Coordination Microenvironment Regulation in Carbon−Based Atomically Dispersed Metal Catalysts for Clean Energy−Conversion DOI
Junjie Cui,

Zhenjie Yao,

Boyuan Zhu

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: June 17, 2024

Abstract Emerging atomically dispersed metal catalysts (ADCs), especially carbon−based ADCs have arguably received enormous attention in diverse electrochemical energy conversion processes. Such well−defined active centers, and their geometric electronic structures depend greatly on coordination microenvironments, which, turn, govern the performances realm of electrocatalysis. In this review, it is focused state−of−the−art synthesis strategies for ADCs, with particular emphasis microenvironment modulations. The advances characterizing alongside understanding synthetic pathway are outlined, exemplified applications, including electrocatalytic H 2 evolution, O evolution/reduction, CO reduction, Li polysulfides reactions. Rather than focusing catalysis metrics, review delved deeply into underly science associated reaction mechanisms these systems. fundamental impacts microenvironments activities, selectivities, stabilities discussed. end, concluded by highlighting current issues engineering propose prospects future opportunities challenges.

Language: Английский

The mechanism of water oxidation using transition metal-based heterogeneous electrocatalysts DOI
Shujiao Yang, Xiaohan Liu, Sisi Li

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(11), P. 5593 - 5625

Published: Jan. 1, 2024

The oxygen evolution reaction (OER) mechanisms using transition metal-based electrocatalysts are instrumental in providing novel insights into both natural and artificial energy conversion processes.

Language: Английский

Citations

63
Tuning synergy between nickel and iron in Ruddlesden–Popper perovskites through controllable crystal dimensionalities towards enhanced oxygen‐evolving activity and stability DOI Creative Commons
Haijuan Zhang, Daqin Guan,

Yuxing Gu

et al.

Carbon Energy, Journal Year: 2024, Volume and Issue: 6(6)

Published: Feb. 8, 2024

Abstract Ni–Fe‐based oxides are among the most promising catalysts developed to date for bottleneck oxygen evolution reaction (OER) in water electrolysis. However, understanding and mastering synergy of Ni Fe remain challenging. Herein, we report that between can be tailored by crystal dimensionality Ni, Fe‐contained Ruddlesden–Popper (RP)‐type perovskites (La 0.125 Sr 0.875 ) n +1 (Ni 0.25 0.75 O 3 ( = 1, 2, 3), where material with shows best OER performance alkaline media. Soft X‐ray absorption spectroscopy spectra before after reveal enhanced Ni/Fe–O covalency boost electron transfer as compared those 1 2. Further experimental investigations demonstrate ion is active site stable this system, such unique reaches optimum at 3. Besides, increases, proportion unstable rock‐salt layers accordingly decreases leaching ions (especially 2+ into electrolyte suppressed, which induces a decrease ions, ultimately leading stability. This work provides new avenue rational catalyst design through dimensional strategy.

Language: Английский

Citations

36
Metal‐Organic Frameworks: Direct Synthesis by Organic Acid‐Etching and Reconstruction Disclosure as Oxygen Evolution Electrocatalysts DOI
Xiao Wang, Wei Zhou,

Shengliang Zhai

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(11)

Published: Jan. 22, 2024

Abstract Metal‐organic frameworks (MOFs) have emerged as promising oxygen evolution reaction (OER) electrocatalysts. Chemically bonded MOFs on supports are desirable yet lacking in routine synthesis, they may allow variable structural and the underlying structure‐activity relationship to be disclosed. Herein, direct MOF synthesis is achieved by an organic acid‐etching strategy (AES). Using π‐conjugated ferrocene (Fc) dicarboxylic acid etching agent ligand, a series of MFc‐MOF (M=Ni, Co, Fe, Zn) nanosheets synthesized metal supports. The crystal structure studied using X‐ray diffraction low‐dose transmission electron microscopy, which quasi ‐lattice‐matched with that metal, enabling situ growth. Operando Raman attenuated total reflectance Fourier transform infrared spectroscopy disclose NiFc‐MOF features dynamic rebuilding during OER. reconstructed one showing optimized electronic structures upshifted d ‐band center, high M−O bonding state occupancy, localized electrons adsorbates indicated density functional theory calculations, exhibits outstanding OER performance fairly low overpotential (130 mV at 10 mA cm −2 ) good stability (144 h). newly established approach for reconstruction disclosure stimulate development more prudent catalysts advancing

Language: Английский

Citations

30
Coordination Tuning of Metal Porphyrins for Improved Oxygen Evolution Reaction DOI

Haoyuan Lv,

Xuepeng Zhang, Kai Guo

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(38)

Published: Aug. 8, 2023

Abstract The nucleophilic attack of water or hydroxide on metal‐oxo units forms an O−O bond in the oxygen evolution reaction (OER). Coordination tuning to improve this is intriguing but has been rarely realized. We herein report improved OER catalysis by metal porphyrin 1‐M (M=Co, Fe) with a coordinatively unsaturated ion. designed and synthesized sterically blocking one side tethered tetraazacyclododecane unit. With protection, species generated can maintain unoccupied trans axial site. Importantly, displays higher activity alkaline solutions than analogues lacking such protection decreasing up 150‐mV overpotential achieve 10 mA/cm 2 current density. Theoretical studies suggest that site, unit becomes more positively charged thus favoured for as compared bearing ligands.

Language: Английский

Citations

36
Bioinspired Binickel Catalyst for Carbon Dioxide Reduction: The Importance of Metal–ligand Cooperation DOI Creative Commons
Yao Xiao, Fei Xie,

Hongtao Zhang

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(3), P. 1207 - 1218

Published: March 11, 2024

Catalyst design for the efficient CO2 reduction reaction (CO2RR) remains a crucial challenge conversion of to fuels. Natural Ni–Fe carbon monoxide dehydrogenase (NiFe-CODH) achieves reversible and CO at nearly thermodynamic equilibrium potential, which provides template developing CO2RR catalysts. However, compared with natural enzyme, most biomimetic synthetic complexes exhibit negligible catalytic activities, emphasizes significance effective bimetallic cooperation activation. Enlightened by synergy, we herein report dinickel complex, NiIINiII(bphpp)(AcO)2 (where NiNi(bphpp) is derived from H2bphpp = 2,9-bis(5-tert-butyl-2-hydroxy-3-pyridylphenyl)-1,10-phenanthroline) electrocatalytic CO, exhibits remarkable reactivity approximately 5 times higher than that mononuclear Ni catalyst. Electrochemical computational studies have revealed redox-active phenanthroline moiety effectively modulates electron injection transfer akin [Fe3S4] cluster in NiFe-CODH, secondary site facilitates C–O bond activation cleavage through mediation Lewis acid characteristics. Our work underscores significant role catalysis valuable guidance rational

Language: Английский

Citations

13
Pivotal Role of Geometry Regulation on O−O Bond Formation Mechanism of Bimetallic Water Oxidation Catalysts DOI
Qi‐Fa Chen,

Ke‐Lin Xian,

Hongtao Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(9)

Published: Jan. 5, 2024

Abstract In this study, we highlight the impact of catalyst geometry on formation O−O bonds in Cu 2 and Fe catalysts. A series complexes with diverse linkers are designed as electrocatalysts for water oxidation. Interestingly, catalytic performance these is enhanced their molecular skeletons become more rigid, which contrasts behavior observed our previous investigation analogs. Moreover, mechanistic studies reveal that reactivity bridging O atom results distinct pathways bond systems, coupling takes place between a terminal III −OH μ −O⋅ radical. Whereas it involves two Fe–oxo entities. Furthermore, an in‐depth structure–activity analysis uncovers spatial geometric prerequisites OH radical, ultimately leading to formation. Overall, study emphasizes critical role precisely adjusting catalysts align bonding pathway.

Language: Английский

Citations

10
Metal‐Organic Frameworks: Direct Synthesis by Organic Acid‐Etching and Reconstruction Disclosure as Oxygen Evolution Electrocatalysts DOI
Xiao Wang, Zhou Wei,

Shengliang Zhai

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(11)

Published: Jan. 22, 2024

Abstract Metal‐organic frameworks (MOFs) have emerged as promising oxygen evolution reaction (OER) electrocatalysts. Chemically bonded MOFs on supports are desirable yet lacking in routine synthesis, they may allow variable structural and the underlying structure‐activity relationship to be disclosed. Herein, direct MOF synthesis is achieved by an organic acid‐etching strategy (AES). Using π‐conjugated ferrocene (Fc) dicarboxylic acid etching agent ligand, a series of MFc‐MOF (M=Ni, Co, Fe, Zn) nanosheets synthesized metal supports. The crystal structure studied using X‐ray diffraction low‐dose transmission electron microscopy, which quasi ‐lattice‐matched with that metal, enabling situ growth. Operando Raman attenuated total reflectance Fourier transform infrared spectroscopy disclose NiFc‐MOF features dynamic rebuilding during OER. reconstructed one showing optimized electronic structures upshifted d ‐band center, high M−O bonding state occupancy, localized electrons adsorbates indicated density functional theory calculations, exhibits outstanding OER performance fairly low overpotential (130 mV at 10 mA cm −2 ) good stability (144 h). newly established approach for reconstruction disclosure stimulate development more prudent catalysts advancing

Language: Английский

Citations

9
Non‐Noble‐Metal‐Based Electrocatalysts for Acidic Oxygen Evolution Reaction: Recent Progress, Challenges, and Perspectives DOI
Tingting Liu, Chen Chen, Zonghua Pu

et al.

Small, Journal Year: 2024, Volume and Issue: 20(48)

Published: Aug. 25, 2024

Abstract The oxygen evolution reaction (OER) plays a pivotal role in diverse renewable energy storage and conversion technologies, including water electrolysis, electrochemical CO 2 reduction, nitrogen fixation, metal‐air batteries. Among various electrolysis techniques, proton exchange membrane (PEM)‐based devices offer numerous advantages, high current densities, exceptional chemical stability, excellent conductivity, high‐purity H . Nevertheless, the prohibitive cost associated with Ir/Ru‐based OER electrocatalysts poses significant barrier to broad‐scale application of PEM‐based splitting. Consequently, it is crucial advance development non‐noble metal catalysis substance acid‐activity thereby fostering their widespread integration into PEM electrolyzers (PEMWEs). In this review, comprehensive analysis acidic mechanism, encompassing adsorbate mechanism (AEM), lattice (LOM) oxide path (OPM) offered. Subsequently, systematic summary recently reported noble‐metal‐free catalysts transition metal‐based, carbon‐based other types provided. Additionally, compilation situ/operando characterization techniques provided, serving as invaluable tools for furnishing experimental evidence comprehend catalytic mechanism. Finally, present challenges future research directions concerning precious‐metal‐free are comprehensively summarized discussed review.

Language: Английский

Citations

9
Electrocatalytic Water Oxidation by Mononuclear Copper Complexes of Bis-amide Ligands with N4 Donor: Experimental and Theoretical Investigation DOI
Sahanwaj Khan, Swaraj Sengupta, Md. Adnan Khan

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(4), P. 1888 - 1897

Published: Jan. 17, 2024

The present work describes electrocatalytic water oxidation of three monomeric copper complexes [CuII(L1)] (1), [CuII(L2)(H2O)] (2), and [CuII(L3)] (3) with bis-amide tetradentate ligands: L1 = N,N′-(1,2-phenylene)dipicolinamide, L2 N,N′-(4,5-dimethyl-1,2-phenylene)bis(pyrazine-2-carboxamide), L3 N,N′-(1,2-phenylene)bis(pyrazine-2-carboxamide), for the production molecular oxygen by at pH 13.0. Ligands all have been synthesized characterized single crystal XRD, analytical, spectroscopic techniques. X-ray crystallographic data show that ligand coordinates to in a dianionic fashion through deprotonation two −NH protons. Cyclic voltammetry study shows reversible copper-centered redox couple one ligand-based event. occurs an onset potential 1.16 (overpotential, η ≈ 697 mV), 1.2 (η 737 1.23 V 767 mV) 1, 2, 3 respectively. A systematic variation scaffold has found display profound effect on rate evolution. results theoretical (density functional theory) studies stepwise ligand-centered process formation O–O bond during passes nucleophilic attack complexes. At 13, turnover frequencies experimentally obtained as 88, 1462, 10 s–1 (peak current measurements) 3, Production gas controlled electrolysis was detected chromatography.

Language: Английский

Citations

7
Improvement of electrocatalytic water oxidation activity of novel copper complex by modulating the axial coordination of phosphate on metal center DOI
Jieying Wang,

Yezi Ping,

Yanmei Chen

et al.

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(11), P. 5222 - 5229

Published: Jan. 1, 2024

Two Cu complexes were studied as electrocatalyst for water oxidation. Experiment and theoretical research indicate that the tertiary amine-coordinated structure abates coordination of phosphate anion on center benefits oxygen evolution.

Language: Английский

Citations

6