Total conversion of centimeter-scale nickel foam into single atom electrocatalysts with highly selective CO2 electrocatalytic reduction in neutral electrolyte

Fan, Qikui; Gao, Pengfei; Ren, Shan; Kong, Chuncai; Yang, Jian; Wu, Yuen

doi:10.1007/s12274-022-4472-6

Cited by 25 publications

(19 citation statements)

References 52 publications

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“…14,34 More details to the references can be found in Table 2. 5,8,12,16,[19][20][21]23,41,46,[54][55][56][57][58][59] Despite the lack of comprehensive data, general trends can be derived. Fig.…”

Section: Discussion and Comparison Of Strategiesmentioning

confidence: 99%

Strategies for the mitigation of salt precipitation in zero-gap CO₂ electrolyzers producing CO

et al. 2023

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Section: Discussion and Comparison Of Strategiesmentioning

confidence: 99%

Strategies for the mitigation of salt precipitation in zero-gap CO₂ electrolyzers producing CO

et al. 2023

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“…atoms highly dispersed and anchored in functional carbon substrates, for example, nitrogen-doped carbon (N−C) is the most frequently explored. 17,18 In these developed (Figure S7a), 28,29 +2 (Figure S8a), 19,30,31 and +2 (Figure S9a), 32 respectively. The FT-EXAFS (Figures S7b, S8b S3), implying the independence of CO 2 RR performances on the metal contents, the CO turnover frequency (TOF) was further calculated to evaluate the activity of the Ni−N 4 coordination structure as active sites for CO 2 -to-CO conversion (Figure S17).…”

Section: ■ Introductionmentioning

confidence: 91%

“…In recent years, featured with remarkable stability, superior activity, and maximum atom utilization efficiency, single-atom catalysts (SACs) have been deemed as a kind of promising catalysts with great practical value for electrochemical CO 2 RR, especially those with earth-abundant transition-metal (M: Fe, Co, Ni, and Cu, etc.) atoms highly dispersed and anchored in functional carbon substrates, for example, nitrogen-doped carbon (N–C) is the most frequently explored. , In these developed single-atom transition-metal-anchored N–C (M–N–C) catalysts, the coordination environments and the electronic structures of transition-metal atoms have been evidenced as the determinants to the electrochemical activity and selectivity of M–N–C SACs for CO 2 RR. For example, Wu et al successfully prepared Co–N x –C ( x = 2, 3, and 4) SACs with tuned coordination numbers via a simple pyrolysis method and illustrated that the low-coordinated Co–N 2 –C could gain a high Faradaic efficiency (FE) of 94% for CO production, outperforming the high-coordinated Co–N 3 –C (62.5%).…”

Section: Introductionmentioning

confidence: 99%

Atomically Dispersed Metal–Nitrogen–Carbon Catalysts with d-Orbital Electronic Configuration-Dependent Selectivity for Electrochemical CO₂-to-CO Reduction

et al. 2023

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A variety of atomically dispersed transition-metal-anchored nitrogen-doped carbon (M−N−C) electrocatalysts have shown encouraging electrochemical CO 2 reduction reaction (CO 2 RR) performance, with the underlying fundamentals of central transition-metal atom determined CO 2 RR activity and selectivity yet remaining unclear. Herein, a universal impregnation-acid leaching method was exploited to synthesize various M− N−C (M: Fe, Co, Ni, and Cu) single-atom catalysts (SACs), which revealed d-orbital electronic configuration-dependent activity and selectivity toward CO 2 RR for CO production. Notably, Ni−N−C exhibits a very high CO Faradaic efficiency (FE) of 97% at −0.65 V versus RHE and above 90% CO selectivity in the potential range from −0.5 to −0.9 V versus RHE, much superior to other M−N−C (M: Fe, Co, and Cu). With the d-orbital electronic configurations of central metals in M−N−C SACs well elucidated by crystal-field theory, Dewar−Chatt−Duncanson (DCD) and differential charge density analysis reveal that the vacant outermost dorbital of Ni 2+ in a Ni−N−C SAC would benefit the electron transfer from the C atoms in CO 2 molecules to the Ni atoms and thuseffectively activate the surface-adsorbed CO 2 molecules. However, the outermost d-orbital of Fe 3+ , Co 2+ , and Cu 2+ occupied by unpaired electrons would weaken the electron-transfer process and then impede CO 2 activation. In situ spectral investigations demonstrate that the generation of *COOH intermediates is favored over Ni−N−C SAC at relatively low applied potentials, supporting its high CO 2 -to-CO conversion performance. Gibbs free energy difference analysis in the rate-limiting step in CO 2 RR and hydrogen evolution reaction (HER) reveals that CO 2 RR is thermodynamically favored for Ni−N−C SAC, explaining its superior CO 2 RR performance as compared to other SACs. This work presents a facile and general strategy to effectively modulate the CO 2to-CO selectivity from the perspective of electronic configuration of central metals in M−N−C SACs.

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“…Three strategies are mainly used in "bottom-up" route: 1) coordination sites construction strategy: selecting supports with abundant coordination atoms like nitrogen, phosphorus, and sulfur atoms to tightly anchor the metal atoms 30 ; 2) spatial confinement strategy: porous materials containing ample coordination sites (N, P, S) in skeletons and uniform pores, e.g., zeolite, metalorganic frameworks (MOFs), and covalent-organic frameworks (COFs) are almost always served as hosts to evenly confine the metal atoms [31][32][33][34][35] ; 3) defects design strategy: the vacancies and unsaturated coordination sites generated from the defects of supports could be utilized to capture mononuclear metal complexes 36 . Reversely, metal nanoparticles or bulk metal are the starting precursors of "top-down" synthetic route 37,38 . Regulating the competition between metal-metal bonds and metal-supports bonds is essential for dispersing metal species atomically, which requires strong EMSI from abundant coordination sites or defects in supports to anchor metal atoms as well as high temperature to overcome the barrier of cracking metal-metal bonds 39,40 .…”

Section: Introductionmentioning

confidence: 99%

Enhancing Heterogeneous Catalysis by Electronic Property Regulation of Single Atom Catalysts

Luo¹,

Wang²

2023

Acta Physico Chimica Sinica

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Past decades have witnessed the flourish of single atom catalysts (SACs) owing to their high atom-utilization efficiency and completely exposed active sites, which endows SACs with remarkably enhanced catalytic activities for various reactions. In the early development stage of SACs, researchers focus on the improvement of the catalytic performance of the catalysts, whereas the intrinsic catalytic reaction mechanism and the relationship between the electronic states of the metal sites and catalytic performance are usually ignored. Moreover, some sophisticated and complex structures, such as dualatom SACs, heteroatomic doped SACs, SACs with precise second coordination shell, and other synergetic catalysts containing SACs, were fabricated recently. The insight into electronic metal-support interaction (EMSI) aids the understanding of the catalytic mechanism and thus serves as a guide for the fabrication of heterogeneous catalysts. Notably, the uniform active sites and characteristic local coordination configuration of SACs provide excellent platforms to study EMSI and bridge the gap between homogeneous and heterogeneous catalysts, which will contribute to the understanding of structure-performance relationships and enhance the development of SACs and rational design of heterogeneous catalysts. EMSI is especially important in heterogeneous catalysis. Through the rational design of the local coordination environment of SACs, the electronic structure of active sites can be accurately regulated, which will shift their d-band centers. This significantly alters the adsorption capability of intermediates and influences the final catalytic performance of the catalysts. With the development of advanced operando characterization techniques, the evolution of configuration, electronic properties, and local coordination environment could be revealed, thus providing researchers with a clear picture of the intrinsic mechanism of the catalytic system. In addition, with the aid of theoretical calculations, catalyst screening will be considerably more convenient, which will significantly reduce the number of aimless trials. After the optimal structure is determined, researchers should devise precise fabrication methods to realize the configuration. Herein, we initially introduce the basic principles and effects of EMSI. The stabilization, electronic property regulation, and electron transfer tunneling effects of EMSI are the foundation of SACs synthesis and catalytic mechanism elucidation, of which the former requires strong coordination stabilization energies while the latter focuses on the electronic state evolution of the active sites. Subsequently, EMSI applications in several important heterogeneous catalysis processes, such as selective hydrogenation, alcohol oxidation, water-gas shift reaction, and hydroformylation, are reviewed. Finally, the review discusses the challenges and future prospects for the future development of EMSI on SACs.

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Total conversion of centimeter-scale nickel foam into single atom electrocatalysts with highly selective CO2 electrocatalytic reduction in neutral electrolyte

Cited by 25 publications

References 52 publications

Strategies for the mitigation of salt precipitation in zero-gap CO₂ electrolyzers producing CO

Strategies for the mitigation of salt precipitation in zero-gap CO₂ electrolyzers producing CO

Atomically Dispersed Metal–Nitrogen–Carbon Catalysts with d-Orbital Electronic Configuration-Dependent Selectivity for Electrochemical CO₂-to-CO Reduction

Enhancing Heterogeneous Catalysis by Electronic Property Regulation of Single Atom Catalysts

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Total conversion of centimeter-scale nickel foam into single atom electrocatalysts with highly selective CO2 electrocatalytic reduction in neutral electrolyte

Cited by 25 publications

References 52 publications

Strategies for the mitigation of salt precipitation in zero-gap CO2 electrolyzers producing CO

Strategies for the mitigation of salt precipitation in zero-gap CO2 electrolyzers producing CO

Atomically Dispersed Metal–Nitrogen–Carbon Catalysts with d-Orbital Electronic Configuration-Dependent Selectivity for Electrochemical CO2-to-CO Reduction

Enhancing Heterogeneous Catalysis by Electronic Property Regulation of Single Atom Catalysts

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Strategies for the mitigation of salt precipitation in zero-gap CO₂ electrolyzers producing CO

Strategies for the mitigation of salt precipitation in zero-gap CO₂ electrolyzers producing CO

Atomically Dispersed Metal–Nitrogen–Carbon Catalysts with d-Orbital Electronic Configuration-Dependent Selectivity for Electrochemical CO₂-to-CO Reduction