Construction of Two-Dimensional Organometallic Coordination Networks with Both Organic Kagome and Semiregular Metal Lattices on Au(111) DOI

Li‐Xia Kang,

Bingxin Wang, Xin-Yu Zhang

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(23), P. 6108 - 6114

Published: June 3, 2024

Two-dimensional metal-organic networks (2D MONs) having heterogeneous coordination nodes (HCNs) could exhibit excellent performance in catalysis and optoelectronics because of the unbalanced electron distribution coordinating metals. Therefore, design construction 2D MONs with HCNs are highly desirable but remain challenging. Here, we report organometallic an organic Kagome lattice a semiregular metal on Au(111) via situ formation HCNs. Using bifunctional precursor 1,4-dibromo-2,5-diisocyanobenzene, isocyano Au adatom room-temperature yielded chains isocyano-Au-isocyano nodes. In contrast, high-temperature Au(111), selective debromination/coordination cascade reaction occurred, affording phenyl-Au-isocyano By combining scanning tunneling microscopy density functional theory calculations, determined structures products nature nodes, demonstrating thermodynamically favorable pathway for forming

Language: Английский

CO2 electrolysis to multi-carbon products in strong acid at ampere-current levels on La-Cu spheres with channels DOI Creative Commons
Jiaqi Feng, Limin Wu, Xinning Song

et al.

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

Published: June 6, 2024

Abstract Achieving satisfactory multi-carbon (C 2+ ) products selectivity and current density under acidic condition is a key issue for practical application of electrochemical CO 2 reduction reaction (CO RR), but challenging. Herein, we demonstrate that combining microenvironment modulation by porous channel structure intrinsic catalytic activity enhancement via doping effect could promote efficient RR toward C in electrolyte (pH ≤ 1). The La-doped Cu hollow sphere with channels exhibits Faradaic efficiency (FE) 86.2% partial −775.8 mA cm −2 . single-pass conversion can reach 52.8% at −900 Moreover, the catalyst still maintains high FE 81.3% −1 A plays crucial role accumulating K + OH - species near surface within channels, which effectively suppresses undesired hydrogen evolution promotes C–C coupling. Additionally, La enhances generation *CO intermediate, also facilitates formation.

Language: Английский

Citations

51
Low-coordinated copper facilitates the *CH2CO affinity at enhanced rectifying interface of Cu/Cu2O for efficient CO2-to-multicarbon alcohols conversion DOI Creative Commons
Yangyang Zhang, Yanxu Chen, Xiaowen Wang

et al.

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

Published: June 18, 2024

Abstract The carbon−carbon coupling at the Cu/Cu 2 O Schottky interface has been widely recognized as a promising approach for electrocatalytic CO conversion into value-added alcohols. However, limited selectivity of C 2+ alcohols persists due to insufficient control over rectifying characteristics required precise bonding oxyhydrocarbons. Herein, we present an investigation manipulation coordination environment Cu sites through in-situ electrochemical reconstruction strategy, which indicates that construction low-coordinated facilitates enhanced interfaces, and induces asymmetric electronic perturbation faster electron exchange, thereby boosting C-C oxyhydrocarbons towards nucleophilic reaction process *H CCO-CO. Impressively, exhibit superior faradic efficiency 64.15 ± 1.92% energy ~39.32% production, while maintaining stability 50 h (faradic >50%, total current density = 200 mA cm −2 ) in flow-cell electrolyzer. Theoretical calculations, operando synchrotron radiation Fourier transform infrared spectroscopy, Raman experiments decipher can enhance coverage *CO adsorption *CH CH CHO, facilitating formation

Language: Английский

Citations

32
MOF-Based Electrocatalysts: An Overview from the Perspective of Structural Design DOI

Nana Sun,

Syed Shoaib Ahmad Shah, Zhongyuan Lin

et al.

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 18, 2025

The electrocatalytic technique, as an efficient energy storage and conversion technology, has attracted significant attention to address exhaustion environmental pollution. Usually, the activity selectivity of reactions are largely dominated by dynamic process occurring on electrocatalysts. Therefore, high-performance electrocatalysts, which can dominate pathway barrier reactions, great significance for advancement technique. Metal-organic frameworks (MOFs), emerging crystalline porous materials, present structural component advantages including well-defined structure, high surface area, large porosity, diverse components, easy tailorability, demonstrating fantastic potential precise fabrication In this Review, strategies in electrocatalysts based MOF-related materials specifically introduced from aspects catalytic site design microenvironment modulation around sites. Furthermore, representative progress achieved various applications employing MOF-based is systematically summarized, with special emphasis MOFs performance optimization. Finally, remaining challenges future perspectives further highlighted.

Language: Английский

Citations

5
Metal‐Organic Frameworks‐Based Copper Catalysts for CO2 Electroreduction Toward Multicarbon Products DOI Creative Commons
Qin Chen,

Xuheng Li,

Ting Wang

et al.

Exploration, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 12, 2025

ABSTRACT Copper (Cu) is the most promising catalyst for electrochemical CO 2 ‐to‐C 2+ conversion, whereas performance remains below practical thresholds due to high energy barrier of C−C coupling and lack effective approaches steer reaction pathway. Recent advances show that metal‐organic frameworks (MOF) could be a platform as support, pre‐catalyst, co‐catalyst modify electronic structure local environment Cu catalysts promoting reduction by virtue their great tunability over compositions pore architectures. In this review, we discussed general design principles, catalytic mechanisms, achievements MOF‐based catalysts, aiming boost refinement steering pathway C products. The fundamentals challenges are first introduced. Then, summarized conceptions from three aspects: engineering properties Cu, regulating environment, managing site exposure mass transport. Further, latest progress products namely Cu‐based MOF, MOF‐derived Cu@MOF hybrid discussed. Finally, future research opportunities strategies suggested innovate rational advanced electrifying transformation.

Language: Английский

Citations

2
Spatially and Temporally Resolved Dynamic Response of Co-Based Composite Interface during the Oxygen Evolution Reaction DOI

Xia Zhong,

Jingyao Xu,

Junnan Chen

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7467 - 7479

Published: March 6, 2024

Interfacial interaction dictates the overall catalytic performance and behavior rules of composite catalyst. However, understanding interfacial active sites at microscopic scale is still limited. Importantly, identifying dynamic action mechanism "real" site interface necessitates nanoscale, high spatial-time-resolved complementary-operando techniques. In this work, a Co3O4 homojunction with well-defined effect developed as model system to explore spatial-correlation response toward oxygen evolution reaction. Quasi in situ scanning transmission electron microscopy–electron energy-loss spectroscopy spatial resolution visually confirms size characteristics dimension, showing that activation originates from strong interactions 3 nm. Multiple time-resolved operando techniques explicitly capture changes adsorption for key reaction intermediates. Combined density functional theory calculations, we reveal adjustment multiple configurations intermediates by highly activated facilitates O–O coupling *OOH deprotonation processes. The dual regulation accelerates kinetics serves pivotal factor promoting activity structure. resulting catalyst (Co–B@Co3O4/Co3O4 NSs) exhibits an approximately 70-fold turnover frequency 20-fold mass than monomer structure (Co3O4 leads significant (η10 ∼257 mV). visual complementary analysis multimodal operando/in provides us powerful platform advance our fundamental structure–activity relationships structured catalysts.

Language: Английский

Citations

15
Modulating the localized electronic distribution of Cu species during reconstruction for enhanced electrochemical CO2 reduction to C2+ products DOI

Zongmiao Li,

Zhu Liu, Shiju Li

et al.

Journal of Materials Chemistry A, Journal Year: 2024, Volume and Issue: 12(25), P. 15082 - 15089

Published: Jan. 1, 2024

ZrO 2 stabilized Cu + can optimize *CO adsorption and promote the following C–C coupling to achieve 70+% FE C 2+ in a wide potential range.

Language: Английский

Citations

13
Asymmetrically Coordinated Cu Dual‐Atom‐Sites Enables Selective CO2 Electroreduction to Ethanol DOI
Changli Chen,

Zhiyi Sun,

Gangzhi Qin

et al.

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

Published: Oct. 6, 2024

Abstract Electrochemical reduction of CO 2 (CO RR) to value‐added liquid fuels is a highly attractive solution for carbon‐neutral recycling, especially C 2+ products. However, the selectivity control preferable products great challenge due complex multi‐electron proton transfer process. In this work, series Cu atomic dispersed catalysts are synthesized by regulating coordination structures optimize RR selectivity. ‐SNC catalyst with uniquely asymmetrical coordinated CuN ‐CuNS site shows high ethanol selective FE 62.6% at −0.8 V versus RHE and 60.2% 0.9 in H‐Cell Flow‐Cell test, respectively. Besides, nest‐like structure beneficial mass process selection catalytic situ experiments theory calculations reveal reaction mechanisms such ethanol. The S atoms weaken bonding ability adjacent carbon atom, which accelerates from *CHCOH generate *CHCHOH, resulting This work indicates promising strategy rational design asymmetrically single, dual, or tri‐atom provides candidate material produce

Language: Английский

Citations

9
Rectifying Heterointerface Facilitated C‐N Coupling Dynamics Enables Efficient Urea Electrosynthesis Under Ultralow Potentials DOI
Mingyu Cheng,

Shao Wang,

Zechuan Dai

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Sept. 25, 2024

Electrocatalytic C-N coupling for urea synthesis from carbon dioxide (CO

Language: Английский

Citations

4
Electrocatalytic C–C coupling of CO2 and formaldehyde to synthesize acetate via membrane electrode assembly DOI

Shaohan Xu,

Jingui Zheng,

Lingzhi Sun

et al.

Green Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A novel strategy for acetate production from electrocatalytic coupling of carbon dioxide and formaldehyde in a membrane electrode assembly cell is reported.

Language: Английский

Citations

0
Hydroxide-Oxide-Sulfur-Stabilized Bismuth Nanorod Conversion: Selective Induction of the Electrochemical Reduction of CO2 to Formate DOI

Naveenkumar Palanimuthu,

Ramasamy Santhosh Kumar,

Saleem Sidra

et al.

ACS Applied Nano Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 14, 2025

The electrochemical CO2 reduction reaction (e-CO2RR) converts value-added chemicals into formate. Bismuth-based resources exhibit promising potential in the of to formate due their low toxicity and ability enhance *OCHO intermediate pathway. However, there are numerous hurdles optimizing activity applicability. Here, we describe assembly structurally stable bismuth hydroxide, oxide, sulfide nanorods supported by a reduced graphene oxide (rGO) nanosheet through simple hydrothermal method. obtained optimized rGO-Bi2S3 improved e-CO2RR conversions H-cell systems compared hydroxide electrocatalysts. maintain high within wide window (−0.76 −1.26 V vs RHE) obtain overall Faradaic efficiency ±84% at −1.16 RHE, current density ±41.50 mA cm–2, stability for longer than 12 h, with greater ±86% an system. Theoretical calculations reveal that strong interaction between rGO Bi2S3 stabilizes adsorption e-CO2RR. resulting structural transformation based on sulfur, provides encouraging avenue future energy conversion.

Language: Английский

Citations

0