Hierarchical Tandem Catalysis Promotes CO Spillover and Trapping for Efficient CO₂ Reduction to C₂₊ Products

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

Published: Feb. 27, 2025

The electrochemical CO2 reduction reaction (CO2RR) to produce multicarbon (C2+) hydrocarbons or oxygenate compounds is a promising route obtain renewable fuel valuable chemicals; however, producing C2+ at high current densities still challenge. Herein, we design hierarchically structured tandem catalysis electrode for greatly improved catalytic activity and selectivity products. constructed of sputtered Ag nanoparticle layer on hydrophobic polytetrafluoroethylene (PTFE) membrane nitrogen-doped carbon (NC)-modified Cu nanowire arrays. arrays are in situ grown PTFE by oxidation CuAl alloy, which the chemical etching metal Al induces formation array structure. Within hierarchical configuration, CO can be efficiently generated an active then spillover transfer NC-modified layer, Cu/NC interfaces enhance *CO trapping adsorption. During CO2RR, optimized achieves superior Faradaic efficiencies 53.5% 87.5% ethylene (C2H4) products density 519.0 mA cm–2, respectively, with C2+/C1 ratio 10.42 long-term stability up 50 h. In Raman attenuated total reflection-surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) confirm that Ag–Cu–NC system significantly enhances linear adsorption intermediates dissociation H2O, improves C–C coupling capability, stabilizes key intermediate *OCCOH

Language: Английский

---

Electrochemical CO2 Reduction: Advances, Insights, Challenges, and Future Directions

Materials Today Sustainability, Journal Year: 2025, Volume and Issue: unknown, P. 101089 - 101089

Published: Feb. 1, 2025

Language: Английский

---

In situ/Operando Investigation for Heterogeneous Electro-Catalysts: From Model Catalysts to State-of-the-Art Catalysts

ACS Energy Letters, Journal Year: 2024, Volume and Issue: 9(9), P. 4414 - 4440

Published: Aug. 17, 2024

Electrochemical reactions, including water splitting, oxygen reduction, hydrogen oxidation, carbon dioxide nitrogen oxide etc., are critical for sustainable energy conversion and storage. Achieving high efficiency in these reactions requires catalysts with superior activity, selectivity, stability, often realized through nanostructured metal catalysts. However, practical challenges such as low selectivity catalytic degradation persist. In situ operando characterization techniques offer real-time insights into catalyst behavior under reaction conditions, enabling a deeper understanding of structure–performance relationships and, therefore, guiding the design optimization electro-catalysts. This review discusses common situ/operando techniques, highlights their applications model catalysts, single-atom single-crystal further explores combinational analysis to study complex nanocatalysts. Finally, we provide suggestions perspectives on development advance field electrochemical catalysis.

Language: Английский

---

Gold Single Atom Doped Defective Nanoporous Copper Octahedrons for Electrocatalytic Reduction of Carbon Dioxide to Ethylene

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

Published: Jan. 24, 2025

Electrocatalytic CO2 reduction into high-value multicarbon products offers a sustainable approach to closing the anthropogenic carbon cycle and contributing neutrality, particularly when renewable electricity is used power reaction. However, lack of efficient durable electrocatalysts with high selectivity for multicarbons severely hinders practical application this promising technology. Herein, nanoporous defective Au1Cu single-atom alloy (De-Au1Cu SAA) catalyst developed through facile low-temperature thermal in hydrogen subsequent dealloying process, which shows toward ethylene (C2H4), Faradaic efficiency 52% at current density 252 mA cm–2 under potential −1.1 V versus reversible electrode (RHE). In situ spectroscopy measurements functional theory (DFT) calculations reveal that C2H4 product results from synergistic effect between Au single atoms Cu sites on surface catalysts, where promote *CO generation defects stabilize key intermediate *OCCO, altogether enhances C–C coupling kinetics. This work provides important insights design electrochemical products.

Language: Английский

---

Progress in Cu‐Based Catalyst Design for Sustained Electrocatalytic CO₂ to C₂₊ Conversion

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

Published: Feb. 27, 2025

Abstract The electrocatalytic conversion of CO 2 into valuable multi‐carbon (C 2+ ) products using Cu‐based catalysts has attracted significant attention. This review provides a comprehensive overview recent advances in catalyst design to improve C selectivity and operational stability. It begins with an analysis the fundamental reaction pathways for formation, encompassing both established emerging mechanisms, which offer critical insights design. In situ techniques, essential validating these by real‐time observation intermediates material evolution, are also introduced. A key focus this is placed on how enhance through manipulation, particularly emphasizing catalytic site construction promote C─C coupling via increasing * coverage optimizing protonation. Additionally, challenge maintaining activity under conditions discussed, highlighting reduction active charged Cu species materials reconstruction as major obstacles. To address these, describes strategies preserve sites control including novel utilization mitigation reconstruction. By presenting developments challenges ahead, aims guide future conversion.

Language: Английский

---

Enhanced electrocatalytic CO2 reduction through surface modification of Cu-based catalysts

Fuel, Journal Year: 2025, Volume and Issue: 392, P. 134576 - 134576

Published: March 5, 2025

Language: Английский

---

Deciphering Electrocatalytic Activity in Cu Nanoclusters: Interplay Between Structural Confinement and Ligands Environment

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

---

Ethylene Electrosynthesis via Selective CO₂ Reduction: Fundamental Considerations, Strategies, and Challenges

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

Published: June 11, 2024

Abstract The electrochemical carbon dioxide reduction reaction (CO 2 RR) is a promising approach for reducing atmospheric ) emissions, allowing harmful CO to be converted into more valuable carbon‐based products. On one hand, single (C 1 products have been obtained with high efficiency and show great promise industrial capture. However, multi‐carbon 2+ possess market value demonstrated significant as potential RR. Due RR's multiple pathways similar equilibrium potentials, the extended mechanisms necessary form C continue reduce overall selectivity of ‐to‐C electroconversion. Meanwhile, RR whole faces many challenges relating system optimization, owing an intolerance low surface pH, systemic stability utilization issues, competing side in H evolution (HER). Ethylene 4 remains incredibly within chemical industry; however, current established method producing ethylene (steam cracking) contributes emission atmosphere. Thus, strategies significantly increase this technology are essential. This review will discuss vital factors influencing forming summarize recent advancements electrosynthesis.

Language: Английский

---

In Situ Phase Transformation-Enabled Metal–Organic Frameworks for Efficient CO₂ Electroreduction to Multicarbon Products in Strong Acidic Media

ACS Nano, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 22, 2024

The electrochemical CO

Language: Английский

---

Criteria and cutting-edge catalysts for CO₂ electrochemical reduction at the industrial scale

Journal of CO2 Utilization, Journal Year: 2024, Volume and Issue: 83, P. 102819 - 102819

Published: May 1, 2024

Converting waste or hazardous chemicals into valuable products is a paramount consideration from economic, environmental, and sustainability standpoints. Diverse strategies are under exploration to convert CO₂ fine chemicals, encompassing electrocatalysis, thermo- photo-catalysis, chemical fixation. Amid these avenues, the electrochemical reduction reaction (CO₂RR) emerges as exceptionally promising, driven by its manifold advantages growing accessibility of renewable electricity sources. While CO₂RR has witnessed substantial advancements, most endeavors remain in proof-of-concept phase, necessitating improved catalytic efficiency stability enable industrialization. Realizing industrial viability technology mandates meticulous myriad electrocatalyst-related factors. This review delves critical criteria recent materials with potential drive at an scale. These factors, akin other processes, closely relate activity, product selectivity, catalyst/system stability, catalyst cost. In this context, we investigated that define electrocatalysts industrially feasible, considering factors such Faradaic efficiency, current density, energy overpotential, choice materials. Furthermore, highlight prime examples demonstrating high for process categorize them based on products. To offer comprehensive perspective, also discusses fundamental principles CO₂RR, covering physicochemical properties CO₂, cell configurations, electrolyte compositions, role electrocatalysts. We address economic significance various

Language: Английский

---