多金属氧酸盐材料在二氧化碳电催化还原领域中的研究进展

随着工业发展和全球人口的持续增长,人类对化石燃料的消耗日益增加,从而导致大气中二氧化碳含量的显著增加以及与之相伴的一系列环境问题.电化学还原二氧化碳制备高附加值的燃料和化学品具有稳定的效率和较高的经济可行性等特点,目前已成为一种有前景的策略来缓解当前全球面临的能源短缺和气候变暖问题.然而,电催化二氧化碳还原过程存在反应能垒高和复杂的多电子/质子耦合过程等不足,因此,合理有效的电催化剂设计成为该领域的关键问题.近年,理解和明确电化学二氧化碳还原反应过程的活性起源、选择性调控机制和催化反应机理已成为高效电催化剂设计过程中的重要指导原则.作为一类独特的纳米尺度的金属氧簇,多金属氧酸盐(多酸)已成为二氧化碳还原领域的热点材料.尤其是,多酸明确的结构、优越的电子/质子存储转移能力和二氧化碳吸附活化能力有助于探究二氧化碳还原反应过程中的活性起源和构效机制.因此,利用多酸阐明电化学二氧化碳还原反应中的这些关键问题对于开发高效、可实用化的电催化剂意义重大.本文综述了近年多酸在电催化二氧化碳还原反应中取得的进展,重点介绍了多酸阴离子均相分子催化剂、多酸基无机-有机杂化材料催化剂、多酸电解质溶液、多酸-纳米复合材料在电催化二氧化碳还原反应中的应用.利用密度泛函理论结合原位实验证据推测了可能的反应机理,探讨了多酸对电催化活性和产物选择性的影响,揭示了电子/质子存储-转移过程和多酸表面修饰工程在电催化二氧化碳还原过程中的重要作用.最后,本文还分析了多酸基材料存在的问题与面临的挑战,并对多酸基材料在二氧化碳还原领域的未来发展进行了展望,这对理解电催化二氧化碳还原反应中的关键步骤和开发新型高效的电催化二氧化碳还原电催化剂具有启发意义.     

Recent advances in single atom catalysts for the electrochemical carbon dioxide reduction reaction

The electrochemical carbon dioxide reduction reaction (CO₂RR) offers a promising solution to mitigate carbon emission and at the same time generate valuable carbonaceous chemicals/fuels. Single atom catalysts (SACs) are encouraging to catalyze the electrochemical CO₂RR due to the tunable electronic structure of the central metal atoms, which can regulate the adsorption energy of reactants and reaction intermediates. Moreover, SACs form a bridge between homogeneous and heterogeneous catalysts, providing an ideal platform to explore the reaction mechanism of electrochemical reactions. In this review, we first discuss the strategies for promoting the CO₂RR performance, including suppression of the hydrogen evolution reaction (HER), generation of C₁ products and formation of C₂₊ products. Then, we summarize the recent developments in regulating the structure of SACs toward the CO₂RR based on the above aspects. Finally, several issues regarding the development of SACs for the CO₂RR are raised and possible solutions are provided.

The electrochemical carbon dioxide reduction reaction (CO₂RR) offers a promising solution to mitigate carbon emission and at the same time generate valuable carbonaceous chemicals/fuels.     

Is Cu instability during the CO2 reduction reaction governed by the applied potential or the local CO concentration?

Cu-based catalysts have shown structural instability during the electrochemical CO₂ reduction reaction (CO₂RR). However, studies on monometallic Cu catalysts do not allow a nuanced differentiation between the contribution of the applied potential and the local concentration of CO as the reaction intermediate since both are inevitably linked. We first use bimetallic Ag-core/porous Cu-shell nanoparticles, which utilise nanoconfinement to generate high local CO concentrations at the Ag core at potentials at which the Cu shell is still inactive for the CO₂RR. Using operando liquid cell TEM in combination with ex situ TEM, we can unequivocally confirm that the local CO concentration is the main source for the Cu instability. The local CO concentration is then modulated by replacing the Ag-core with a Pd-core which further confirms the role of high local CO concentrations. Product quantification during CO₂RR reveals an inherent trade-off between stability, selectivity and activity in both systems.

The stability of bimetallic AgCu and PdCu catalysts for electrochemical CO₂RR is investigated using the combination of operando and ex situ TEM. The local CO concentration is identified as the main link between activity, stability and selectivity.     

In Situ Bismuth Nanosheet Assembly for Highly Selective Electrocatalytic CO2 Reduction to Formate

The reduction of carbon dioxide (CO₂) into value-added fuels using an electrochemical method has been regarded as a compelling sustainable energy conversion technology. However, high-performance electrocatalysts for CO₂ reduction reaction (CO₂RR) with high formate selectivity and good stability need to be improved. Earth-abundant Bi has been demonstrated to be active for CO₂RR to formate. Herein, we fabricated an extremely active and selective bismuth nanosheet (Bi-NSs) assembly via an in situ electrochemical transformation of (BiO)₂CO₃ nanostructures. The as-prepared material exhibits high activity and selectivity for CO₂RR to formate, with nearly 94% faradaic efficiency at −1.03 V (versus reversible hydrogen electrode (vs. RHE)) and stable selectivity (>90%) in a large potential window ranging from −0.83 to −1.18 V (vs. RHE) and excellent durability during 12 h continuous electrolysis. In addition, the Bi-NSs based CO₂RR/methanol oxidation reaction (CO₂RR/MOR) electrolytic system for overall CO₂ splitting was constructed, evidencing the feasibility of its practical implementation.     

Polyoxometalate-Based Compounds for Photo- and Electrocatalytic Applications

Photo/electrocatalysis of water (H₂O) splitting and CO₂ reduction reactions is a promising strategy to alleviate the energy crisis and excessive CO₂ emissions. For the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and CO₂ reduction reaction (CO₂RR) involved, the development of effective photo/electrocatalysts is critical to reduce the activation energy and accelerate the sluggish dynamics. Polyoxometalate (POM)-based compounds with tunable compositions and diverse structures are emerging as unique photo/electrocatalysts for these reactions as they offer unparalleled advantages such as outstanding solution and redox stability, quasi-semiconductor behaviour, etc. This Minireview provides a basic introduction related to photo/electrocatalytic HER, OER and CO₂RR, followed by the classification of pristine POM-based compounds toward different catalytic reactions. Recent breakthroughs in engineering POM-based compounds as efficient photo/electrocatalysts are highlighted. Finally, the advantages, challenges, strategies and outlooks of POM-based compounds on improving photo/electrocatalytic performance are discussed.     

Why do RuO2 electrodes catalyze electrochemical CO2 reduction to methanol rather than methane or perhaps neither of those?

The electrochemical CO₂ reduction reaction (CO₂RR) on RuO₂ and RuO₂-based electrodes has been shown experimentally to produce high yields of methanol, formic acid and/or hydrogen while methane formation is not detected. This CO₂RR selectivity on RuO₂ is in stark contrast to copper metal electrodes that produce methane and hydrogen in the highest yields whereas methanol is only formed in trace amounts. Density functional theory calculations on RuO₂(110) where only adsorption free energies of intermediate species are considered, i.e. solvent effects and energy barriers are not included, predict however, that the overpotential and the potential limiting step for both methanol and methane are the same. In this work, we use both ab initio molecular dynamics simulations at room temperature and total energy calculations to improve the model system and methodology by including both explicit solvation effects and calculations of proton–electron transfer energy barriers to elucidate the reaction mechanism towards several CO₂RR products: methanol, methane, formic acid, CO and methanediol, as well as for the competing H₂ evolution. We observe a significant difference in energy barriers towards methane and methanol, where a substantially larger energy barrier is calculated towards methane formation than towards methanol formation, explaining why methanol has been detected experimentally but not methane. Furthermore, the calculations show why RuO₂ also catalyzes the CO₂RR towards formic acid and not CO(g) and methanediol, in agreement with experimental results. However, our calculations predict RuO₂ to be much more selective towards H₂ formation than for the CO₂RR at any applied potential. Only when a large overpotential of around −1 V is applied, can both formic acid and methanol be evolved, but low faradaic efficiency is predicted because of the more facile H₂ formation.

Energy barriers are calculated for the electrochemical CO₂ reduction reaction on the RuO₂(110) surface towards methanol, methane, formic acid, methanediol, CO and the competing H₂ formation and compared with experimental literature.     

Organic molecules involved in Cu-based electrocatalysts for selective CO2 reduction to C2+ products

Electrocatalytic carbon dioxide (CO₂) reduction reaction (CO₂RR) is a promising process to mitigate the environmental issues caused by CO₂, as well as to produce valuable multicarbon (C₂₊) products. Significant progresses have been made to explore highly efficient Cu-based electrocatalysts for CO₂RR in recent years. Adding organic molecules into electrocatalytic systems can tune the CO₂ interaction with the electrocatalysts for CO₂RR, therefore, the final C₂₊ products, which are not solely achieved by inorganic modification. In this review, we will summarize the recent progress of the organic molecules participation in CO₂ electroreduction to C₂₊ products on Cu-based electrocatalysts. The applied organic molecules are reviewed based on the heteroatoms (N and S), with the emphasis on their roles in activity and selectivity toward C₂₊ products. A perspective on the application of organic molecules for efficient and selective CO₂RR has been provided.     

Tailoring Copper Nanocrystals towards C2 Products in Electrochemical CO2 Reduction

Favoring the CO₂ reduction reaction (CO2RR) over the hydrogen evolution reaction and controlling the selectivity towards multicarbon products are currently major scientific challenges in sustainable energy research. It is known that the morphology of the catalyst can modulate catalytic activity and selectivity, yet this remains a relatively underexplored area in electrochemical CO₂ reduction. Here, we exploit the material tunability afforded by colloidal chemistry to establish unambiguous structure/property relations between Cu nanocrystals and their behavior as electrocatalysts for CO₂ reduction. Our study reveals a non‐monotonic size‐dependence of the selectivity in cube‐shaped copper nanocrystals. Among 24 nm, 44 nm and 63 nm cubes tested, the cubes with 44 nm edge length exhibited the highest selectivity towards CO2RR (80 %) and faradaic efficiency for ethylene (41 %). Statistical analysis of the surface atom density suggests the key role played by edge sites in CO2RR.     

The atomic-level regulation of single-atom site catalysts for the electrochemical CO2 reduction reaction

The electrochemical CO₂ reduction reaction (CO₂RR) is viewed as a promising way to remove the greenhouse gas CO₂ from the atmosphere and convert it into useful industrial products such as methane, methanol, formate, ethanol, and so forth. Single-atom site catalysts (SACs) featuring maximum theoretical atom utilization and a unique electronic structure and coordination environment have emerged as promising candidates for use in the CO₂RR. The electronic properties and atomic structures of the central metal sites in SACs will be changed significantly once the types or coordination environments of the central metal sites are altered, which appears to provide new routes for engineering SACs for CO₂ electrocatalysis. Therefore, it is of great importance to discuss the structural regulation of SACs at the atomic level and their influence on CO₂RR activity and selectivity. Despite substantial efforts being made to fabricate various SACs, the principles of regulating the intrinsic electrocatalytic performances of the single-atom sites still needs to be sufficiently emphasized. In this perspective article, we present the latest progress relating to the synthesis and catalytic performance of SACs for the electrochemical CO₂RR. We summarize the atomic-level regulation of SACs for the electrochemical CO₂RR from five aspects: the regulation of the central metal atoms, the coordination environments, the interface of single metal complex sites, multi-atom active sites, and other ingenious strategies to improve the performance of SACs. We highlight synthesis strategies and structural design approaches for SACs with unique geometric structures and discuss how the structure affects the catalytic properties.

Electrochemical CO₂ reduction reaction (CO₂RR) is a promising way to remove CO₂ and convert it into useful industrial products. Single-atom site catalysts provide opportunities to regulate the active sites of CO₂RR catalysts at the atomic level.     

Effect of pore diameter and length on electrochemical CO2 reduction reaction at nanoporous gold catalysts

In this work, we employ differential electrochemical mass spectrometry (DEMS) to track the real-time evolution of CO at nanoporous gold (NpAu) catalysts with varying pore parameters (diameter and length) during the electrochemical CO₂ reduction reaction (CO₂RR). We show that due to the increase in the local pH with increasing catalyst roughness, NpAu catalysts suppress the bicarbonate-mediated hydrogen evolution reaction (HER) compared to a flat Au electrode. Additionally, the geometric current density for CO₂RR increases with the roughness of NpAu catalysts, which we attribute to the increased availability of active sites at NpAu catalysts. Together, the enhancement of CO₂RR and the suppression of competing HER results in a drastic increase in the faradaic selectivity for CO₂RR with increasing pore length and decreasing pore diameter, reaching near 100% faradaic efficiency for CO in the most extreme case. Interestingly, unlike the geometric current density, the specific current density for CO₂RR has a more complicated relation with the roughness of the NpAu catalysts. We show that this is due to the presence of ohmic drop effects along the length of the porous channels. These ohmic drop effects render the pores partially electrocatalytically inactive and hence, they play an important role in tuning the CO₂RR activity on nanoporous catalysts.

In this work, we employ differential electrochemical mass spectrometry (DEMS) to track the real-time evolution of CO at nanoporous gold (NpAu) catalysts with varying pore parameters (diameter and length) during the electrochemical CO₂ reduction reaction (CO₂RR).     

Electrochemical Reduction of Carbon Dioxide to Ethanol: An Approach to Transforming Greenhouse Gas to Fuel Source

Converting carbon dioxide (CO₂) into high-value fuels or chemicals is considered as a promising way to utilize CO₂ and alleviate the excessive greenhouse gas emission. Among multiple catalysis approaches, electrochemical reduction of CO₂ to ethanol has an important prospect due to the high energy density and widely applications of ethanol. In recent years, many electrocatalysts for CO₂ reduce reaction (CO₂RR) have shown promising catalytic activity for ethanol production. In this review, we will introduce the recent progress in this field. The basic principles and electrochemical performances of CO₂RR are reviewed at first. Then, several categories of active electrocatalysts for CO₂RR to ethanol are summarized, including the discussion of reaction mechanism and catalytic sites. Finally, several possible strategies are proposed, providing guidance for future design and preparation of high-performance catalysts.     

Circumventing the scaling relationship on bimetallic monolayer electrocatalysts for selective CO2 reduction

Electrochemical conversion of CO₂ into value-added chemicals continues to draw interest in renewable energy applications. Although many metal catalysts are active in the CO₂ reduction reaction (CO₂RR), their reactivity and selectivity are nonetheless hindered by the competing hydrogen evolution reaction (HER). The competition of the HER and CO₂RR stems from the energy scaling relationship between their reaction intermediates. Herein, we predict that bimetallic monolayer electrocatalysts (BMEs) – a monolayer of transition metals on top of extended metal substrates – could produce dual-functional active sites that circumvent the scaling relationship between the adsorption energies of HER and CO₂RR intermediates. The antibonding interaction between the adsorbed H and the metal substrate is revealed to be responsible for circumventing the scaling relationship. Based on extensive density functional theory (DFT) calculations, we identify 11 BMEs which are highly active and selective toward the formation of formic acid with a much suppressed HER. The H–substrate antibonding interaction also leads to superior CO₂RR performance on monolayer-coated penta-twinned nanowires.

Dual-functional active sites are designed to circumvent the scaling relationship between the HER and CO₂RR on bimetallic monolayer electrocatalysts.     

Key factors for designing single-atom metal-nitrogen-carbon catalysts for electrochemical CO2 reduction

The electrochemical CO₂ reduction (CO₂RR) is a sustainable approach to mitigate the increased CO₂ emissions and simultaneously produce value-added chemicals and fuels. Metal-nitrogen-carbon (M-N-C) based single-atom catalysts (SACs) have emerged as promising electrocatalysts for CO₂RR with high activity, selectivity, and stability. To design efficient SACs for CO₂RR, the key influence factors need to be understood. Here, we summarize recent achievements on M-N-C SACs for CO₂RR and highlight the significance of the key constituting factors, metal sites, the coordination environment, and the substrates, for achieving high CO₂RR performance. The perspective views and guidelines are provided for the future direction of developing M-N-C SACs as CO₂RR catalysts.     

Nanocrystal/Metal–Organic Framework Hybrids as Electrocatalytic Platforms for CO2 Conversion

The tunable chemistry linked to the organic/inorganic components in colloidal nanocrystals (NCs) and metal–organic frameworks (MOFs) offers a rich playground to advance the fundamental understanding of materials design for various applications. Herein, we combine these two classes of materials by synthesizing NC/MOF hybrids comprising Ag NCs that are in intimate contact with Al‐PMOF ([Al₂(OH)₂(TCPP)]) (tetrakis(4‐carboxyphenyl)porphyrin (TCPP)), to form Ag@Al‐PMOF. In our hybrids, the NCs are embedded in the MOF while still preserving electrical contact with a conductive substrate. This key feature allows the investigation of the Ag@Al‐PMOFs as electrocatalysts for the CO₂ reduction reaction (CO₂RR). We show that the pristine interface between the NCs and the MOFs accounts for electronic changes in the Ag, which suppress the hydrogen evolution reaction (HER) and promote the CO₂RR. We also demonstrate a minor contribution of mass‐transfer effects imposed by the porous MOF layer under the chosen testing conditions. Furthermore, we find an increased morphological stability of the Ag NCs when combined with the Al‐PMOF. The synthesis method is general and applicable to other metal NCs, thus revealing a new way to think about rationally tailored electrocatalytic materials to steer selectivity and improve stability.     

Metal–ligand bond strength determines the fate of organic ligands on the catalyst surface during the electrochemical CO2 reduction reaction

Colloidally synthesised nanocrystals (NCs) are increasingly utilised as catalysts to drive both thermal and electrocatalytic reactions. Their well-defined size and shape, controlled by organic ligands, are ideal to identify the parameters relevant to the activity, selectivity and stability in catalysis. However, the impact of the native surface ligands during catalysis still remains poorly understood, as does their fate. CuNCs are among the state-of-the-art catalysts for the electrochemical CO₂ reduction reaction (CO₂RR). In this work, we study CuNCs that are capped by different organic ligands to investigate their impact on the catalytic properties. We show that the latter desorb from the surface at a cathodic potential that depends on their binding strength with the metal surface, rather than their own electroreduction potentials. By monitoring the evolving surface chemistry in situ, we find that weakly bound ligands desorb very rapidly while strongly bound ligands impact the catalytic performance. This work provides a criterion to select labile ligands versus ligands that will persist on the surface, thus offering opportunity for interface design.

The metal–ligand binding strength is a key parameter in determining the role and fate of the surface ligands on nanoparticle catalysts during the electrochemical CO₂ reduction reaction.     

Solvent-mediated outer-sphere CO2 electro-reduction mechanism over the Ag111 surface

The electrocatalytic CO₂ reduction reaction (CO₂RR) is one of the key technologies of the clean energy economy. Molecular-level understanding of the CO₂RR process is instrumental for the better design of electrodes operable at low overpotentials with high current density. The catalytic mechanism underlying the turnover and selectivity of the CO₂RR is modulated by the nature of the electrocatalyst, as well as the electrolyte liquid, and its ionic components that form the electrical double layer (EDL). Herein we demonstrate the critical non-innocent role of the EDL for the activation and conversion of CO₂ at a high cathodic bias for electrocatalytic conversion over a silver surface as a representative low-cost model cathode. By using a multiscale modeling approach we demonstrate that under such conditions a dense EDL is formed, which hinders the diffusion of CO₂ towards the Ag111 electrocatalyst surface. By combining DFT calculations and ab initio molecular dynamics simulations we identify favorable pathways for CO₂ reduction directly over the EDL without the need for adsorption to the catalyst surface. The dense EDL promotes homogeneous phase reduction of CO₂via electron transfer from the surface to the electrolyte. Such an outer-sphere mechanism favors the formation of formate as the CO₂RR product. The formate can undergo dehydration to CO via a transition state stabilized by solvated alkali cations in the EDL.

In addition to the commonly accepted inner-sphere mechanism for e⁻ transfer, we show that an outer-sphere electron transfer from the cathode to CO₂ is operable at high overpotentials.     

Recent advances in carbon-based materials for electrochemical CO2 reduction reaction

The increase of atmospheric CO₂ concentration has caused many environmental issues. Electrochemical CO₂ reduction reaction（CO₂RR） has been considered as a promising strategy to mitigate these challenges. The electrocatalysts with a low overpotential, high Faradaic efficiency, and excellent selectivity are of great significance for the CO₂RR. Carbon-based materials including metal-free carbon catalysts and metal-based carbon catalysts have shown great p...     

Boosting electrocatalytic selectivity in carbon dioxide reduction: The fundamental role of dispersing gold nanoparticles on silicon nanowires

Carbon dioxide electrochemical reduction (CO₂RR) has been recognized as an efficient way to mitigate CO₂ emissions and alleviate the pressure on global warming and associated environmental consequences. Gold (Au) is reported as stable and active electrocatalysts to convert CO₂ to CO at low overpotential due to its moderate adsorption strength of *COOH and *CO. The request for improved catalytic performance, however, is motivated by current unsatisfied catalytic selectivity because of the side hydrogen evolution reaction. In this context, the design of Au based binary catalysts that can boost CO selectivity is of great interest. In the present work, we report that Au nanoparticles can be feasibly dispersed and anchored on silicon nanowires to form Au-Si binary nanomaterials. The Au-Si may stably drive CO₂RR with a CO Faraday efficiency of 95.6% at ?0.6 V vs. RHE in 0.5 mol/L KHCO₃ solution. Such selectivity outperforms Au particles by up to 61%. Controlled experiments illustrate that such catalytic enhancement can chiefly be ascribed to electronic effects of binary catalysts. Theoretical calculations reveal that spontaneously produced silicon oxide may not only inhibit hydrogen evolution reaction, but also stabilize the key intermediate *COOH in CO formation.     

Elucidating the Electrocatalytic CO2 Reduction Reaction over a Model Single‐Atom Nickel Catalyst

Designing effective electrocatalysts for the carbon dioxide reduction reaction (CO₂RR) is an appealing approach to tackling the challenges posed by rising CO₂ levels and realizing a closed carbon cycle. However, fundamental understanding of the complicated CO₂RR mechanism in CO₂ electrocatalysis is still lacking because model systems are limited. We have designed a model nickel single‐atom catalyst (Ni SAC) with a uniform structure and well‐defined Ni‐N₄ moiety on a conductive carbon support with which to explore the electrochemical CO₂RR. Operando X‐ray absorption near‐edge structure spectroscopy, Raman spectroscopy, and near‐ambient X‐ray photoelectron spectroscopy, revealed that Ni⁺ in the Ni SAC was highly active for CO₂ activation, and functioned as an authentic catalytically active site for the CO₂RR. Furthermore, through combination with a kinetics study, the rate‐determining step of the CO₂RR was determined to be *CO₂^?+H⁺→*COOH. This study tackles the four challenges faced by the CO₂RR; namely, activity, selectivity, stability, and dynamics.     

Elucidating the Electrocatalytic CO2 Reduction Reaction over a Model Single-Atom Nickel Catalyst

Designing effective electrocatalysts for the carbon dioxide reduction reaction (CO₂RR) is an appealing approach to tackling the challenges posed by rising CO₂ levels and realizing a closed carbon cycle. However, fundamental understanding of the complicated CO₂RR mechanism in CO₂ electrocatalysis is still lacking because model systems are limited. We have designed a model nickel single-atom catalyst (Ni SAC) with a uniform structure and well-defined Ni-N₄ moiety on a conductive carbon support with which to explore the electrochemical CO₂RR. Operando X-ray absorption near-edge structure spectroscopy, Raman spectroscopy, and near-ambient X-ray photoelectron spectroscopy, revealed that Ni⁺ in the Ni SAC was highly active for CO₂ activation, and functioned as an authentic catalytically active site for the CO₂RR. Furthermore, through combination with a kinetics study, the rate-determining step of the CO₂RR was determined to be *CO₂⁻+H⁺→*COOH. This study tackles the four challenges faced by the CO₂RR; namely, activity, selectivity, stability, and dynamics.