碱性介质中氢氧化反应电催化剂的开发: 从机理认识到材料设计

doi:10.1016/S1872-2067(21)64088-3

摘要/Abstract

摘要：

阴离子交换膜(AEM)燃料电池因具有使用非贵金属作为催化剂的优点而受到广泛关注. 然而, 在碱性体系中, AEM燃料电池中氢氧化反应(HOR)的反应动力学比在酸性介质中的慢两个数量级. 针对HOR在碱中动力学缓慢的问题, 有两种主要的理论来解释, (1)pH相关的氢结合能作为主要影响因素来控制HOR动力学的理论; (2) 质子和氢氧根离子的吸附共同作为影响因子来控制HOR在碱性条件下的动力学的双功能理论.

本文首先讨论了在碱性电解质中可能的HOR反应机理及其Tafel性能变化. 除了传统的Tafel-Volmer和Heyrovsky-Volmer-HOR机理外, 还讨论了最新提出的氢氧根离子吸附参与的HOR机理来说明在酸性和碱性介质中HOR机理的差异. 然后, 总结了具有代表性的碱性HOR催化剂(如贵金属、合金、金属间化合物、镍基合金、碳化物、氮化物等), 简要介绍了它们相应的HOR反应机理, 从而进一步理解在碱性介质中不同基元反应步骤给HOR性能带来的差异. 最后, 提出了一种未来设计HOR碱性催化剂的可行性方案, 为今后碱性环境下的HOR催化剂设计提供参考.

关键词: 氢氧化反应, 碱性电解质, 燃料电池, 电催化剂, 电催化, 氢和氢氧离子结合能

Abstract:

Anion exchange membrane (AEM) fuel cells have gained great attention partially due to the advantage of using non-precious metal as catalysts. However, the reaction kinetics of hydrogen oxidation reaction (HOR) is two orders of magnitude slower in alkaline systems than in acid. To understand the slower kinetics of HOR in base, two major theories have been proposed, such as (1) pH dependent hydrogen binding energy as a major descriptor for HOR; and (2) bifunctional theory based on the contributions of both hydrogen and hydroxide adsorption for HOR in alkaline electrolyte. Here, we discuss the possible HOR mechanisms in alkaline electrolytes with the corresponding change in their Tafel behavior. Apart from the traditional Tafel-Volmer and Heyrovsky-Volmer HOR mechanisms, the recently proposed hydroxide adsorption step is also discussed to illustrate the difference in HOR mechanisms in acid and base. We further summarize the representative works of alkaline HOR catalyst design (e.g., precious metals, alloy, intermetallic materials, Ni-based alloys, carbides, nitrides, etc.), and briefly describe their fundamental HOR reaction mechanism to emphasize the difference in elementary reaction steps in alkaline medium. The strategy of strengthening local interaction that facilitates both H₂ desorption and H_ads + OH_ads recombination is finally proposed for future HOR catalyst design in alkaline environment.

Key words: Hydrogen oxidation reaction, Alkaline electrolyte, Fuel cell, Electrocatalyst, Electrocatalysis, Hydrogen and hydroxide binding energy

仇暘, 谢小红, 李文震, 邵玉艳. 碱性介质中氢氧化反应电催化剂的开发: 从机理认识到材料设计[J]. 催化学报, 2021, 42(12): 2094-2104.

Yang Qiu, Xiaohong Xie, Wenzhen Li, Yuyan Shao. Electrocatalysts development for hydrogen oxidation reaction in alkaline media: From mechanism understanding to materials design[J]. Chinese Journal of Catalysis, 2021, 42(12): 2094-2104.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)64088-3

https://www.cjcatal.com/CN/Y2021/V42/I12/2094

图/表 10

Fig. 1. Relationship between HOR electrocatalysis and electrochemical double-layer structure. Generic mechanistic reaction schemes for HOR in dilute alkaline electrolytes on mono and bi-metallic catalyst systems. M1 represents a metal site capable of dissociative adsorption of molecular hydrogen. In scheme 2, alloy element Mp represents a precious metal site capable of forming Hupd in alkaline electrolyte. In scheme 3, alloy element Mb represents a base-metal site passivated with adsorbed (hydr)oxide species in dilute alkaline electrolytes. (Reproduced from Ref. [40] with permission from Elsevier. Copyright (2017)).

Table 1 Tafel slope and kinetic expressions for HOR.

HOR mechanism	Tafel slope at 25 °C	Note
Heyrovsky-Volmer(RDS)	2.303RT/[(2-α)F] = ~39 mV dec^-1	θ_H< 0.4 (low η_Vol) TS = 39 θ_H> 0.6 (high η_Vol) TS = 118 (close to Heyrovsky-RDS)
Tafel-Volmer(RDS)	2.303RT/[(1-α)F] = ~118 mV dec^-1	θ_H is govern by P_H2 Reaction rate is governed by both η and θ_H (P_H2)
Heyrovsky(RDS)-Volmer	2.303RT/[(1-α)F] = ~118 mV dec^-1	H_ads consumes rapidly (θ_H≈ 0); fast Volmer step
Tafel(RDS)-Volmer^*	2.303RT/2F = ~29 mV dec^-1	H_ads consumes rapidly (θ_H≈ 0); fast Volmer step Reaction rate could be independent to η (I = nFAk^o_TP_H2)

Fig. 2. Reaction energy diagram showing the complete reaction pathway with rate determining steps for hydrogen oxidation for a catalyst which has a hydroxide adsorption strength from weak to strong. Reproduced from Ref. [37] with the permission from Springer Nature. Copyright (2020).

Table 2 Calculated hydroxide binding energy (ΔEOH*) over the most close packed surface of different metals at a quarter monolayer coverage, data is cited from Ref. [50].

Metal	ΔE_OH*/eV	Metal	ΔE_OH*/eV	Metal	ΔE_OH*/eV
Ag	0.72	Au	1.49	Co	-0.08
Cu	0.37	Fe	-0.88	Ir	0.63
Mo	-0.61	Ni	0.13	Pd	0.92
Pt	1.05	Rh	0.34	Ru	-0.01
W	-0.80

Fig. 3. (a) Trassati’s volcano plot for the hydrogen evolution reaction in acid solutions. j00 (same to j0) denotes the exchange current density, and EMH is the energy of hydride formation. (Data is taken from Ref. [24]. Reproduced from Ref. [51] with the permission from Dr. Wolfgang Schmickler). (b) Schematic illustrating the research need to establish HBEapp as the descriptor for HOR/HER: (1) Measuring and/or calculating water adsorption energy of PGMs in different pHs; (2) Measuring and/or calculating water adsorption energy of metals on the weakly binding branch in different pHs; (3) Measuring HOR/HER activities on metals on the weakly binding branch. Exchange current density data represents the activity at 20 °C, and is from [18,20,25,32,57,70,71]. (Reproduced from Ref. [31] with open access).

Fig. 4. (a) Bar graph highlighting experimental HOR exchange current densities as a function of the corresponding trend on the basis of calculated surface hydrogen binding energy (HBE) values for models of “near surface alloys” for Pt, Pt7Ru3, Pt7Fe3, Pt7Co3, Pt7Cu3, and Pt7Au3 NWs, respectively. The trend shown for the theoretical HBE values was based upon the data presented in Ref. [72]. (Figure is reproduced from Ref. [58] with the permission from American Chemical Society. Copyright (2016)). (b) The volcano plot of the experimentally measured exchange current density versus the adsorption hydrogen free energy of Ru-Ni (magenta), Ru (red) and Pt (blue) calculated by DFT in this study where the ΔGH of Ru and Pt were taken from the value most close to 0, and common metal catalysts. (Reproduced from Ref. [65] with the permission from Royal Society of Chemistry. Copyright (2020)).

Fig. 5. (a) Schematic representation of the HOR on Ni(OH)2/Pt(111), Ni(OH)2 provides the active sites for adsorption of reactive OHads, and Pt provides the active sites for dissociative adsorption of H2 and production of Hads, which then react with reactive OHads. (Reproduced from Ref. [33] with the permission from Springer Nature. Copyright (2013)). (b) 3D HER activity volcano for catalyst design. Logarithm of the rate of hydrogen evolution (contours) as a function of hydrogen binding energy and hydroxide binding energy. The water dissociation rate was derived from the binding energies and kinetics on (211) surfaces calculated previously and modified to reference solution-phase hydroxide as the product of water dissociation and then extrapolated to 0 VRHE and to reproduce the barriers calculated here for water dissociation on Pt(111) and Pt(553) (which include the effects of solvation and alkali cation). Black circles correspond to DFT-calculated hydrogen and hydroxide adsorption energies on Pt(111), Pt(553), Ru* adsorbed at the step of Pt(553), a PtRu(111) alloy and Ru* clusters on Pt(111). (c) Rate of the HER or the HOR as a function of the free energy of adsorption of hydroxide. (Figure b and c are reproduced from Ref. [37] with the permission from Springer Nature. Copyright (2020)). (d) Experimentally measured exchange current density, log(i0,s), for hydrogen oxidation in base over different metals plotted with calculated H and OH adsorption potentials. The two dashed lines represent the optimal *H adsorption potential (～0.28 V) and the optimal *OH adsorption potential (～0.75 V), respectively. (Reproduced from Ref. [36] with the permission from American Chemical Society. Copyright (2018)).

Fig. 6. (a) Heat map of the local hydrogen adsorption energy for Ni/graphene (top), Ni/N-graphene (bottom left), and Ni/B-graphene (bottom right). (b) Heat map of the local HOR/HER exchange current density for Ni/graphene (top), Ni/N-graphene (bottom left), and Ni/B-graphene (bottom right). (Reproduced from Ref. [78] with the permission from American Chemical Society. Copyright (2019)).

Table 3 Summary of the HOR performance over representative electrocatalysts in alkaline electrolyte.

Catalyst	Reaction conditions			HOR performance
Catalyst	Electrolyte	Temperature (°C)	Loading (µg cm^-2)	η to achieve i_l (mV vs. RHE)	Exchange current density (mA cm^-2)	Tafel slope (mV dec^-1)	Ref.
Pt(pc)	0.1 M KOH	21 ± 1.5	RDE	250-300	0.69 ± 0.03	109	[18]
Pt/C	0.1 M KOH	21 ± 1.5	7.0	~300	0.57 ± 0.07	—	[18]
Pt/C	0.1 M NaOH	40 ± 0.0	3.0	—	1.0 ± 0.01	—	[15]
Pt/Cu NW	0.1 M KOH	23 ± 3.0	16.0 (Pt)	~100	2.1 (Pt)	—	[56]
Pt_0.8Ru_0.2/C	0.1 M KOH	23 ± 3.0	7.09 (PtRu)	~140	1.42 (Pt)	35	[60]
PtRu/C	0.1 M KOH	23 ± 3.0	3.8 (PtRu)	~90	0.7 (Pt)	—	[34]
PtFe	0.1 M KOH	23 ± 3.0	8.0 (Pt)	>250	0.459 (Pt)	43.3	[58]
PtCo	0.1 M KOH	23 ± 3.0	8.0 (Pt)	>250	0.394 (Pt)	45.7	[58]
PtAu	0.1 M KOH	23 ± 3.0	8.0 (Pt)	—	0.162 (Pt)	49.6	[58]
Acid-PtNi/C	0.1 M KOH	23 ± 3.0	10.0 (Pt)	~250	1.89 ± 0.09 (Pt)	—	[63]
Pd/C	0.1 M NaOH	40 ± 0.0	16.0	—	0.06 ± 0.02	—	[15]
Pd/C-500C	0.1 M KOH	20 ± 0.0	20	~350	0.122 ± 0.005	108	[44]
Pd/Cu NW	0.1 M KOH	23 ± 3.0	12.5	>200	1.01 (Pd)	—	[57]
Pd_0.8Ru_0.2/C	0.1 M KOH	23 ± 3.0	7.06 (PdRu)	~375	0.148 (Pd)	219	[60]
Pd/C-CeO₂	0.1 M KOH	23 ± 3.0	6.5 (Pd)	—	0.089	100	[64]
Ir/C	0.1 M NaOH	40 ± 0.0	8.0	—	0.37 ± 0.12	—	[15]
Ir/C	0.1 M KOH	20 ± 0.0		~250	0.21 ± 0.02	116	[43]
Ir₉Ru₁/C	0.1 M KOH	23 ± 3.0	3.5 (IrRu)	~110	0.9 (IrRu)	—	[69]
Ir₃Pd₁Ru₆/C	0.1 M KOH	23 ± 3.0	3.5 (IrPdRu)	~100	0.6 (IrPdRu)	—	[69]
Ru/C	0.1 M KOH	25 ± 0.0	10.0	~120	0.064	—	[92]
Ru₁@Pt₁(2 ML)	1.0 M KOH	23 ± 0.0	~3.0	—	1.5 (Pt)	—	[55]
Ru7Ni₃/C	0.1 M KOH	23 ± 0.0	3.9 (Ru)	~100	1.09	—	[59]
CoNiMo	0.1 M KOH	20 ± 0.0	—	—	0.015 ± 0.009	—	[23]
Ni₁Cu₁/C	0.1 M KOH	25 ± 0.0	25 (NiCu)	—	0.0145	—	[85]
Ni/Graphene	0.1 M KOH	23 ± 3.0	250 (Ni)	—	0.030	—	[79]
Ni/N-CNT	0.1 M KOH	23 ± 3.0	250 (Ni)	—	0.028	—	[79]
Ni1@(h-BN)₁/C	0.1 M NaOH	23 ± 3.0	250 (Ni)	—	0.023	—	[86]
NiMo/KB	0.1 M KOH	25 ± 0.0	100 (w/C)	—	0.027 ± 0.002	—	[87]
WNi₄	0.1 M KOH	23 ± 3.0	500 (WNi)	~90	0.068	—	[89]
MoNi₄	0.1 M KOH	23 ± 3.0	500 (MoNi)	~80	0.065	—	[89]
Ni/SC	0.1 M KOH	23 ± 3.0	50 (w/C)	—	0.04	—	[83]

Table 3 Summary of the HOR performance over representative electrocatalysts in alkaline electrolyte.

Catalyst	Reaction conditions			HOR performance
Catalyst	Electrolyte	Temperature (°C)	Loading (µg cm^-2)	η to achieve i_l (mV vs. RHE)	Exchange current density (mA cm^-2)	Tafel slope (mV dec^-1)	Ref.
Pt(pc)	0.1 M KOH	21 ± 1.5	RDE	250-300	0.69 ± 0.03	109	[18]
Pt/C	0.1 M KOH	21 ± 1.5	7.0	~300	0.57 ± 0.07	—	[18]
Pt/C	0.1 M NaOH	40 ± 0.0	3.0	—	1.0 ± 0.01	—	[15]
Pt/Cu NW	0.1 M KOH	23 ± 3.0	16.0 (Pt)	~100	2.1 (Pt)	—	[56]
Pt_0.8Ru_0.2/C	0.1 M KOH	23 ± 3.0	7.09 (PtRu)	~140	1.42 (Pt)	35	[60]
PtRu/C	0.1 M KOH	23 ± 3.0	3.8 (PtRu)	~90	0.7 (Pt)	—	[34]
PtFe	0.1 M KOH	23 ± 3.0	8.0 (Pt)	>250	0.459 (Pt)	43.3	[58]
PtCo	0.1 M KOH	23 ± 3.0	8.0 (Pt)	>250	0.394 (Pt)	45.7	[58]
PtAu	0.1 M KOH	23 ± 3.0	8.0 (Pt)	—	0.162 (Pt)	49.6	[58]
Acid-PtNi/C	0.1 M KOH	23 ± 3.0	10.0 (Pt)	~250	1.89 ± 0.09 (Pt)	—	[63]
Pd/C	0.1 M NaOH	40 ± 0.0	16.0	—	0.06 ± 0.02	—	[15]
Pd/C-500C	0.1 M KOH	20 ± 0.0	20	~350	0.122 ± 0.005	108	[44]
Pd/Cu NW	0.1 M KOH	23 ± 3.0	12.5	>200	1.01 (Pd)	—	[57]
Pd_0.8Ru_0.2/C	0.1 M KOH	23 ± 3.0	7.06 (PdRu)	~375	0.148 (Pd)	219	[60]
Pd/C-CeO₂	0.1 M KOH	23 ± 3.0	6.5 (Pd)	—	0.089	100	[64]
Ir/C	0.1 M NaOH	40 ± 0.0	8.0	—	0.37 ± 0.12	—	[15]
Ir/C	0.1 M KOH	20 ± 0.0		~250	0.21 ± 0.02	116	[43]
Ir₉Ru₁/C	0.1 M KOH	23 ± 3.0	3.5 (IrRu)	~110	0.9 (IrRu)	—	[69]
Ir₃Pd₁Ru₆/C	0.1 M KOH	23 ± 3.0	3.5 (IrPdRu)	~100	0.6 (IrPdRu)	—	[69]
Ru/C	0.1 M KOH	25 ± 0.0	10.0	~120	0.064	—	[92]
Ru₁@Pt₁(2 ML)	1.0 M KOH	23 ± 0.0	~3.0	—	1.5 (Pt)	—	[55]
Ru7Ni₃/C	0.1 M KOH	23 ± 0.0	3.9 (Ru)	~100	1.09	—	[59]
CoNiMo	0.1 M KOH	20 ± 0.0	—	—	0.015 ± 0.009	—	[23]
Ni₁Cu₁/C	0.1 M KOH	25 ± 0.0	25 (NiCu)	—	0.0145	—	[85]
Ni/Graphene	0.1 M KOH	23 ± 3.0	250 (Ni)	—	0.030	—	[79]
Ni/N-CNT	0.1 M KOH	23 ± 3.0	250 (Ni)	—	0.028	—	[79]
Ni1@(h-BN)₁/C	0.1 M NaOH	23 ± 3.0	250 (Ni)	—	0.023	—	[86]
NiMo/KB	0.1 M KOH	25 ± 0.0	100 (w/C)	—	0.027 ± 0.002	—	[87]
WNi₄	0.1 M KOH	23 ± 3.0	500 (WNi)	~90	0.068	—	[89]
MoNi₄	0.1 M KOH	23 ± 3.0	500 (MoNi)	~80	0.065	—	[89]
Ni/SC	0.1 M KOH	23 ± 3.0	50 (w/C)	—	0.04	—	[83]

Fig. 7. Pyramidical graph of HOR electrocatalyst development based on reaction mechanism understanding and materials innovation.

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