A Critical Review on Hydrogen Evolution Electrocatalysis: Re‐exploring the Volcano‐relationship

Žeradjanin, Aleksandar R.; Grote, Jan-Philipp; Polymeros, George; Mayrhofer, Karl Johann Jakob

doi:10.1002/elan.201600270

Cited by 270 publications

(255 citation statements)

References 62 publications

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“…In the literature, commonly, conventional volcano analyses are used to comprehend activity trends in a homologous series of materials . Despite of the success of the volcano approach in the field of electrocatalysis, critical voices are heard: it has been reported that the simple Volcano picture, relying on binding energies only, does not describe activity trends always correctly . This finding is directly visible when assessing activity trends of RuO 2 (110) or IrO 2 (110) in the CER or OER, based on ab initio studies, from the literature.…”

Section: Resultsmentioning

confidence: 99%

Overpotential‐Dependent Volcano Plots to Assess Activity Trends in the Competing Chlorine and Oxygen Evolution Reactions

Exner

2020

ChemElectroChem

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The selectivity problem of the competing chlorine evolution (CER) and oxygen evolution (OER) reactions at the anode in chlor−alkali electrolysis is a major challenge in the chemical industry. The development of electrode materials with enhanced stability and CER selectivity could result in a significant reduction of the overall process costs. In order to gain an atomic‐scale understanding of the CER versus OER selectivity, commonly, density functional theory (DFT) calculations are employed that are analyzed by the construction of a volcano plot to comprehend trends. Herein, the binding energy of oxygen, ΔEO, has been established as a descriptor in such analyses. In the present article, it is demonstrated that ΔEO is not suitable to assess activity trends in the OER over transition‐metal oxides, such as RuO2(110) and IrO2(110). Quite in contrast, the free‐formation energy of oxygen with respect to hydroxide, ΔGO−OH, reproduces activity trends of RuO2(110) and IrO2(110) in the CER and OER correctly. Consequently, re‐investigation of the CER versus OER selectivity issue, using ΔGO−OH as a descriptor, is strongly suggested.

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Section: Resultsmentioning

confidence: 99%

Overpotential‐Dependent Volcano Plots to Assess Activity Trends in the Competing Chlorine and Oxygen Evolution Reactions

Exner

2020

ChemElectroChem

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“…Although oxygen can be considered a useless by‐product in artificial photosynthesis, water oxidation provides the reducing equivalents necessary for the synthesis of fuels, typically by reduction of protons to hydrogen, or by reduction of carbon dioxide to carbon monoxide, formic acid, methanol or methane . Efforts in this field have been focused on the development of new and efficient catalysts, but also on the mechanistic investigation for the identification of reaction rates and intermediates involved in breaking and formation of bonds, in particular the most challenging one related to the formation of the oxygen–oxygen bond , …”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into Light‐Activated Catalysis for Water Oxidation

et al. 2019

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The development of catalysts for water oxidation to oxygen has been the subject of intense investigation in the last decade. In parallel to the search for high catalytic performance, many works have focused on the mechanistic analysis of the process. In this perspective, the oxidation of water through light‐assisted cycles composed of an electron acceptor (EA), a photosensitizer (PS), and a water oxidation catalyst (WOC) can provide insightful and complementary information with respect to the use of chemical oxidants or to electrochemical techniques. In this minireview, we discuss the mechanistic aspects of the EA/PS/WOC photoactivated cycles, and in particular: (i) the general elementary steps; (ii) the required features and the nature of the PS employed; (iii) the electron transfer processes and kinetics from the WOC to PS+ (hole scavenging); (iv) the detrimental quenching of the PS by the WOC and the alternative mechanistic routes; (v) the identification of WOC intermediates and, finally, (vi) the transposition of the above processes into a dye‐sensitized photoanode embedding a WOC.

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“…11 In this article we address the overpotential of hydrogen evolution on the Cu(111) electrode. To do this, we employ theoretically calculated Gibbs energies, which are equal to the internal energies plus p V and T S contributions.…”

mentioning

confidence: 99%

“…10 The multitude of variables that affect the exchange current densities used in volcano plots continue to be explored. 11 In this article we address the overpotential of hydrogen evolution on the Cu(111) electrode. To do this, we employ theoretically calculated Gibbs energies, which are equal to the internal energies plus p V and T S contributions.…”

mentioning

confidence: 99%

Theory of Hydrogen Deposition and Evolution on Cu(111) Electrodes

Zhao¹,

Anderson²

2017

J. Electrochem. Soc.

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The amount of under-potential-deposited (UPD) H(ads), if it forms on Cu(111), is small compared to what forms on Pt(111). According to experimental literature, current density on polycrystalline copper increases slowly in the over-potential-deposited (OPD) potential range beginning at 0 V and rises rapidly at several hundred mV negative potential. Using a comprehensive density functional theory for the electrochemical interface, including Fermi level shifts, in this article we attribute this behavior to calculated weak H adsorption which requires the potential to be reduced to ∼0.0 V(SHE) in order for H(ads) deposition to commence. A literature estimate, based on exchange current densities, of the activation energy for H 2 evolution at 0 V is ∼0.32 eV. As the coverage increases with increasingly negative potentials, we calculate the H adsorption energy decreases at a rate 0.27 eV/V for Cu(111), and this will decrease the effective activation energy. We propose that the observed rapid increase in current density at approximately −0.4 V corresponds to ∼0.5 ML coverage by H(ads) and reflects the decreasing activation energy at more negative potentials. We also relate our calculated findings to the literature for electroless copper deposition and to literature for palladium-doped copper as a heterogeneous hydrogenation catalyst. In this article we used quantum theory to explore hydrogen evolution from Cu(111) electrode surfaces. Hydrogen atoms bond weakly to copper surfaces and for significant hydrogen evolution to take place, an overpotential relative to the 0.0 V standard reversible potential must be applied. The first step is deposition of H(ads). In acidic electrolyte the reaction isand in alkaline electrolyteThere are additional ways in which hydrogen can be introduced to copper surfaces as H(ads). In alkaline electrolytes hydrogen is evolved from copper surfaces when aldehyde groups are oxidized without potential control in alkaline electrolyte, that is at the potentials of zero charge (PZC), during electroless copper deposition. [1][2][3][4] In this case the goal is depositing copper atoms on selected substrates and H 2 , formed from combination of H(ads) on copper, 4 is a secondary product. Hydrogen can also be introduced to copper surfaces as H(ads) by spillover of H bonded to Pd atoms on the copper surface. [5][6][7] In this case H 2 dissociation is activated by the Pd ad-atom and the weakly held spilled-over H(ads) performs hydrogenation of organic molecules.To reduce water to hydrogen in alkaline electrolytes over copper electrodes requires high overpotentials of around 0.2 V. 8,9 This contrasts with the small overpotential over platinum. Exchange current densities for hydrogen evolution in alkaline electrolyte for several transition metals, including copper, have been correlated to theoretically calculated H 2 (g) chemisorption energies in a volcano plot. 9 In the plot Pt is near the peak on the left hand side and Pd, Fe, Ni, Co, and W were also on the left (too strongly adsorbed) and Cu, Au, and Ag wer...

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A Critical Review on Hydrogen Evolution Electrocatalysis: Re‐exploring the Volcano‐relationship

Cited by 270 publications

References 62 publications

Overpotential‐Dependent Volcano Plots to Assess Activity Trends in the Competing Chlorine and Oxygen Evolution Reactions

Overpotential‐Dependent Volcano Plots to Assess Activity Trends in the Competing Chlorine and Oxygen Evolution Reactions

Mechanistic Insights into Light‐Activated Catalysis for Water Oxidation

Theory of Hydrogen Deposition and Evolution on Cu(111) Electrodes

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