Metal oxide-based materials as an emerging family of hydrogen evolution electrocatalysts

Zhu, Yinlong; Lin, Qian; Zhong, Yijun; Tahini, Hassan A.; Shao, Zongping; Wang, Huanting

doi:10.1039/d0ee02485f

Cited by 489 publications

(301 citation statements)

References 294 publications

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“…[ 6 ] Pushing the HER activities of the non‐noble metal‐based catalysts to a similar level of Pt metal by modulating the electronic properties together with unraveling the underlying mechanisms are thus urgently demanded. Throughout the past few years, a large number of non‐noble metal‐based catalysts, including non‐noble metal sulfides, [ 7 ] nitrides, [ 8 ] carbides, [ 9 ] metal oxides, [ 10 ] etc., and their composites have been developed. [ 5b ] The reactivity of these catalysts, unfortunately, is still not comparable to that of commercial Pt/C.…”

Section: Introductionmentioning

confidence: 99%

Heteroatom‐Doping of Non‐Noble Metal‐Based Catalysts for Electrocatalytic Hydrogen Evolution: An Electronic Structure Tuning Strategy

et al. 2021

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Electrocatalytic water splitting for hydrogen production is an appealing way to reduce carbon emissions and generate renewable fuels. This promising process, however, is limited by its sluggish reaction kinetics and high‐cost catalysts. Construction of low‐cost and high‐performance non‐noble metal‐based catalysts have been one of the most effective approaches to address these grand challenges. Notably, the electronic structure tuning strategy, which could subtly tailor the electronic states, band structures, and adsorption ability of the catalysts, has become a pivotal way to further enhance the electrochemical water splitting reactions based on non‐noble metal‐based catalysts. Particularly, heteroatom‐doping plays an effective role in regulating the electronic structure and optimizing the intrinsic activity of the catalysts. Nevertheless, the reaction kinetics, and in particular, the functional mechanisms of the hetero‐dopants in catalysts yet remains ambiguous. Herein, the recent progress is comprehensively reviewed in heteroatom doped non‐noble metal‐based electrocatalysts for hydrogen evolution reaction, particularly focus on the electronic tuning effect of hetero‐dopants in the catalysts and the corresponding synthetic pathway, catalytic performance, and activity origin. This review also attempts to establish an intrinsic correlation between the localized electronic structures and the catalytic properties, so as to provide a good reference for developing advanced low‐cost catalysts.

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Section: Introductionmentioning

confidence: 99%

Heteroatom‐Doping of Non‐Noble Metal‐Based Catalysts for Electrocatalytic Hydrogen Evolution: An Electronic Structure Tuning Strategy

et al. 2021

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“…However, this process not only operates under harsh environments involving high temperatures (400-500 °C) and activities toward NRR and others (e.g., oxygen evolution, hydrogen evolution) of perovskite oxides can be effectively enhanced through oxygen vacancy engineering. [20][21][22][23][24][25][26] The main mechanism has been certified to be that B-site cations combining with their adjacent oxygen vacancies can serve as unsaturated active centers that strengthen the ability to adsorb/ activate N 2 molecule and thus lead NRR on the optimal reaction pathway. [14] Despite these efforts, their preparation methods involving special atmosphere (e.g., 5% H 2 /Ar) annealing had made it challenging to rationally tailor the oxygen vacancies, not mentioning the instability of most of the perovskite oxides under those conditions.…”

Section: Introductionmentioning

confidence: 99%

A General Strategy to Boost Electrocatalytic Nitrogen Reduction on Perovskite Oxides via the Oxygen Vacancies Derived from A‐Site Deficiency

Chu

Liu

Zhu

et al. 2021

Advanced Energy Materials

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pressures (10-30 MPa), but also demands a large deal of H 2 mainly from natural gas reforming which causes abundant consumption of fossil fuels and huge CO 2 emissions. [3-6] As a result, for energy conservation and environmental protection, it is of crucial importance to explore a clean and sustainable route for NH 3 production. Electrocatalytic N 2 reduction reaction (NRR) under ambient conditions has been emerged recently as an attractive strategy for the green synthesis of NH 3 through utilizing inexhaustible N 2 and H 2 O. [7-12] However, due to the competition with H 2 evolution reaction (HER) and ultra-stable NN covalent triple bond, NRR suffers from unsatisfactory Faradaic efficiency (FE) and sluggish reaction kinetics. [13] It is of eager desire, but very challenging to develop selective and efficient electrocatalysts toward NRR that can inhibit the competitive HER and activate the N 2 molecule. Among various developed electrocatalysts, perovskite oxides have proven their great potential toward NRR because of their low cost, good adjustability in intriguing physicochemical properties, as well as economic and environmental friendliness. Typical examples include a few simple perovskite oxides, such as LaCoO 3 , LaCrO 3 , LaFeO 3 , La 2 Ti 2 O 7 , and Ce 1/3 NbO 3. [14-19] Although significant progress has been made, their NRR performance is still far from the requirements of commercial NH 3 synthesis. Most recently, several studies have shown that the electrocatalytic The electrocatalytic N 2 reduction reaction (NRR) under ambient conditions is an attractive strategy for green synthesis of NH 3. Due to the ultra-stable NN covalent triple bond, it is very challenging to develop highly selective and efficient electrocatalysts toward NRR. Here a general strategy to enhance the NRR activity through modulating A-site-deficiency-induced oxygen vacancies of perovskite oxides is reported. One successful example is La x FeO 3−δ (L x F, x = 1, 0.95, and 0.9) perovskite oxides with tunable oxygen vacancies that are directly proportional to the La-site deficiencies. As compared to the pristine LF, the L 0.95 F and L 0.9 F exhibit significantly improved NRR activities, which are positively correlated with the La-site deficiency and the amount of oxygen vacancies. Among them, the L 0.9 F delivers the best activity, with an NH 3 yield rate of 22.1 µg•h −1 •mg −1 cat. at −0.5 V and a Faradaic efficiency of 25.6% at −0.3 V, which are 2.2 and 1.6 times those of the pristine LF, respectively. Both experimental characterizations and theoretical calculations suggest that the enhanced NRR activity can be mainly attributed to the favorable merits produced by the oxygen vacancies: the promoted adsorption/activation of reaction species, and thus optimized reaction pathways. Application of this strategy to other perovskite oxides generates similarly successful results.

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“…Metal oxides are traditionally inactive towards HER. In recent years, some progress was achieved for alkaline HER using metal oxide-based catalysts, [25] and very few oxide electrocatalysts for HER in acid media were developed by creating oxygen vacancies in metal oxide or doping of metals/ non-metals in oxides. The HER activity and stability of oxide catalysts are still inferior to commercial Pt/C in both acid and base media.…”

Section: Introductionmentioning

confidence: 99%

Interface‐ and Surface‐Engineered PdO−RuO₂ Hetero‐Nanostructures with High Activity for Hydrogen Evolution/Oxidation Reactions

2021

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Active catalysts for HER/HOR are crucial to develop hydrogenbased renewable technologies. The interface of hetero-nanostructures can integrate different components into a single synergistic hybrid with high activity. Here, the synthesis of PdOÀ RuO 2 À C with abundant interfaces/defects was achieved for the hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR). It exhibited a current density of 10 mA cm À 2 at 44 mV with a Tafel slope of 34 mV dec À 1 in 1 m KOH. The HER mass activity was 3 times higher in base and comparable to Pt/C in acid. The stability test confirmed high HER stability. The catalyst also exhibited excellent HOR activity in both media; in alkaline HOR it outperformed Pt/C. The exchange current density i 0,m of PdOÀ RuO 2 /C was 522 mA mg À 1 in base, which is 58 and 3.4 times higher than those of Pd/C and Pt/C. The HOR activity of PdOÀ RuO 2 /C was 22 and 300 times higher than those of PdO/C in acid and base. Improve-ment of HER/HOR kinetics in different alkaline electrolytes was observed in the order K + < Na + < Li + , and increase of HER as well decrease of HOR kinetics was observed with increasing Li + concentration. It was proposed that OH ad -M + -(H 2 O) x in the double-layer region could influence HER/HOR activity in base. Based on the hard and soft acid and base (HSAB) theory, the OH ads -M + -(H 2 O) x could help to remove more OH ads into the bulk, leading to increase in HER/HOR activity in alkaline electrolyte (K + < Na + < Li + ) and increasing the HER with increasing Li + concentration. The decrease of HOR activity of PdOÀ RuO 2 /C with increasing M + was due to M + -induced OH ads destabilization through the bifunctional mechanism. The high HER/HOR activity of PdOÀ RuO 2 /C could be attributed, among other factors, to interface engineering and strong synergistic interaction. This work provides an opportunity to design oxidebased catalysts for renewable energy technologies.

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Metal oxide-based materials as an emerging family of hydrogen evolution electrocatalysts

Abstract: Metal oxide-based materials are emerging as a promising family of hydrogen evolution reaction (HER) electrocatalysts.

Cited by 489 publications

References 294 publications

Heteroatom‐Doping of Non‐Noble Metal‐Based Catalysts for Electrocatalytic Hydrogen Evolution: An Electronic Structure Tuning Strategy

Heteroatom‐Doping of Non‐Noble Metal‐Based Catalysts for Electrocatalytic Hydrogen Evolution: An Electronic Structure Tuning Strategy

A General Strategy to Boost Electrocatalytic Nitrogen Reduction on Perovskite Oxides via the Oxygen Vacancies Derived from A‐Site Deficiency

Interface‐ and Surface‐Engineered PdO−RuO₂ Hetero‐Nanostructures with High Activity for Hydrogen Evolution/Oxidation Reactions

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Metal oxide-based materials as an emerging family of hydrogen evolution electrocatalysts

Abstract: Metal oxide-based materials are emerging as a promising family of hydrogen evolution reaction (HER) electrocatalysts.

Cited by 489 publications

References 294 publications

Heteroatom‐Doping of Non‐Noble Metal‐Based Catalysts for Electrocatalytic Hydrogen Evolution: An Electronic Structure Tuning Strategy

Heteroatom‐Doping of Non‐Noble Metal‐Based Catalysts for Electrocatalytic Hydrogen Evolution: An Electronic Structure Tuning Strategy

A General Strategy to Boost Electrocatalytic Nitrogen Reduction on Perovskite Oxides via the Oxygen Vacancies Derived from A‐Site Deficiency

Interface‐ and Surface‐Engineered PdO−RuO2 Hetero‐Nanostructures with High Activity for Hydrogen Evolution/Oxidation Reactions

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Interface‐ and Surface‐Engineered PdO−RuO₂ Hetero‐Nanostructures with High Activity for Hydrogen Evolution/Oxidation Reactions