Structure Engineering and Electronic Modulation of Transition Metal Interstitial Compounds for Electrocatalytic Water Splitting DOI
Yanqing Jiao, Haijing Yan, Chungui Tian

et al.

Accounts of Materials Research, Journal Year: 2022, Volume and Issue: 4(1), P. 42 - 56

Published: Dec. 1, 2022

ConspectusHydrogen is deemed as an ideal energy carrier because of its high density and clean nature. Water electrolysis fairly competitive for hydrogen production due to the conversion renewable electricity high-purity H2 with no carbon emission, in comparison traditional industrial technology. However, large-scale application hampered by cost partially from use noble metal-based catalysts promote kinetics oxygen evolution reactions. Developing cost-efficient transition electrocatalysts, therefore, a hopeful prospect, they can provide d-orbital lone-pair electrons or empty d-orbitals adsorbing different intermediates (such H*, OH*, O*, OOH*). As compared metals their oxides, metal interstitial compounds (TMICs) formed inserting C, N, P atoms into sites parent hold distinct advantages Pt-like electronic structure, conductivity, superior chemical stability over wide pH range, beneficial overcoming consumption faced alkaline water intractable issue acid electrolysis. Nevertheless, major drawbacks are large size, density, sluggish ionic kinetics, resulting ordinary electrochemical activity low mass efficiency. Electrocatalytic performance dominated intrinsic activity, number accessible active sites, capacity charge transfer. Engineering micronano structure (small-size particles, porous ultrathin nanosheet) expose more catalytical facilitate transport gas diffusion. Meanwhile, modulating optimize adsorption boost activity. Apparently, synergistic modulation TMICs expected achieve multiobjective optimization targeting highly effective catalysts.In this Account, we summarize our recent efforts designed synthesis engineering utilizing polyoxometalates (POMs) precursors associated strategies advance electrocatalytic toward HER OER. We start brief summary OER mechanisms, which play crucial roles elaborate design relevant electrocatalysts. The disadvantages pointed out, apart opportunities offered POMs constructing novel component, interface structure. Several efficient enhancement proposed including reducing size heterojunctions interfaces, doping heteroatoms regulate binding intermediates, creating pores accelerate transfer, etc. Accordingly, controllable well-defined highlighted, positive role tailoring on enhancing catalytic efficiency confirmed. Furthermore, paired electrocatalysis using species produce value-added chemicals reduce consumption. Finally, remaining challenges, opportunities, future development directions TMICs-based materials discussed.

Language: Английский

Microenvironment Engineering of Single/Dual‐Atom Catalysts for Electrocatalytic Application DOI Open Access
Yun Gao, Baozhong Liu, Dingsheng Wang

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(31)

Published: Feb. 23, 2023

Single/dual-metal atoms supported on carbon matrix can be modulated by coordination structure and neighboring active sites. Precisely designing the geometric electronic uncovering structure-property relationships of single/dual-metal confront with grand challenges. Herein, this review summarizes latest progress in microenvironment engineering single/dual-atom sites via a comprehensive comparison single-atom catalyst (SACs) dual-atom catalysts (DACs) term design principles, modulation strategy, theoretical understanding structure-performance correlations. Subsequently, recent advances several typical electrocatalysis process are discussed to get general reaction mechanisms finely-tuned SACs DACs. Finally, full-scaled summaries challenges prospects given for This will provide new inspiration development atomically dispersed electrocatalytic application.

Language: Английский

Citations

181
Fundamental Understanding of Structural Reconstruction Behaviors in Oxygen Evolution Reaction Electrocatalysts DOI Creative Commons
Haoyin Zhong, Qi Zhang, Junchen Yu

et al.

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(31)

Published: June 29, 2023

Abstract Transition metal‐based oxyhydroxides (MOOH) derived from the irreversible structural reconstruction of precatalysts are often acknowledged as real catalytic species for oxygen evolution reaction (OER). Typically, reconstruction‐derived MOOH would exhibit superior OER activity compared to their directly synthesized counterparts, despite being fundamentally similar in chemistry. As such, has emerged a promising strategy boost electrocatalysts. However, in‐depth understanding origin reconstructed materials still remains ambiguous, which significantly hinders further developments highly efficient electrocatalysts based on In this review, comprehensive overview behaviors reported is provided and intrinsic chemical origins high efficiency toward unveiled. The fundamentals mechanisms, along with recommended characterization techniques dynamic process analyzing structure also interpreted. Finally, view chemistry, potential perspectives facilitate design synthesis durable electrocatalyst presented.

Language: Английский

Citations

151
Geometric and Electronic Engineering of Atomically Dispersed Copper‐Cobalt Diatomic Sites for Synergistic Promotion of Bifunctional Oxygen Electrocatalysis in Zinc–Air Batteries DOI
Zhijun Li, Siqi Ji, Chun Wang

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(25)

Published: April 11, 2023

The development of rechargeable zinc-air batteries is heavily dependent on bifunctional oxygen electrocatalysts to offer exceptional reduction/evolution reaction (ORR/OER) activities. However, the design such with high activity and durability challenging. Herein, a strategy proposed create an electrocatalyst comprised copper-cobalt diatomic sites highly porous nitrogen-doped carbon matrix (Cu-Co/NC) abundantly accessible metal optimal geometric electronic structures. Experimental findings theoretical calculations demonstrate that synergistic effect Cu-Co dual-metal metal-N4 coordination induce asymmetric charge distributions moderate adsorption/desorption behavior intermediates. This exhibits extraordinary electrocatalytic activities in alkaline media, half-wave potential 0.92 V for ORR low overpotential 335 mV at 10 mA cm-2 OER. In addition, it demonstrates acidic (0.85 V) neutral (0.74 media. When applied battery, achieves operational performance outstanding (510 h), ranking as one most efficient reported date. work importance engineering isolated boosting electrochemical energy devices.

Language: Английский

Citations

148
Review of Carbon Support Coordination Environments for Single Metal Atom Electrocatalysts (SACS) DOI Creative Commons

Wanqing Song,

Caixia Xiao,

Jia Ding

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(1)

Published: April 20, 2023

This topical review focuses on the distinct role of carbon support coordination environment single-atom catalysts (SACs) for electrocatalysis. The article begins with an overview atomic configurations in SACs, including a discussion advanced characterization techniques and simulation used understanding active sites. A summary key electrocatalysis applications is then provided. These processes are oxygen reduction reaction (ORR), evolution (OER), hydrogen (HER), nitrogen (NRR), dioxide (CO

Language: Английский

Citations

139
Continuous electroproduction of formate via CO2 reduction on local symmetry-broken single-atom catalysts DOI Creative Commons
Juncai Dong, Yangyang Liu, Jiajing Pei

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Oct. 27, 2023

Abstract Atomic-level coordination engineering is an efficient strategy for tuning the catalytic performance of single-atom catalysts (SACs). However, their rational design has so far been plagued by lack a universal correlation between symmetry and properties. Herein, we synthesised planar-symmetry-broken CuN 3 (PSB-CuN ) SACs through microwave heating electrocatalytic CO 2 reduction. Remarkably, as-prepared exhibited selectivity 94.3% towards formate at −0.73 V vs. RHE, surpassing symmetrical 4 catalyst (72.4% −0.93 RHE). In flow cell equipped with PSB-CuN electrode, over 90% was maintained average current density 94.4 mA cm −2 during 100 h operation. By combining definitive structural identification operando X-ray spectroscopy theoretical calculations, revealed that intrinsic local breaking from planar D configuration induces unconventional dsp hybridisation, thus strong activity microenvironment metal centre (i.e., number distortion), high preference production in moiety. The finding opens avenue designing specific symmetries selective electrocatalysis.

Language: Английский

Citations

112
Bifunctional Single Atom Catalysts for Rechargeable Zinc–Air Batteries: From Dynamic Mechanism to Rational Design DOI

Peng Zhang,

Kuo Chen, Jiaye Li

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(35)

Published: June 7, 2023

Ever-growing demands for rechargeable zinc-air batteries (ZABs) call efficient bifunctional electrocatalysts. Among various electrocatalysts, single atom catalysts (SACs) have received increasing attention due to the merits of high utilization, structural tunability, and remarkable activity. Rational design SACs relies heavily on an in-depth understanding reaction mechanisms, especially dynamic evolution under electrochemical conditions. This requires a systematic study in mechanisms replace current trial error modes. Herein, fundamental oxygen reduction is first presented combining situ and/or operando characterizations theoretical calculations. By highlighting structure-performance relationships, rational regulation strategies are particularly proposed facilitate SACs. Furthermore, future perspectives challenges discussed. review provides thorough SACs, which expected pave avenue exploring optimum effective ZABs.

Language: Английский

Citations

105
Cooperation between Dual Metal Atoms and Nanoclusters Enhances Activity and Stability for Oxygen Reduction and Evolution DOI
Zhe Wang, Xiaoyan Jin,

Ruojie Xu

et al.

ACS Nano, Journal Year: 2023, Volume and Issue: 17(9), P. 8622 - 8633

Published: April 27, 2023

We have achieved the synthesis of dual-metal single atoms and atomic clusters that co-anchor on a highly graphitic carbon support. The catalyst comprises Ni4 (and Fe4) nanoclusters located adjacent to corresponding NiN4 FeN4) single-atom sites, which is verified by systematic X-ray absorption characterization density functional theory calculations. A distinct cooperation between Fe4 (Ni4) FeN4 (NiN4) sites optimizes adsorption energy reaction intermediates reduces barrier potential-determining steps. This exhibits enhanced oxygen reduction evolution activity long-cycle stability compared counterparts without commercial Pt/C. fabricated Zn-air batteries deliver high power long-term cyclability, demonstrating their prospects in storage device applications.

Language: Английский

Citations

84
Inter-site structural heterogeneity induction of single atom Fe catalysts for robust oxygen reduction DOI Creative Commons
Peng Zhang, Hsiao‐Chien Chen, Houyu Zhu

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 7, 2024

Abstract Metal-nitrogen-carbon catalysts with hierarchically dispersed porosity are deemed as efficient geometry for oxygen reduction reaction (ORR). However, catalytic performance determined by individual and interacting sites originating from structural heterogeneity is particularly elusive yet remains to be understood. Here, an porous Fe single atom catalyst (Fe SAs-HP) prepared atoms densely resided at micropores mesopores. SAs-HP exhibits robust ORR half-wave potential of 0.94 V turnover frequency 5.99 e −1 s site 0.80 V. Theoretical simulations unravel a induced optimization, where mesoporous Fe-N 4 acts real active centers result long-range electron regulation adjacent microporous sites, facilitating O 2 activation desorption key intermediate *OH. Multilevel operando characterization results identify undergo dynamic evolution basic 3 under working conditions. Our findings reveal the origin enhanced intrinsic activity sites.

Language: Английский

Citations

82
Identification of Dynamic Active Sites Among Cu Species Derived from MOFs@CuPc for Electrocatalytic Nitrate Reduction Reaction to Ammonia DOI Creative Commons
Xue-Yang Ji, Ke Sun, Zhikun Liu

et al.

Nano-Micro Letters, Journal Year: 2023, Volume and Issue: 15(1)

Published: April 30, 2023

Direct electrochemical nitrate reduction reaction (NITRR) is a promising strategy to alleviate the unbalanced nitrogen cycle while achieving electrosynthesis of ammonia. However, restructuration high-activity Cu-based electrocatalysts in NITRR process has hindered identification dynamical active sites and in-depth investigation catalytic mechanism. Herein, Cu species (single-atom, clusters, nanoparticles) with tunable loading supported on N-doped TiO2/C are successfully manufactured MOFs@CuPc precursors via pre-anchor post-pyrolysis strategy. Restructuration behavior among co-dependent potential, as evidenced by advanced operando X-ray absorption spectroscopy, there exists an incompletely reversible transformation restructured structure initial state. Notably, CuN4&Cu4 deliver high NH3 yield 88.2 mmol h-1 gcata-1 FE (~ 94.3%) at - 0.75 V, resulting from optimal adsorption NO3- well rapid conversion *NH2OH *NH2 intermediates originated modulation charge distribution d-band center for site. This work not only uncovers have but also identifies dynamic that play critical role efficient electrocatalytic

Language: Английский

Citations

79
Research progress on the construction of synergistic electrocatalytic ORR/OER self-supporting cathodes for zinc–air batteries DOI
Qi Liu, Lei Wang, Honggang Fu

et al.

Journal of Materials Chemistry A, Journal Year: 2023, Volume and Issue: 11(9), P. 4400 - 4427

Published: Jan. 1, 2023

The synthetic strategies, application and future development of non-precious metal-based self-supporting electrodes for Zn–air batteries have been systematically summarized according to the recent research progress.

Language: Английский

Citations

78