Hierarchical Assembly of High-Nuclearity Copper(I) Alkynide Nanoclusters: Highly Effective CO2 Electroreduction Catalyst toward Hydrocarbons DOI

Wen-Lei Mu,

Lanyan Li,

Xuzi Cong

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 4, 2024

The pursuit of precision in the engineering metal nanoparticle assemblies has long fascinated scientists, but achieving atomic-level accuracy continues to pose a significant challenge. This research sheds light on hierarchical assembly processes two high-nuclearity Cu(I) nanoclusters (NCs). By employing multiligand cooperative stabilization strategy, we have isolated series thiacalix[4]arene (TC4A)/alkynyl coprotected NCs (

Language: Английский

Understanding the Role of Potential and Cation Effect on Electrocatalytic CO2 Reduction in All-Alkynyl-Protected Ag15 Nanoclusters DOI
Yuping Chen, Xia Zhou,

Xunying Liu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 8, 2025

Atomically precise metal nanoclusters (NCs) have emerged as an intriguing class of model catalysts for electrochemical CO2 reduction reactions (CO2RR). However, the interplay between interface environment (e.g., potential, cation concentration) and electron–proton transfer (ET/PT) kinetics─particularly in alkynyl-protected NCs─remains poorly understood. Here, we combined first-principles simulations experiments to investigate role potential effect on CO2RR performance a prototype all-alkynyl-protected Ag15(C≡C–CH3)+ cluster. Our revealed that applied triggers elimination alkynyl ligand via sequentially breaking two π-type Ag–C bonds one σ-type bond expose catalytically active Ag sites, barrier breakage monotonically decreases with lowering potential. Furthermore, show introducing inner-sphere Na+ ions greatly enhances *CO2 activation promotes proton generate *COOH *CO by forming Na+–CO2(*COOH) complexes, while competitive hydrogen evolution reaction (HER) from water dissociation is suppressed, thus dramatically improving selectivity electroreduction. The measurements further validated our predictions, where CO Faradaic efficiency (FECO) current density (jCO) pronounced dependence concentration. At optimal concentration 0.1 M NaCl, FECO can reach up ∼96%, demonstrating crucial cations promoting CO2RR. findings provide vital insights into atomic-level mechanism Ag15 NCs highlight important electrolyte governing electron/proton kinetics.

Language: Английский

Citations

5
Ligand-induced Changes in the Electrocatalytic Activity of Atomically Precise Au₂₅ Nanoclusters DOI Creative Commons

Lipan Luo,

Xia Zhou, Yuping Chen

et al.

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

Published: Jan. 1, 2025

Using ligand-protected Au 25 nanoclusters as a prototype model, we demonstrated that hydrophilic ligands enhance the hydrogen evolution reaction while hydrophobic improve efficiency of CO 2 electroreduction to CO.

Language: Английский

Citations

5
Enigma of Sustainable CO2 Conversion to Renewable Fuels and Chemicals Through Photocatalysis, Electrocatalysis, and Photoelectrocatalysis: Design Strategies and Atomic Level Insights DOI Open Access

Diksha Suri,

Srimanta Das,

Shivani Choudhary

et al.

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

Published: Jan. 2, 2025

Growing global population, escalating energy consumption, and climate change threaten future security. Fossil fuel combustion, primarily coal, oil, natural gas, exacerbates the greenhouse effect driving warming through CO

Language: Английский

Citations

4
Unveiling Key Descriptors of Ionomer Materials for Enhanced Electrochemical CO2 Reduction DOI

Wonsang Jung,

Sang‐Hun Shin, Sejin Park

et al.

ACS Energy Letters, Journal Year: 2025, Volume and Issue: 10(1), P. 620 - 628

Published: Jan. 3, 2025

Polymeric ionomers near the catalyst surface of CO2 reduction reaction (CO2RR) electrodes affect their efficiency; however, multifaceted properties complicate structure–activity relationship elucidation. Here, we synthesized polycarbazole-based anion-exchange (QPC) bearing varying functionalized side chains to explore this relationship. Comprehensive analysis in physicochemical properties, electrochemical activity, and operando ATR-SEIRAS revealed that functional group modification significantly influenced intrinsic ionomer thereby affecting Ag microenvironments interfacial water structures, kinetics protonation step for CO2RR hydrogen evolution (HER). Notably, QPC-trimethyl phosphonium (TMP) induced favorable having a high proportion strong H-bonded with low Stark tuning slopes, which inhibit HER promote CO2RR. A CO Faradaic efficiency (>90%) was maintained using QPC-TMP membrane electrode assembly, even under concentrations (100–15%) elevated temperatures (28–72 °C). These findings suggest catalytic environment can be optimized by fine-tuning structure, contributing advancement high-performance ionomers.

Language: Английский

Citations

2
Understanding the Ag-S Interface Stability and Electrocatalytic Activity of CO2 Electroreduction in Atomically Precise Ag25 Nanoclusters DOI
Yuting Ye, Xia Zhou, Yuping Chen

et al.

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

Published: Jan. 1, 2025

The leaching dynamics of the Ag–S interface and mechanism CO 2 electroreduction for Ag 25 (SR) 18 nanocluster differ significantly from those its Au analogue.

Language: Английский

Citations

2
Emerging Supported Metal Atomic Clusters for Electrocatalytic Renewable Conversions DOI
Hanqi Xu, Wenqi Zhao, Di Li

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 2434 - 2458

Published: Jan. 27, 2025

Subnanometric supported metal atomic clusters (SMACs) composed of several to tens surface atoms have attracted increased research interest in electrocatalysis. SMACs been known show distinct properties compared their nanoparticles and single atom counterparts long developed for functional improvements. Tremendous advancements made the past few years, with a notable trend more precise design down an atomic/molecular level investigation transferring into practical devices, which motivates this timely review. To begin, review presents classifies classic latest synthetic strategies state-of-the-art characterization techniques SMACs. It then outlines discusses basic structure principles SMACs, highlighting importance organic ligands, size effect clusters, support-cluster interactions determining catalytic activity device stability. Thereafter, recent advances typical electrocatalysis processes from laboratory scale industrial are discussed obtain general understanding structure–activity correlations Current challenges future perspectives emerging field also discussed, aiming at practicing SMAC catalysts energy conversion devices.

Language: Английский

Citations

2
Probing Temperature Effect on Enhanced Electrochemical CO2 Reduction of Hydrophobic Au25(SR)18 Nanoclusters DOI

Fang Sun,

Xia Zhou, Lubing Qin

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4605 - 4617

Published: March 4, 2025

Language: Английский

Citations

2
Boosting the Electroreduction of CO2 to CO by Ligand Engineering of Gold Nanoclusters DOI Creative Commons
Sang Myeong Han,

Minyoung Park,

Ji-Young Kim

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 17, 2024

The electrochemical CO

Language: Английский

Citations

10
In2Cu3O6 Nanocluster in Siliceous Zeolite for Efficient CO2 Methanation DOI
Yanbin Zhu,

Xiaoju Yang,

Yan Wei

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3339 - 3349

Published: Feb. 10, 2025

Language: Английский

Citations

1
Deciphering Electrocatalytic Activity in Cu Nanoclusters: Interplay Between Structural Confinement and Ligands Environment DOI Creative Commons
Sourav Biswas,

Yamato Shingyouchi,

Maho Kamiyama

et al.

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

Published: March 6, 2025

Ligand-protected copper nanoclusters (Cu NCs) with atomic precision have emerged rapidly due to their fascinating structural architectures and versatile catalytic properties, making them ideal for investigating structure-activity relationships. Despite potential, challenges such as stability issues limited diversity restricted deeper exploration. In this study, three distinct Cu NCs are synthesized using a one-pot reduction strategy by carefully modifying reaction conditions. Intriguingly, the same p-toluenethiol ligand produces two different geometries, while varying ligands m-aminobenzethiol-yielded clusters similar geometric architectures. These evaluated electrocatalytic CO2 reduction, uncovering diverse activities product selectivity. Experimental theoretical analyses reveal that interplay between core structure confinement surface environment governs behavior. Specifically, Cu11 NC exhibits selectivity toward HCOOH production (FEHCOOH∼45% at -1.2 V vs RHE), whereas substituting m-aminobenzethiol shifted competitive side (FEH2∼82% RHE). Conversely, altering geometry of Cu18 retaining decreases (FEHCOOH∼35% findings highlight tunability tailored applications through precise control chemistry.

Language: Английский

Citations

1