Fabrication of Ultrahigh‐Loading Dual Copper Sites in Nitrogen‐Doped Porous Carbons Boosting Electroreduction of CO2 to C2H4 Under Neutral Conditions DOI
Jin‐Meng Heng, Haolin Zhu, Zhen‐Hua Zhao

et al.

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

Published: Nov. 16, 2024

Abstract Synthesis of high‐loading atomic‐level dispersed catalysts for highly efficient electrochemical CO 2 reduction reaction (eCO RR) to ethylene (C H 4 ) in neutral electrolyte remain challenging tasks. To address common aggregation issues, a host‐guest strategy is employed, by using metal‐azolate framework ( MAF‐4 with nanocages as the host and dinuclear Cu(I) complex guest, form precursors pyrolysis into series nitrogen‐doped porous carbons (NPCs) varying loadings dual copper sites, namely NPC ‐Cu ‐21 (21.2 wt%), ‐11 (10.6 ‐7 (6.9 wt%). Interestingly, loading sites increased from 6.9 21.2 wt%, partial current density eCO RR yield C also gradually 38.7 93.6 mA cm −2 . In 0.1 m KHCO 3 electrolyte, at −1.4 V versus reversible hydrogen electrode vs RHE), exhibits excellent performance Faradaic efficiency 52% 180 Such can be attributed presence ultrahigh‐loading which promotes C─C coupling formation products. The findings demonstrate confinement effect conducive preparation catalysts.

Language: Английский

Metal-ligand dual-site single-atom nanozyme mimicking urate oxidase with high substrates specificity DOI Creative Commons
Kaiyuan Wang, Qing Hong,

Caixia Zhu

et al.

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

Published: July 8, 2024

Abstract In nature, coenzyme-independent oxidases have evolved in selective catalysis using isolated substrate-binding pockets. Single-atom nanozymes (SAzymes), an emerging type of non-protein artificial enzymes, are promising to simulate enzyme active centers, but owing the lack recognition sites, realizing substrate specificity is a formidable task. Here we report metal-ligand dual-site SAzyme (Ni-DAB) that exhibited selectivity uric acid (UA) oxidation. Ni-DAB mimics catalytic mechanism urate oxidase, which Ni metal center and C atom ligand serve as specific UA O 2 binding respectively, characterized by synchrotron soft X-ray absorption spectroscopy, situ near ambient pressure photoelectron isotope labeling. The theoretical calculations reveal high derived from not only delicate interaction between also complementary oxygen reduction at beta site ligand. As potential application, Ni-DAB-based biofuel cell human urine constructed. This work unlocks approach enzyme-like dual sites boosting enzymes.

Language: Английский

Citations

25
Hydrophobic SiO2 Armor: Stabilizing Cuδ+ to Enhance CO2 Electroreduction toward C2+ Products in Strong Acidic Environments DOI
Meiling Wang, Zewen Wang, Zihao Huang

et al.

ACS Nano, Journal Year: 2024, Volume and Issue: 18(23), P. 15303 - 15311

Published: May 28, 2024

Electroreduction of CO2 in highly acidic environments holds promise for enhancing utilization efficiency. Due to the HER interference and structural instability, however, challenges improving selectivity stability toward multicarbon (C2+) products remain. In this study, we proposed an "armor protection" strategy involving deposition ultrathin, hydrophobic SiO2 onto Cu surface (Cu/SiO2) through a simple one-step hydrolysis. Our results confirmed effective inhibition by layer, leading high Faradaic efficiency (FE) up 76.9% C2+ at current density 900 mA cm–2 under strongly condition with pH 1. The observed performance surpassed reported most previously studied Cu-based catalysts CO2RR systems. Furthermore, ultrathin shell was demonstrated effectively prevent reconstruction preserve oxidation state Cuδ+ active sites during CO2RR. Additionally, it hindered accumulation K+ ions on catalyst diffusion situ generated OH– away from electrode, thereby favoring product generation. Raman analyses coupled DFT simulations further elucidated that proficiently modulated *CO adsorption behavior Cu/SiO2 reducing energy, facilitating C–C coupling. This work offers compelling rationally designing exploiting stable environments.

Language: Английский

Citations

23
Electrocatalytic conversion of CO2 into selective carbonaceous fuels using metal-organic frameworks: An overview of recent progress and perspectives DOI

E. Sivasurya,

Raji Atchudan,

Mohamed Gamal Mohamed

et al.

Materials Today Chemistry, Journal Year: 2025, Volume and Issue: 44, P. 102538 - 102538

Published: Jan. 21, 2025

Language: Английский

Citations

2
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
Interstitial carbon induces enriched Cuδ+ sites in Cu2O nanoparticles to facilitate CO2 electroreduction to C2+ products DOI
Haoran Wang, Rongbo Sun, Peigen Liu

et al.

Nano Research, Journal Year: 2024, Volume and Issue: 17(8), P. 7013 - 7019

Published: June 26, 2024

Language: Английский

Citations

12
Atomically Dispersed Metal Catalysts for the Conversion of CO2 into High‐Value C2+ Chemicals DOI
Qihao Yang,

Hao Liu,

Yichao Lin

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(37)

Published: May 19, 2024

Abstract The conversion of carbon dioxide (CO 2 ) into value‐added chemicals with two or more carbons (C 2+ is a promising strategy that cannot only mitigate anthropogenic CO emissions but also reduce the excessive dependence on fossil feedstocks. In recent years, atomically dispersed metal catalysts (ADCs), including single‐atom (SACs), dual‐atom (DACs), and single‐cluster (SCCs), emerged as attractive candidates for fixation reactions due to their unique properties, such maximum utilization active sites, tunable electronic structure, efficient elucidation catalytic mechanism, etc. This review provides an overview significant progress in synthesis characterization ADCs utilized photocatalytic, electrocatalytic, thermocatalytic toward high‐value C compounds. To provide insights designing chemical originating from , key factors influence activity selectivity are highlighted. Finally, relevant challenges opportunities discussed inspire new ideas generation ‐based products over ADCs.

Language: Английский

Citations

10
In Situ Reconstruction of Scalable Amorphous Indium-Based Metal–Organic Framework for CO2 Electroreduction to Formate over an Ultrawide Potential Window DOI
Ziyun Liu, Xinxin Han, Junhui Liu

et al.

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: 16(22), P. 28655 - 28663

Published: May 22, 2024

Amorphous metal–organic frameworks (aMOFs) are highly attractive for electrocatalytic applications due to their exceptional conductivity and abundant defect sites, but harsh preparation conditions of "top-down" strategy have hindered widespread use. Herein, the scalable production aMIL-68(In)-NH2 was successfully achieved through a facile "bottom-up" involving ligand competition with 2-methylimidazole. Multiple in situ ex characterizations reveal that evolutes into In/In2O3–x as genuine active sites during CO2 reduction (CO2RR) process. Moreover, retained amino groups could enhance adsorption. As expected, reconstructed catalyst demonstrates high formate Faradaic efficiency values (>90%) over wide potential range 800 mV flow cell, surpassing most top-ranking electrocatalysts. Density functional theory calculations oxygen vacancies induce more local charges around electroactive thereby promoting formation HCOO* intermediates. Furthermore, 16 g samples can be readily prepared one batch exhibit almost identical CO2RR performances. This work offers feasible batch-scale design amorphous MOFs efficient electrolytic CO2RR.

Language: Английский

Citations

10
Recent strategies to improve the electroactivity of metal–organic frameworks for advanced electrocatalysis DOI Creative Commons

Runzhi Wei,

Xiao Li, Aziz B. Ibragimov

et al.

Deleted Journal, Journal Year: 2024, Volume and Issue: 1(2), P. 181 - 206

Published: Aug. 4, 2024

Abstract Metal–organic frameworks (MOFs) have emerged as promising materials in the realm of electrocatalysis due to their high surface area, tunable porosity, and versatile chemical functionality. However, practical application has been hampered by inherent limitations such low electrical conductivity a limited number active metal sites. Researchers addressed these challenges through various strategies, including enhancing incorporating conductive nanoparticles, modifying structure composition MOFs replacing nodes functionalizing linkers, preparing catalysts thermal processes decarburization conversion into oxides, phosphides (MPs), sulfides (MSs). This review provided comprehensive summary strategies that were employed enhance electroactivity for improved electrocatalytic performance recent years. It also explored future directions potential innovations design synthesis MOF‐based electrocatalysts, offering valuable insights advancing sustainable energy technologies.

Language: Английский

Citations

10
Confinement Synthesis of Atomic Copper‐Anchored Polymeric Carbon Nitride in Crystalline UiO‐66‐NH2 for High‐Performance CO2‐to‐CH3OH Photocatalysis DOI Open Access

Xingbing Liu,

Changyan Zhu,

Mengying Li

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(45)

Published: July 29, 2024

Photocatalytic CO

Language: Английский

Citations

9
Promotion of C─C Coupling in the CO2 Electrochemical Reduction to Valuable C2+ Products: From Micro‐Foundation to Macro‐Application DOI Open Access
Yanjun Guan,

Youzhi Li,

Zhongjian Li

et al.

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 2, 2025

Abstract The electrochemical CO 2 reduction reaction (CO RR) to valuable C 2+ products emerges as a promising strategy for converting intermittent renewable energy into high‐energy‐density fuels and feedstock. Leveraging its substantial commercial potential compatibility with existing infrastructure, the conversion of multicarbon hydrocarbons oxygenates (C ) holds great industrial promise. However, process is hampered by complex multielectron‐proton transfer reactions difficulties in reactant activation, posing significant thermodynamic kinetic barriers commercialization production. Addressing these necessitates comprehensive approach encompassing multiple facets, including effective control C─C coupling electrolyzers using efficient catalysts optimized local environments. This review delves advancements outstanding challenges spanning from microcosmic macroscopic scales, design nanocatalysts, optimization microenvironment, development electrolyzers. By elucidating influence electrolyte environment, exploring flow cells, guidelines are provided future research aimed at promoting coupling, thereby bridging microscopic insights applications field electroreduction.

Language: Английский

Citations

1