tried with and without RDE setup. In both cases, In the working electrode Bubble formation, was there. How to avoid this?
I am getting a chronoamperometry graph after 1h (electrocatalysis starts) current value increases, then decreases, again steady state, and repeated after 30 min once.
I am using ametek potentiostat.
May I know about this?
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Mayilvel Dinesh Meganathan
Thank you, sir. I will read.
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How can we combine photocatalysis with other technologies, such as electrocatalysis, to achieve more efficient and versatile energy conversion and storage?
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Thank you Umar Farooq for your contribution.
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We are studying on PEMFC electrocatalysts via magnetron sputter systems on carbon paper substrates. By this way we can perform CV and RDE experiments without using ionomer dispersion.
Right now i have to decide on the preparation method of MEA.
-I am worried about if micropippet drop or spray bottle is the best ionomer coated method? (I don't have any other option, maybe paint brush)
-What should be starting value for the ionomer/catalyst mass ratio?
-Can temperature of hot press be a reason of agglomeration of particles (above T=100C)?
-Thickness of the catalytic thin film is blow 50 nm.
Thank you.
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Hi Ceyhun Yıldırım, I wonder How do you perform RDE/RRDE using a carbon paper substrate? Thank you
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I want to do BET surface area analysis of Ni foam sample. what will be the degassing time and temperature and number of points to be consider for analysis. and any other specific details to follow?
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The degassing time and temperature for BET surface area analysis of Ni foam samples depend on various factors such as the type of instrument, the nature of the sample, and the adsorbate used. Typically, the following degassing conditions can be used as a starting point:
  1. Heat the sample at 100°C for 1 hour under vacuum to remove any moisture or volatile impurities.
  2. Increase the temperature to 200°C and hold for 2 hours to remove any remaining moisture and adsorbed gases.
  3. Finally, increase the temperature to 300°C and hold for 3-4 hours to remove any strongly adsorbed impurities.
However, it is always best to follow the manufacturer's guidelines for the specific instrument being used.
Regarding the number of points to consider for analysis, it is recommended to analyze at least three data points for the BET analysis. These data points should be taken from a nitrogen adsorption isotherm that covers a wide range of relative pressures (typically from 0.05 to 0.30). The data points should be evenly distributed along the isotherm to ensure accurate determination of the BET surface area.
Other specific details to follow for BET surface area analysis of Ni foam samples include:
  1. The Ni foam samples should be prepared by cleaning them thoroughly using an appropriate solvent such as ethanol or acetone to remove any impurities or contaminants that may affect the analysis.
  2. The sample should be pre-dried to remove any moisture before conducting the analysis.
  3. The adsorbate used should be nitrogen gas, and the analysis should be conducted at liquid nitrogen temperature (-196°C) to ensure accurate measurements.
  4. The analysis should be conducted using an automated BET analyzer, and the results should be verified using other techniques such as mercury porosimetry or helium pycnometry.
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Hi everyone I want to test the electrocatalytic activity (Overall potential at 10 mA/cm2 and long-term stability) of my Bifunctional electrodes in a two-electrode system which means that I have to take both anode and cathode of the same materials. I am a bit confused about the setup and how will I assemble my experimental setup (Potentiostat) to measure these parameters? Expert answers will be highly appreciated.
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Dear Shahid Zaman,
I want to ask a question in similar direction. I have a two electrode setup flow cell for co2 electroreduction. How can I control the potential at working electrode (cathode) vs RHE? Because I read in the literature that people report potential vs RHE. How can I measure that in two electrode setup?
Best,
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Please anyone give us what is the significant difference between photocatalysis, electrocatalysis, and photoelectrocatalysis
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What is the catalysis of water? Which reaction?
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NIL
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Hi Gohain,
Tafel slope is an important parameter to predict the type of HER mechanism i.e whether the HER process will proceed by Volmer Heyrovsky or Volmer Tafel mechanism. For instance, if the value of Tafel slope is in the range of 30 to 40, it means the HER follows Vomer-Tafel mechanism. Tafel step and Heyrovsky step both are related to desorption of hydrogen molecule from electrocatalyst surface. So, depending on the properties of your electrocatalyst, desorption of H2 will occur either by Heyrovsky step or Tafel step. The role of Tafel slope is to predict this mechanism.
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Hi, I'm graduate student working on electrocatalyst.
Most of the research article about electrocatalysis HER only measure the electrochemical performance ,such as LSV, Tafel slope, overpotentail. The production rate of hydrogen is seldom measured by research group.
Is the alkaline electrolyte won't have other reaction except HER?
I appreciate your help and sorry for my poor english.
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You raise the extremely important question. Based on the current state of the art in the catalytic water splitting (HER and OER), the formation of H2(O2) must be confirmed, if you submit your manuscript for publication. Otherwise, the submitted manuscript must be rejected. Unfortunately, the journals are flooded by highly questionable papers.
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Can anyone suggest a fundamental book Or review for a beginner.
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I recommend this book
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I have calibrated my reference electrode and it is showing the correct onset on par with reported literature. However in doubting my results and want to double check the authenticity of my reference. Please suggest any such measures
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Hi Darren
to check the viability of a reference electrode you need to do
Perform an EIS test with a two-electrode system. Choose Galvano Mode EIS (GEIS) to avoid polarization of your reference electrode. The reference electrode (working electrode) and a platinum or gold electrode ( counter electrode. The impedance of the reference electrode should come below 1 kΩ. If it is higher, then it is not viability. perform an EIS test with a two-electrode system. Choose Galvano Mode EIS (GEIS) to avoid polarization of your reference electrode.
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I am doing oxygen reduction in 0.1M KOH at a glassy carbon electrode coated with an electrocatalyst (with conductive carbon support, ethanol, nafion). When I do impedance at OCP I get the red Nyquist plot. When I apply an ORR potential I get the blue Nyquist plot.
I can't work out why I have the initial semi-circle (present both at OCP and during ORR) as it isn't in any literature examples. I can't find a circuit model that models these data well.
Any help would be appreciated.
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Matthew Bird Is it possible to measure the blue curve at few potentials where ORR takes place? It might be more informative as with current red and blue plots, it seems that the initial semi-circle could be just the contact resistance as it did not seem to change with applied potential. Also, can you show the Bode's plot.
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Hello everyone,
My PhD research includes degradation and stability study of fuel cell Pt/C catalysts for ORR. This is a new area of research, both for me (I'm coming from TEM background) and my lab, which is why I'm learning most experimental procedures and parameters from papers rather than more experienced colleagues.
Unfortunately, it seems to me that there's no agreement in electrochemical community regarding said procedures/parameters and here I would like to specify what causes my confusion:
- regarding CV and LSV procedures, from what I've already read and from my experimental data, it seems that scan speed influences ECSA data (extracted from H2 adsorption region on cyclic voltammograms) and activity data (extracted from linear scan voltammograms). Yet, I see different papers publishing data obtained with different parameters, which for me makes the results virtually impossible to compare. Additionally, some procedures include the so called electrochemical cleaning and stabilisation of the working electrode by performing 40-100 CV scans with higher speeds (100-200 mV/s), yet some papers seem to omit it. With LSV some procedures call for background subtraction of LSV data obtained from the measurement performed in N2 saturated electrolyte but again, not all papers include that step (yet both approached seem to be acceptable for publication).
Regarding accelerated degradation testing, the procedures seem to be a lot more all over the place:
-different scan speeds
100-500 mV/s, and from my experimental data I already see that scan speed influences degradation rate,
-different approaches to experiment
continuous scan vs 'sample and hold' (square wave) scan,
-different potential ranges
lower limit being 0,4 - 0,6 V, higher 0,9 - 1,2 V for operating condition testing, start-stop testing seems to be consistant 1 - 1,5 V,
-different "atmosphere" of electrolyte
O2 saturated, deoxygenated and "as prepared" electrolyte, all of those seem to be leading to publishable results.
So to sum up my stream of consciousness:
I'm not looking for specific experimental parameters (although getting some suggestion on those would be more than great) but rather some insight on the general consensus in electrochemical community regarding said parameters and why discrepancies in them seem to be widely accepted. Also, if someone feels like they have more spare time than they can utilise, I would be more than willing to participate in an internship in a unit focused on degradation/stability study of catalysts.
Thank you and have a great day,
Szymon
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Hi,
Very good points Szymon! To me also it seems sometimes impossible to compare the results in electrocatalysis due to different measurement and calculation procedures.
Talking about degradation tests, I am not sure about ORR, but in water splitting electrocatalysis the reason why different procedures are all accepted may be that these tests are usually performed in much harsher conditions that is required for industrial applications and they all pass the criteria defined for them to be called "stable".
I suggest reading this paper which is in water splitting electrocatalysis but can be a help for you too!
"Anantharaj, S., et al. "Precision and correctness in the evaluation of electrocatalytic water splitting: revisiting activity parameters with a critical assessment." Energy & Environmental Science 11.4 (2018): 744-771."
Good luck!
Arash
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Hello everyone.
For quite some time now we're trying to employ IL-TEM technique in our lab. In this method the catalyst is deposited on TEM grid, some regions on the sample are chosen for detailed investigation, then the grid is placed in electrochemical cell and the accelerated degradation test is performed (several thousand CV scans). After degradation test the sample is placed back in the microscope, and regions chosen before are examined again.
Literature on the topic is rather ambiguous regarding potential ranges, number of scans, methods of holding the TEM grid in the cell.
Recently we've managed to obtain some promising results, but we're still dealing with a massive problem of gold (originating from grid) dissolution and re-deposition on the sample (most visible in image A3_after_2). This problem seems to be dependant on the upper limiting voltage I'm choosing - the higher the voltage the more of a problem gold becomes. Images I'm attaching come from the measurement performed in 0,4 - 1,2 V (RHE) range, with 200 mV/s scan speed in air saturated electrolyte. The sample was removed from cell after 6000 CV scans, examined, then placed back in the cell for another 12000 scans. It was possible to find some places without gold, but the success of a procedure is hugely luck-dependant. During that measurement the sample was held in self-locking tweezers, which were not in contact with electrolyte. Regarding the sample mounting method I tried few things:
1. Sandwiching the sample between 2 glassy carbon plates.
The plates were immersed in the electrolyte. For some reason this method, with same parameters as the tweezer method, resulted in higher gold contamination.
2. Using 3d printed caps to attach the grid to the electrode
No changes in the catalyst were observed. There was no gold either, which suggest problems with the contact
3. Attaching grid to the electrode or the glassy carbon plate with teflon tape.
Same case as 2., no changes.
4. Attaching grid to the gold plate using teflon tape, resulted in massive gold contamination.
I'm more experienced microscopist than electrochemist, so it's more than possible that I made some electrochemistry-related errors (obvious for someone with experience) during my measurements and I would be more than grateful if someone could point them out.
What I'm most interested in is some advice regarding how can I limit gold contamination during the experiment, as well as some general IL-TEM tips.
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Thanks a lot, I've known the second paper, but the IL-SEM one is new for me. This is actually the first time I see someone mentioning potential degradation of gold as an issue to be aware of in identical-localization microscopy. Their upper potential (1,17 V) seems not to be so far from mine (1,2 V), which for me caused significant gold contamination. Is that 0,3 V really a make-or-break kind of difference? Also, since that paper SEM-based, some gold could precipitate in the form of particles outside of instrument's detection limit.
What I haven't clarified in my first post - I'm conducting the experiments in 0,1 M HClO4.
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Literature shows methanol oxidation in direct methanol fuel cell (DMFC) takes place by noble metals like Pt, Ru etc. Could we use other transition metals or non-metal nanocomposites for the oxidation of methanol. what are the things to be considered for selecting electrode material for DMFC or DEFC
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Dear Vishnu,
many thanks for sharing this interesting and important technical question with the RG community. In view of the extremely high current prices of noble metals like Pt, Ru etc. it is not surprising that researchers make serious efforts to replace these platinum-group metals by cheap transition metals or even non-metallic materials. In this context I can suggest to you the fowlloing very interesting literature reference:
Methanol-Tolerant M–N–C Catalysts for Oxygen Reduction Reactions in Acidic Media and Their Application in Direct Methanol Fuel Cells
Fortunately this article has been posted by the authors as public full text on RG. Thus it can be freely accessed and downloaded as pdf file. Please also check the references 18 and 19 in this article. They also describe cheap replacements of expensive platinum-group metals for use in methanol fuel cells (DMFCs).
Good luck with your research and best wishes, Frank Edelmann
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Which porous materials (Micro/Meso/Macroporous) are very suitable for the electrocatalysis application (ORR, OER and HER)
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Sincerely,
Microporous with dimensions less than 2 nm are suitable for adsorption applications, but for electrocatalysis, mesoporous is more suitable to facilitate ion transfer. In general, among all these structures, a hierarchical structure with a variety of porosity dimensions is the best choice for your purpose. Of course, to choose the right type of structure, the ratio of mesopores to macro and microporosity must be at least double. Increasing the pyrolysis temperature in the furnace up to 900 ° C helps to achieve the mesoporosity structure. In addition, the use of steam-assisted physical activation helps to form more mesopores.
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Hi I am trying to synthesize quantum dots for the fabrication of electrodes for HER. I have metal oxide power so conventionally people use plates as target for production of Quantum Dots. So is it possible to use powder as target precurosor for synthesis of Quantum dots?
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Dear Shahbaz Ahmad,
Yes, of course, it is possible to synthesis of TMO QDs using TMO powder as target precurosor.
I hope that my article paper have been helped you.
Modified top-down approach for synthesis of molybdenum oxide quantum dots: sonication induced chemical etching of thin films
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I want to compare the HER and OER results of metal strips that I have prepared now in elecrtochemical workstation I am using those strips of 0.5 cm*0.5 cm as working electrode. Now in order to compare it with standard commercial Pt/C should I deposit Pt/C slurry on glassy carbon electrode and then do analysis to compare the results or there is some alternative method to prepare commercial Pt/C like a those of square metal strips I am using?
If I have to use GC then should the area of GC and metal strips be equal or not ?
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We are sorry. I can not answer because they are not of electrochemical experts.
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I am trying to build an aqueous and solid-state zinc-air battery that will utilize a 3-6M KOH solution as an electrolyte. I would like to order a current collector for the air-cathode side and I have been torn between Ti, Ni, or stainless steel mesh.
Both the Ti and Ni mesh are relatively expensive (£100+ for 15cm by 15cm meshes), with Ni possibly contributing to OER activity during charging however likely corrode to form NiO and Ti being generally known for its chemical stability. Furthermore what kind of wire thickness of the mesh would be most suitable? Am I correct in thinking that smaller wire mesh will provide greater contact area and oxygen permittivity, so I should aim for the smallest available?
Would someone kindly provide me with a little bit of advice on the matter? Many thanks
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Hi Szymon,
From what I have seen for alkaline media:
Nickel is chemically resistant, and a good OER catalyst. Can dislodge catalyst during charging.
Titanium doesn't evolve oxygen during charging, but you may get some dissolution initially.
Steel may release ions such as Fe, Cr, Mn over time that can contaminate the zinc electrode.
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What should be the properties of a dream catalyst (electrocatalyst) for electrochemical CO2 reduction?
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There are couple of issues which equally important for the eelctrochemical reduction, CO2 is highly stable molecule...
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I have several curves of applied potential versus electric current with hundreds of points in each of them. I am trying to analyze their first and second derivatives, but they are too noisy to make sense.
I have tried using the Smooth tool in Origin, however they have several different smooth algorithms. How can I choose which Algorithm is best suited for my data?
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Link will be helpful to smooth XRD data by removing signal noise using origin
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Hello
I've recently reached the point in my work when I will need to conduct some electrochemical measurements, but unfortunately I have to start everything from scratch, because in our lab no one was ever doing measurements of electrocatalysts. Basically, I'm looking for any kind of instructions on how to perform ORR measurements. Right now I'm playing with commercial Pt/C catalyst, I'm using glassy carbon working electrode, platinum counter electrode, Ag/AgCl pseudo-reference electrode and 0,1 M H2SO4 electrolyte. I'm trying out different inks with different Nafion concentrations, but so far all my CV spectra have no resemblance of the ones presented in literature.
Thank you in advance for any suggestions.
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First, commercial Pt/C has to be electrochemically cleaned. In your conditions dozen of CV cycles in the potential range ~ -0.2 V to ~1.35 V. (After that replace the solutions). You can see the procedures in classical papers by Schmit and Gasteiger, for example:
T. J. Schmidt et al 1998 J. Electrochem. Soc. 145 2354 Characterization of High‐Surface‐Area Electrocatalysts Using a Rotating Disk Electrode Configuration, This is added by RG when I put doi?
or
U.A. Paulus, T.J. Schmidt, H.A. Gasteiger, R.J. Behm, Oxygen reduction on a high-surface area Pt/Vulcan carbon catalyst: a thin-film rotating ring-disk electrode study, Journal of Electroanalytical Chemistry 495 (2001) 134 – 145 .
Greetings,
prof. Grgur
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In case of electrocatalysis, if we use gold nanoparticles stabilized by different organic moieties like flavonols, curcumin, curcuminoids, PVA, citrates, etc. Will it decrease the efficiency of the electrocatalysts towards oxidation of electroactive molecules such as dopamine, serotonin, ethanol and methanol? Will it increase the poisoning on the electrode surface?
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It does increase or decrease based upon nature of capping agent
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Hello everyone,
How do magnetic field increase the electrocatalytic activity? How do magnetic field affect the reaction process? Some of the papers mention that magnetic field generate magnetohydrodynamic effect, some of them mention about spin alignment of oxygen as paramagnetic, and others mention that magnetic field helps to lower the binding energy between active material and oxygen.
Does anyone have another hypothesis or opinion?
Thank you.
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First, I would contact the authors of this paper. It's not the best way to start a public discussion of this paper. At least invite the authors to your thread.
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I have just started to gain basic information about gas sensing materials. So here, I want to know what materials are in touch nowadays for efficient gas sensing, and what are the corresponding advantage and disadvantages?
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When it comes to the choice of materials for MOGS (Metal Oxide Gas sensors) applications, materials which exhibit high resistance variation upon exposure to the test gas is considered as most suited. Not all metal oxides can be used as a sensor material. In the last 50 years of sensors research, the choice sensing material has always been empirical. However, the thumb rule for a metal oxide to be used for MGOS application is that, the surface chemistry of the metal oxide should be in such a way that it is sensitive to oxidizing or reducing atmospheres. The details are available in plenty of review articles like this one : doi: 10.3390/s91008158 .
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The ORR polarization plot in the paper (the one with many colors) is very sharp but that of my catalyst is really smooth. I guessed that it is because all the activity sites in my catalyst have high reaction potential (bad thing for a catalyst). Is it right?
And how to improve my catalyst?
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Hello Mr. Huang, In addition to the above suggestions like 1) the film on active geometrical area of RDE is not uniform 2) Roughness is very high, you can think in slightly different line too. Whenever, the mixed and the diffusion controlled regions are not well separated this is another indication of non-uniform distribution of electroactive centers in electrocatalyst it self. In case of commercial Pt-C sometimes the Pt nano particles (d ~ 5nm) may have nonuniform distribution across the carbon support (d~30 nm).
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We are performing electrocatalytic CO2 reduction experiments and are unable to measure the low quantities of CO that we are producing. This may be due to a large excess of CO2 (20 mL/min) that we are flowing through the cell.
We are using Soprane GC machine with Molecular sieve 5A, 10 m long column.
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Dipak Shinde Molecular Sieves %A column is only useful for elution of O2,N2,CH4 and CO when connected to TCD detector .Note That CO2 could not be detected using the same column. The detection limit of your detector needs to be validated first possibly by passing lowest concentration of products that you may form i.e CO gas.Secondly if your detector is sensitive enough to detect the concentration then injector volume,split ratio of injector can be changed to obtain desired peak for CO. Lastly the CO2 electro-reduction i.e. CO2 conversion could be very less which gives lower concentrations of CO which can be improved by process optimization. Find attached document which can help you to develop method for elution of CO and other permanent gases.
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I'm going to synthesize nanoparticles of lead dioxide and then I want to disperse them on the support of TiO2 nanotubes to make a catalyst. So would you please suggest me a procedure that I can almost disperse pbo2 on my support homogeneously?
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We can adopt in situ method towards PbO2 on TiO2 synthesis. This method involves alkaline hydrolysis of Ti isopropoxide and PbCl2 as precursors of Ti and Pb to form hydroxides which is on calcination to form PbO2 loaded on TiO2 composite.
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Whenever I pyrolyzed NaH2PO2, I am facing difficulties in cleaning the left over white residue (may be phosphates) in the tube.
So, I am looking for any effective cleaning protocols to get rid of this issue.
Thanks.
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Yes Mr.
Curtis Guild
Actually, when we try for the annealing of potassium niobate, we suffer from those cracks on the tube. The niobium gets reacted with Si and forms Niobium Silicate. Those cracks are at inner surface of the tube. And cracks get propagated and unfortunately that tube get damaged.
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My trouble here is understanding how to ensure results at different pH are comparable. I am asking this because different buffers have different ions and hence different electrochemical properties right? Can I just use a buffer of X pH and Y mM concentration or do I also have to add some third salt to it to adjust the conductivity somehow?
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You have to find the compromise to avoid the effect of buffer but still to have a sufficient buffer capacity. Roughly, 20 mM NaPi buffer at pH 3 could absorb about no more than 1 mM of H+ or HO-, at pH 7 the buffer capacity is pretty high. 20 mM NaBi at pH 10 could keep pH with change of H+/OH- about 2 mM. If you want to opt for the highest buffer capacity move to pH 2.2, 7.4 and 9.5. The buffer will keep the pH constant, but you need a high conductivity of your solution. Therefore, the concentration of electrolyte must be rather high, minimum 100 mM
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I'm a first year PhD student (1 month in) looking into the activity of an oxidation electrocatalyst, similar to TEMPO. I would like to see what kind of conversion rate I can achieve over a couple of hours. My cell is always made up to 3mL and I use around a 2mM concentration of my catalyst. What kind of ballpark concentration should I be using for my substrate? My CV analyses have been using around 200mM substrate when looking into catalyst diffusion coefficients, as to not limit the current to the diffusion of the substrate, but I have no idea if this is very high, very low, or just right for an amperometry experiment.
Thank you in advance!
Supporting electrolyte concentration: 0.15-0.25M
Solvent used: DCM
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note, if possible, the WE[1], CE (and RE[1] ?) electrodes' materials of your cell, since the amperometric transduction is based on the oxidation and reduction of electroactive species on the biosensor surface (WE)[3].
Also, show, please, some of your CV(s).
1. High Accuracy Amperometric Sense and Control Circuit for Three-electrode Biosensors https://romjist.ro/content/pdf/enache.pdf
2. Chapter 4 - Graphene Functionalization for Biosensor Applications https://www.sciencedirect.com/science/article/pii/B9780128029930000046
3. Sequentially multiplexed amperometry for electrochemical biosensors https://www.sciencedirect.com/science/article/pii/S0956566318304810
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In many areas of electrochemistry (electrocatalytic water splitting, CO2 reduction, N2 reduction, etc.), we must relate electrochemical data (current, potential) to on-line chemical quantification data (from e.g. gas chromatography, mass spectroscopy) to properly characterize processes and determine Faradaic efficiencies of electrochemical transformations under different conditions. The challenge is that this requires multiple different sets of hardware & software, and produces data output in different formats and with different time scales. Such systems typically aren't designed to work together automatically, so the researcher must typically spend significant time on post-run data workup to represent the results in a meaningful way.
To those working in this area: What are some strategies for automating the analysis of these combinations of data? Of course, with clever programming (and considerable effort), one could make their own unified software managing everything (e.g. in LabVIEW), but surely there are examples of simpler approaches which people use. I am curious to hear how you do it -- and hopefully this conversation can be mutually helpful for everyone.
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So I'm not an electrochemist, but I stumbled across this thread and do have some experience building/publishing open-source library code in Python. Is this a problem which simply requires analysis procedures to be codified? I'd be up for a collaboration to try and build a library system which automates some of this grunt work if anyone thinks that's feasible.
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Are the explanations below enough to explain their 20%Pt/C superior performance?
Explanation1: The good stability of N-doped carbons has to be mostly ascribed to the covalent bonding of the catalytically active heteroatom to the carbon structure, unlike the physical bonding of Pt to carbon support. (Antolini, 2016, 10.1016/j.rser.2015.12.330)
Explanation2: The introduction of N atoms into carbon increases the electronic density of states near the Fermi level, thus facilitating the electronic transfer from the electronic bands of C to O2 σ* antibonding orbitals.(Xiaoming Ge, 2015, 10.1021/acscatal.5b00524)
Below are listed some of the properties of the metal-free electrocatalysts:
Elemental analysis: 0.5% wt. nitrogen, 4.5% wt. sulfur, 2% hydrogen EDS: 70% carbon BET: 2000 m2 g-1 Raman: Id/Ig = 1.23 (amorphous, defects) XPS: N-pyridinic and N-graphitic presence
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You can take a look at this article for the nature of active site. It sheds some light on activity of various N-doped carbons in alkaline media. (doi: 10.1039/C8SC04596H). Both sites seem to be active for ORR.
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I am working on synthesis of graphene based ORR catalyst from biomass and examined it in 0.1M KOH and got the results. The CV was done with glassy Carbon electrode(WE), RHE(RE) and platinum electrode(CE). I have synthesized two different catalyst labeled as Catalyst 1 and Catalyst 2 from two different biomass. The catalyst loading on GC electrode was 40mg per sq. cm. For each catalyst sample, First CV was performed with Nitrogen purging condition followed by oxygen purging condition at scan rate of 50 mV/s.
As you can check in picture, that I am getting peaks at different potential for these two catalysts in oxygen purging condition.
a). Why for these two catalysts, ORR reaction starts at two different potential even if both are nitrogen doped graphene?
b). Why the CV of Catalyst 1 is different than catalyst 2?
c). what kind of peaks are observed in catalyst 1 at near about 0 potential(Both in N as well as in Oxygen purging condition)?
d). Why these catalysts do not show any activity in perchloric acid?
e). Is there any use of ORR catalysts showing activity only in alkaline medium?
f). What are other relevant information and conclusion we can draw from this CV result?
It will be very helpful if you help me to get the answer of any of those questions mentioned above.
The file is attached with the question.
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Lakhan,
Question a) The reduction of oxygen is starting earlier in catalyst 1 in comparison with catalyst 2. This means that catalyst 1 is better than 2 for ORR.
Question b) You have a large capacitance behavior in catalyst 1 in comparison with catalyst 2. This means that the surface area of catalyst 1 > catalyst 2. Thus, you need to normalize against the area before you can compare.
Question c) That is the initial charging of the capacitor.
Question d) ORR is easier in basic medium.
Question e) No. The problem is that CO2 will neutralize a basic electrolyte. Here you are touching the holy grail of electrocatalysis. Get a better ORR catalyst in Nafion (acidic). Even traces of CO in the fed hydrogen can go to CO2 and destroy the electrolyte. This will work with ultra-pure hydrogen though. But it is more expensive.
Question f) you have poor electric conductivity in your catalyst 2 composite. This is why catalyst 2 under nitrogen CV is inclined (ohms resistance).
Omar
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Substrate- active material interaction
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Both are okay. Usually porous 3D metallic substrate is preferable. To coated nanoparticle, you may need to apply Nafion binder.
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I made several ORR catalyst for PEMFC but after putting the catalyst in vial/glass bottle/polybags, I observe decrease in onset/peak potentials with the passage of time. e.g. if I test my catalyst today then its performance is good but after some days/month in a vial, I make fresh catalyst ink and its performance is very bad. Is it normal that every NPMC degrades like this (attached) with the passage of time? what's the cause of this sort of degradation and how should we store catalyst powder so that we may test it in future without any performance loss?
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Dear Muhammad,
NPMC are susceptible to various forms of deactivation, particularly oxidation in ambient environments. For instance, if you are looking at a concrete building or wall and notice streaks of reddish brown scattered about, you are observing solubilized iron oxide products (mostly Fe3+) that have spontaneously formed from the metallic iron supports and leached through the concrete.
Humidity, light, and ambient oxygen are all it takes to create these oxide products which may deactivate your material, therefore it is suggested that you purge your containment vessels with an inert gas such as N2 or Ar, and keep them in a dark refrigerator to minimize the rate of these processes.
Furthermore, if you are working with alloy NPMCs you may want to investigate their relative standard potentials (chart link here: https://en.wikipedia.org/wiki/Standard_electrode_potential_(data_page) ). Various transition metals that are in direct contact can spontaneous oxidize others over time, which may be a contributing factor to the deactivation. This idea forms the basis for many batteries!
I hope these suggestions provide a good basis for a better understanding your system, good luck!
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I am doing work on non-precious metal catalyst for ORR. All the times, I get narrow peak using CV while a broader peak using LSV for the same catalyst (as shown in the attached figure) at same scan rate, quiet time and sensitivity. I think I should get same peak potentials in CV and LSV for the same catalyst. So, why I am getting this difference in peak potentials?
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If you record LSV under solution stirring conditions, LSV and CV MUST be different
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Dear All,
I've been thinking about how to simulate the cyclic voltammogram for electrocatalytic reaction (such as HER, ORR or formic acid oxidation).
I've read some papers on the subject, but what I've found is really confusing:
On one hand, there are plenty of works done on simple electron transfer reaction (e.g. Prof. R. G. Compton), they've used the electrochemical kinetics as the boundary condition for solving the diffusion equation.
On the other hand, M. Janik and Rossmeisl et al. have used DFT to calculate the CV for OH adsorption on Pt(111) and other surfaces. But they didn't use diffusion equation at all.
So I wish to start a discussion about what processes that must be considered in modeling the CV curve for electrocatalytic reactions? I think this is a very important topic in electrochemistry (especially in electrocatalysis since CV can tell us a lot of information) and wish to hear as many responses as possible.
Hope we can move the field forward by combining our wisdoms.
Thank you all.
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Dear Zhengda,
In CV, the changed potential will accompany with the generation/consuming of the solute in solution phase.
If such generation/consuming of solute is large or sustaining, the concentration polarization will be established on the surface. The mass transport will hence become notable, thus greatly impact the measured current. In this case, the diffusion equation should be taken into the consideration. On the contrary, while generation/consuming of solute is tiny or not sustaining to establish the concentration polarization, it will be unnecessary to consider the diffusion.
As for CV of electrocatalytic reactions, if the associated reaction are HER/HOR or ORR/OER, generation/consuming of solute should be continuous, because a constant total Gibbs free energy deltaG=-nFU will always exists for these reactions. That is the reason the diffusion equation should be used.
On the other hand, for the DFT studied of OH* adsorption/desorption by, e.g. Rossmeisl et al, they just simulate the CV without the existence of O2/H2. And the reaction they simulate are quite reversible. Like H-upd region or OH adsopriton/desorption region on Pt111. Under this case, the generation/consuming of solute is not continuous. Because quasi-equilibrium of reaction establishes at any given potential. So in this case, the diffusion can be dismissed
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When using a graphite rod as a counter electrode, I find that over the course of an experiment the graphite dissolves and discolours the electrolyte (thus contaminating it). What is the best way to prepare and use a graphite rod as a counter electrode such that this does not happen?
The electrolyte I am using is 1M sulfuric acid. I also observe the same issue in 0.1M KOH.
Where possible please provide literature references.
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Hi Matthew, in general, carbon is not stable at potentials >0.2 V [SHE] and forms HCO3-/CO3- in neutral and alkaline electrolytes. If your counter electrode is polarized in this range, it may dissolve, although the rate should be limited. Do you use a standard Carbon CE? Normally, they are made virtually inert by reducing imperfections and lattice defects in the surface, which interferes with electron transfer reactions. But if the surface is damaged or shows pores and microcracks, anodic reactions become possible.
So in some cases a carbon CE may not be suitable. I would prefer another electrode material, if possible.
Best regards,
Andreas
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Is there any common experimental setup that can test the most electrocatalysis reactions?
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Hello Seungjae Lee
What is the application?
Often the key goal is to determine the current density for a given over potential: kinetics of system and mass transfer effects, useful equations here are: Butler-Volmer and Tafel.
There are a few other practical objectives: to determine activity, stability and selectivity of the bio catalyst.
Experimentation wise, cyclic voltammetry is the most universal technique, a rotating-ring disk and chronoamperometry are also useful.
Best regards,
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Hi,
I am working with noble-metal selenide for electrochemical hydrogen evolution reaction in acidic medium. Using DFT, I found that Se sites are active towards HER. I want to prove it experimentally by blocking the Se site selectively and without affecting the metal sites. Is there any way to block the Se sites?
Thanks,
Saurav
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Methylation is a good idea, or adding a soft metal (gold(I)) to bind to the sites?
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I am unable to understand whether i should draw  2 slopes or 1 for the attached tafel plot. Please help.
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Good
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As the title described, I was asked for changing the Pt wire to carbon rod as COUNTER ELECTRODE for OER process.
In my own opinions, if using Pt as CE, the dissolution and deposition of Pt will enhance the HER process, especially in acid electrolyte. However, it does not happen for OER process in alkaline electrolyte. Besides, some researches showed that Pt is inert for OER process in alkaline electrolyte. But for carbon rod, in my experience, indeed the carbon rod will partly dissolve thus might deposit on working electrode, leading to the coverage of active sites.
Feel unsure.
Thanks for your answer in advance.
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I believe the reasoning for this change from Pt to GC was based on the cathodic reactions taking place in your system. In a standard system, this would be hydrogen evolution (for which Pt is indeed better). The (additional) reactions taking place in your particular system may be made more desirable by the use of GC instead of Pt, but without the full details of your experimental system (and catalysts, which are likely confidential know how at this point) I cannot offer a more confident answer.
The following two works (although focusing on the use of solar energy) include some discussion of cathodic processes in OER:
A. J. Bard, M. A. Fox, Acc. Chem. Res. 1995, 28, 141.
N. S. Lewis, D. G. Nocera, Proc. Natl. Acad. Sci. 2006, 103, 15729
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I am trying to measure ORR of carbon based material in alkaline medium. The observed LSV didn't show any limiting current at higher cathodic potentials. What could be the possible reason?
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Dear Ziyauddin,
Also, a potential region where the current is only limited by the O2 reactant mass-transport (i.e. current plateau independent of the overpotential) take place once the reaction rate is not anymore kinetically limited. The extent of the overpotential applied in your case for such type carbon-based electrode might not be sufficient enough to overcome fully kinetic limitiations for the reaction rate. The reaction rate that you measure experimentally might still be under mixed control (both reactant mass transport and kinetic limitations) despite the large overpotential. This is related to the intrisic reactivity of the catalytic sites for the material under study.
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Dear all,
While use the pseudo reference electrode, internal reference need to introduce. In the non-aqueous electrochemical system, ferrocene is most used in literature.
However, in aqueous system, pseudo reference electrode and internal reference are barely mentioned. Is there any good way to find an internal reference species?
thanks a lot
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For aqueous electrochemistry the internal reference is not needed. The potentials of most common reference electrodes (Ag/AgCl, Hg/Hg2Cl2, Hg/HgO, Hg/Hg2SO4) are very stable and well-defined in aqueous systems. The need for additional (internal) reference in non-aq. systems is because there are no good reference electrodes for non-aq. The silver wire is commonly used, but the potential of a silver wire varies depending on the solvent and electrolyte.
If you really want an internal reference for aq. Echem, you could use a "redox probe" system such as Fe(CN)6 or Ru(NH3)6.
If you're working in alkaline media (pH >11) I would recommend the Hg/HgO RE for stability. But the most common aq.-RE is Ag/AgCl. If your system is sensitive to Cl- ions, don't use Ag/AgCl - or at least use a high quality double junction RE. You could also use a reversible hydrogen electrode (RHE) if you have the custom glassware.
Feel free to follow-up with Q&A. Good luck!
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Development of new electrocatalysts for HER/OER with intended use in water electrolysis is a very active research area. The main motivations found in vritually every research article on these topics are green energy production and off-peak energy storage, and the main goal is to produce a cost-effect alternative to Pt. But the main limitation to large-scale production of hydrogen from water is high costs of electricity. Water electrolysis has been for long an established technology, and only costs of electricity limit its wider use. As of 1995, less than 0.5% of H2 was produced from water electrolysis, around 4% was produced from brine electrolysis (i.e., H2 is by-product of chlorine production), and the rest was produced from hydrocarbon (fossil) sources by steam reforming. Catalysts for alkaline water electrolysis are based on relatively cheap earth-abundant elements (Ni and Fe), and not Pt. Energy efficency of alkaline water electrolysis with this cheap catalysts is around 75--85%, which is high. Even if better catalysts are developed, this will raise the effeciency maybe by few more percents, as there are many other factors, apart from HER/OER overvoltages, that limit the efficiency.
As I can understand, these researches are driven by mostly academic interests rather than real-world applications. I would appreciate if you get involved in this discussion.
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@All. thank you for sharing you thoughts!
@Arun. I used to think that precious metals are used for water splitting. In facts, industrial-scale hydrogen production mainly relies on Ni-based catalysts and even this material is considered a little expensive for the industry.
@Muhammad. The massive interest in renewables is not new, it is renewed :) It is in fact the second "iteration", the first being around 70s-80s. A lot of different "promising" materials were identified for, e.g., photoelectrochemical cells (photoactive and catalutically active). Yet, almost 50 years have passed, we do not see any practical/commercial device of that kind.
@Artur. Overpotential is only one aspect that lowers the efficiency of electrolyzers, there are many more on the list. Suppose, we managed to overcome all the problems and the efficiency is now 100%. This means that actual gain is around 15-20%, becuase modern alkaline electrolyzers are already very efficient. This is not going to solve any problems. It would reduce the price of electrolytical H2 only a little. I think that the real problem is not in HER/OER catalysis, but how to make electricity considerably cheaper.
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Hi I was looking for good books in electrocatalysis for students. Do you know some good books starting from the very basics, reporting also good worked examples and possibly exercises?
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You may refer this book,
Theory and Experiment in Electrocatalysis
by, Stephanus Axnanda, Kyle D. Cummins
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I have been working with oxygen reduction reaction (ORR), using Pd nanocrystals. I found that the in my case, the half-wave potential observed in the reverse scan (1.0 V vs. RHE while sweeping from more –ve potential to less negative potential) is better than in the forward scan (0.9 V vs. RHE). However when I do chronomperometry, I observe a value corresponding to the forward scan. I have not been able to find any literature justifying which scan value should be reported. Can anyone please advise or guide to the right literature. Thanks.
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Thank you for your answer. But reverse scan (more negative potential to less negative potential) gives better half wave potential value. Why can not we consider the reverse scan result? If you can refer me some references it will be very helpful.
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My enquiry is about any chemical/electrochemical species maybe ions or gas, etc. that adsorbs on Pb surface exposed to that species.
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BET method is preferred choice for higher relative surface areas like porous materials, activated carbon ,quantum dots materials,graphene and nanosized metal oxides.I thinck the Lanqmuir model is compatible with metals which have low relative surface areas.
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Currently, I am studying the electrocatalytic activity of transition metal oxides like NiCo2O4 for oxidation of methanol. The electrolyte used is 1M KOH and added 0.5M methanol to see the activity of NiCo2O4. I used GCE, Ag/AgCl, and Pt wire electrodes. But, most of the time when I repeat the CV experiment with the same condition the next day, I don't get the peaks or get very weak peaks. What is the possible reason for this type of inconsistency? 
Thank you.
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Electrochemistry is all about the properties of electrode surface. If you don't polish/clean the electrode, next day you are dealing with another electrode.  Polishing/cleaning of any electrode is highly irreproducible procedure.The answer for question: each time when you start CV, you have different electrode surface
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I plan to load metal oxide based catalyst on a ring electrode in a Rotating Ring-Disk Electrode setup (RRDE).
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Hi Manna,
apologies for shameful self-promotion but we have described a method in some details in our recent paper. See extract:
"Electrochemical performance was investigated using a CH Instruments CHI760D potentiostat with a three electrode setup in 1 M H2SO4 electrolyte unless otherwise stated. Following the procedure by Gao et. al, [26] the catalysts were prepared as inks and deposited on to a glassy carbon working electrode (surface area 0.071 cm2 ). This involved sonicating 1 mL water: ethanol (3:1), 80 µL Nafion and 10 mg catalyst for 1-2 hours. 30 µL of the resulting catalyst ink was then dropcasted onto the surface of the glassy carbon electrode. Platinum wire and 3 M Ag/AgCl were used as the counter and reference electrodes, respectively. The electrode potentials were therefore converted to NHE scale using E(NHE) = E(Ag/AgCl) + 0.209 V and the ohmic resistances were compensated."
REF 26: S. Gao, Y. Lin, X. Jiao, Y. Sun, Q. Luo, W. Zhang, D. Li, J. Yang and Y. Xie, Nature 2016, 529, 68–71.
Good luck,
Alexey
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To conduct electrochemical CO2 reduction experiment, How can I convert Ag/Ag+ reference electrode to RHE reference electrode? To convert reference electrode value, I want to know pH of 1M TBAPF6 in MeCN solution. I would be grateful if you could tell me the correct way.
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Definitely, pH has sense in aqueous solutions. Measurements of pH in nonaqueous solutions require pH meter calibrated for such conditions. Activities of protons are not the same in organic solvent as in water. Some calculations made under other conditions are hard to verify. I agree with Alan F Rawle.
How to convert the potential of the reference electrode to the other one? The simplest way is to measure the system, which is well defined with known redox potential vs. RHE, for ex. ferrocen/ferrocenium couple with your reference electrode.
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When a Bimetallic pair such as Au-Pt comes in contact with an electroactive species, a potential is induced between the electrode surface and the far-field bulk, I have successfully applied techniques such as CV, LSV and chronoamperometry to study the diffusion and reaction kinetics.
But I'm more interested in studying/measuring the induced potential in relation with surface reaction (Damkholers number) when the bimetallic system (Au/Pt) acting as a complete circuit, comes into contact with an electrolyte e.g H2O2.
I'm thinking about Open circuit potential (OCP), but are there other techniques I can use ?
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I'm not entirely sure, but ZRA mode testing may be ideal for that. In that case you would have separate Au and Pt electrodes which are shorted through a ZRA (most potentiostats have a ZRA mode).  In addition to measuring any current flowing you would also be able to measure the potential of the couple relative to a reference electrode in solution.  You should be getting the same info as you would with OCP but with the added measurement of the current flowing between the two metals which you cannot get directly from the bimetallic electrode.
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I want to know the comparison between rare earth and transition metals for use as an electrocatalyst. There are many papers which describe that rare earth can be used as electrocatalyst but none of them describe the role of rare-earth. Can anyone please share some papers relating to the chemistry of rare earth for electrocatalysis.
Thanks,
Saurav
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Mr./Miss/Mrs Sarma,
In general, such as formulation of your question assumes a completely lack of experimental experience in the field of coordination chemistry of both transition metals (TMs) and lanthanides (Lns).
Because of if you have any kind of experience even with a small representatives of these d- and f-elements, you should know that the chemical reactivity is different even within the framework of the series themselves.
There should be more proper question:
Which complexes of which metal ions from TMs and Lns series exhibit superior catalytic activity towards X, Y, etc...?
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i have deleted the question ?
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 If E is applied  vs OCP, it is on a relative scale and it means your system is at equilibrium if E=0. If E is vs REF it is on a relative scale also, but can be converted to an absolute scale (because E for REF is known). 
                            E vs REF = E vs OCP + OCP vs REF = Eabsolute - Eref
You must have a reason to choose a  value for E applied. The simplest way is to first record EIS at   the equilibrium state. Then add recordings outside this equilibrium state. It is easier to use OCP as reference. But it is better to first record OCP (vs. REF); this allows you to define any value on an absolute scale.
Let say you measure EIS with an applied potential E=0.  Eapplied = 0 V vs OCP has a clear meaning (don't forget to add OCP was...V vs REF), but Eapplied = 0 V vs REF is an arbitrary option. 
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I tried several catalytic ink recipes using PVDF in NMP and Nafion as binders but I had problems such as cracked electrode and losses of material. My catalytic ink containing polypyrrole. 
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Hello Raisa
That is a tricky question. The cracks are normally due to many reasons, but I have found the load and the way you let the electrode dry are key factors. If you are spraying on glassy carbon or carbon paper, try pre-heating before spraying your ink on top of that, and be careful not to spray too much, because the overload will make you catalyst crack and fall off.
 By the way, in alkaline media Nafion may not seem the best choice for binder, but it sure will require a lot more NMP to achieve the same effect.
 Good luck
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Dear all,
I was trying to deposit a powder sample onto an electrode and to test its electrocatalytic reactivity. I tried to suspend the powder sample in EtOH and then drop cast this ink solution on the electrode surface. However, I noticed a low electrical current during the CV measurement and I think this is because of the gap between the powder and the electrode surface. Also, I noticed that even the powder sample is physically adsorbed onto the electrode surface, the powder sample is easily detached from the electrode surface. Is there a better way to deposit this kind of powder catalyst onto the electrode surface? Thanks for your suggestion.    
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In a first step,type of electrode must be known.In the second step,you can use some conductive polymers such as pyrrole for electrodeposition or natural polymer such as  chitosan or other type polymer, nafion (a sulfonated tetrafluoroethylene based fluoropolymer-copolymerfor) casting method.Moreover, you can use electrodeposition for directly deposition of metal nanoparticles  on surface of electrodes.
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When the ORR catalyst i synthesized gives five times greater current density than the commercial Pt/C, then the slope of the KL plot for the catalyst synthesized will be higher because of the higher density. In Kouetcky-Levich equation all the parameters except slope are constant as i used the same electrolyte. So when i calculate number of electrons transferred  i am getting wrong answer. Can someone help me with this problem.
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i repeated the measurements. I am not able to get the number correct for Pt/C itself. the value is around 5.
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Hi,
I am trying to determine which parameter (current or voltage) is more important for electrochemical hydrogenation.  I understand that current is directly related to the rate of electron flow but the voltage at the applied current also determines how the reaction proceeds.  Essentially, I want to know that when to determine which parameter is more important for hydrogenation from a CV.
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The voltage WORK - COUNTER is not so relevant, but the potential of your working electrode is critical.
Add to your 2 electrodes set up a REF electrode and a common voltmeter between REF and WORK. Increase voltage until you have a relevant high current. Verify if the potential of WORK electrode vs. REF is in agreement with the intended electrochemical process. The value for current is correct only if it is confirmed by the potential of the WORK electrode. 
The current value is the same in any section of your circuit (including the redox process at electrodes). Thus if you want a constant rate for the electrochemical process, choose to maintain/control a constant current density. Monitor the voltage measured between WORK and REF.   
The voltage between WORK and COUNTER is relevant only to calculate how efficiently the energy is spent. It is not an appropriate way to control the rate of the electrochemical process. 
Voltage and potential are very different things.
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I am studying a nickel based catalyst for water oxidation. While performing chronoamperometry in 1M KOH, I apply 1.6 V vs RHE and probe the current. The value of current is 10 mA initially and gradually decreased to around 4 mA in 3 days. I thought this is because of degradation of catalyst. However, when I replenish the KOH in the cell with the fresh one, the current  restores to its original value (nealy 10mA). What may be the reason behind this? 
Thanks in advance.
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Hi Yuri,stirring the solution just increases current by 0.5mA, however, replacing the electrolyte restores the current to its original value. Also, pH of the electrolyte didn't change much after electrolysis for 3 days.
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I synthesized S-doped graphene as a cathodic catalyst for Oxygen Reduction Reaction (ORR) in Microbial Fuel Cell. I also measured ORR activity using Rotating Disk Electrode (RDE). However, RDE results were not well correlated with MFC performance. In RDE, the electron transfer number (n) of S-GN was 2.67, Pt/C was 3.7. But the performance of S-GN in MFC was higher than Pt/C. Did anyone observe the same phenomenon? What are the possible reasons for that contradictory? 
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It is a difficult task to compare RDE data with performance results from real FC experiments. Further information might be helpful from CV and LSV. One reason, that the performance of the catalyst in FC operation is higher, could simply better utilization of the catalyst material and higher electrochemical active surface area.
Kind regards
Peter
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I'm working with choline-based ionic liquids where the anions differ from: acetate, hexanoate, isobutyrate and propionate. I analyzed the contact angle using water droplet and obtained increased contact angle in the order i described the anions. How can a relate the contact angle with hydrophilicity (all angles were below 90º)?
Thanks in advance :)
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Hydrophilicity should rise in order hexanoate< isobutyrate < propionate < acetate <(formate). The larger is hydrophobic tail, the lower is hydrophilicity (if charged group is same).
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Recently, we studied some common electrolytes (LiTFSI in DMSO or TEGDME) in Li-O2 batteries and found the resistance of the whole cell is a bit large. We believe that the resistance is mainly from the electrolyte. Therefore, we would like to ask other researchers' help on the high conductive electrolytes? Thank you.
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Well. If you are talking about Li-air instead of Li-O2, and you still want to find relatively stable electrolyte, it becomes far more challenging.. In that case, try use DMA solvent with LiNO3.. You may want to look into a paper in JACS 2013, written by Walker et al..  
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The CV curve for ethanol electrooxidation just increases contiunously without a peak, what might be the cause for this?
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The absence of redox peaks in the CV graph indicates towards the non-presence of any redox reactions, well in the voltage window you use. However, if you tune the voltage window as well as the sensitivity level, the potentiostat may catch the redox peaks if there are some. 
However, for studying the ethanol electro-oxidation you may read the following papers where the researchers have used additional electrolyte like sulfuric acid with ethanol.
1.L. Han et al. Ethanol electro-oxidation: Cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic oscillation. international journal of hydrogen energy 37 (2012) 15156 -15163 (http://dx.doi.org/10.1016/j.ijhydene.2012.08.034)
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I have been trying to measure extracellular hydrogen peroxide in basic MEM using electrochemical means. I have been inducing a mimetic state of hypoxia using cobalt chloride hexahydrate and have been struggling to assess the quantity of hydrogen peroxide in my sample. I have ran a calibration using my cobalt standard in blank MEM, spiking with H2O2 and measuring via amperometry. I have found that a cathodic spike/ peak occurs but does not step like classic amperometric measurements. The change in current almost immediately returns to baseline.
I am under the assumption that this may be due to the peroxide acting as a catalyst to CoCl2, and the peroxide is being oxidised. Can someone either confirm or shed some light on this issue.
Regards.
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Dear Craig,
It depends on the applied potential in you cell. You might want to change to an applied potential at which H2O2 is reduced but not the Co. In case that this is not possible, you might try to modify your WE in order to make it selective for H2O2.
I hope this helps, for more detailed help you need to share more details of your experimental set-up.
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Last year i researched carbon felt electrode heat treatment of modification method in vanadium redox flow battery... So.. In this year.. I want know about new modification method of carbon felt electrode in Vanadium Redox Flow Battery.... 
If you have do that, advice for me a lot.....
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You can use for example this review as a starting point to generate new ideas
"A technology review of electrodes and reaction mechanisms in vanadium redox flow batteries"  DOI: 10.1039/C5TA02613J
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My fuel cell shows a smooth ohmic polarization. However, my iE curve has teeth-like or spike-like shapes between 0.2V to 0.4V. Besides flooding, what else can cause this behavior?
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I would say that concentration polarization can cause reverse voltage (in the opposite direction to the normal voltage flow) and that causes the instability shown in I-E curve. It like the so-called back corona discharge. The manifestation of this instability (spike-like shapes in the I-E curve) is more pronounced at low voltages like what you mentioned 0.2V to 0.4V.
Hope this helps answer your question.
Professor Yehia Khalil
Yale University
USA
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I am trying to get distribution coefficient and dissociation constant of tetrabutylammonium sulfide in phase transfer catalysis. I could get tetrabutylammonium bromide values. but still trying to get these constants for tetrabutylammonium sulfide. 
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Dear Anil,
You can run semi-empirical calculations such as PM3, AM1 and etc using the MOPAC program installed in ArgusLab.
ArgusLab is a free download program.
Alternatively, you can conduct ab initio, DFT or any hybrid method using Gaussian 09 (this program is not free, you should pay for it).
Hoping this will be helpful,
Rafik
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The slop is defined as delta Y divide by delta X (change in Y axis/change in X axix).
So in order to have a low slop the change of Y axis must be low as compared to X axis and vice versa. In case of Oxygen evaluation reaction (OER), Tafel slop is the change of delta V (y axis) divided by change of Log (current density), so if the change in delta is low as compared to current density the slop will be low. And if we talk about the V(x-axis) vs. current density (y-axis) graph for OER,  the slop of line is high if we have big change in current density as compared to potential, and this high slop will be low if we plot it with Log (current density) on (x-axis) vs potential on y-axis. Therefore, its means that the material with low over potential should have low Tafel slop, but in literature the peoples chose the region in such a way that either their over potential is good or bad but their Tafel slop is very good, if so then why it’s very important???
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If I have observed a faradaic efficiency of 93% and more, is it still necessary to deduct?
I have been asked to detect the redox current contribution from the OER current by calculating faradaic efficiency as my catalyst have shown a strong redox behaviour within the experimental potential window. But I don't find any standard reference to do so. 
Thanks in advance.
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Dear Wiberg,
                Thank you so much for your answer that gave a clear solution for my problem. 
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I was trying to find a way to accurately report the onset potential but could not come across any accurate definition of when how to report it. The most conveniently way I came across was to report when a non-zero (anodic) current starts to flow. I'm currently investigating doped and non-doped CuWO4 for water splitting applications. For the non-doped sample, the photocurrent is higher the dark current at zero photocurrent density, But for the doped sample this is not the case. Why is happening? Am I measuring the onset potential incorrectly?