Multiple Reaction Pathways for Oxygen Evolution as a Key Factor for the Catalytic Activity of Nickel–Iron (Oxy)Hydroxides DOI
Giuseppe Mattioli, Leonardo Guidoni

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

Published: Jan. 15, 2025

We present a comprehensive theoretical study, using state-of-the-art density functional theory simulations, of the structural and electrochemical properties amorphous pristine iron-doped nickel–(oxy)hydroxide catalyst films for water oxidation in alkaline solutions, referred to as NiCat Fe:NiCat. Our simulations accurately capture changes locally ordered units, reported by X-ray absorption spectroscopy, when are activated exposure positive potential. emphasize critical role proton-coupled electron transfer reversible Ni(II) Ni(III/IV) during this activation. After establishing models Fe:NiCat consistent with experimental data, we used them explore atomistic mechanism oxygen evolution reaction (OER), which is triggered once applied potential exceeds overpotential required production. quantitatively compared seven OER pathways applicable both adsorbate (AEM) lattice-oxygen-mediated (LOM) families, elucidating how iron significantly enhances catalytic activity NiCat. findings suggest that simple metal–oxygen–metal motifs, common on surface crystalline metal (oxy)hydroxide films, can promote AEM LOM mechanisms under typical conditions. Furthermore, propose elusive lies distinct behavior Ni(IV)–O Fe(IV)–O bonds key intermediates preceding formation O–O bond, Fe ions lowering needed form these across investigated pathways.

Language: Английский

Customizing CO2 Electroreduction by Pulse-Induced Anion Enrichment DOI
Jianghao Wang,

Yanyang Qin,

Shoutong Jin

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(48), P. 26213 - 26221

Published: Nov. 9, 2023

Electrochemically converting CO2 into specified high-value products is critical for carbon neutral economics. However, governing the product distribution of electroreduction on Cu-based catalysts remains challenging. Herein, we put forward an anion enrichment strategy to efficiently dictate route *CO reduction by a pulsed electrolysis strategy. Upon periodically applying positive potential cathode, concentration in vicinity electrode increases apparently. By adopting KF, KCl, and KHCO3 as electrolytes, dominant commercial Cu foil can be tuned CO (53% ± 2.5), C2+ (76.6 2.1%), CH4 (42.6 2.1%) under electrolysis. Notably, one delicately tailor ratios CO/CH4, CH4/C2+, C2+/CO simply changing composition electrolyte. Density functional theory calculations demonstrate that locally enriched anions affect key CO2RR intermediates different ways owing their specific electronegativity volume, which leads distinct selectivity. The present study highlights importance tuning ionic species at electrode–electrolyte interface customizing products.

Language: Английский

Citations

33
High selective electrocatalytic reduction of carbon dioxide to ethylene enabled by regulating the microenvironment over Cu-Ag nanowires DOI

Dehe Fan,

Shiji Zhang,

Yumeng Li

et al.

Journal of Colloid and Interface Science, Journal Year: 2024, Volume and Issue: 662, P. 786 - 795

Published: Feb. 15, 2024

Language: Английский

Citations

12
Activating *CO by Strengthening Fe–CO π‐Backbonding to Enhance Two‐Carbon Products Formation toward CO2 Electroreduction on Fe–N4 Sites DOI
Weiwei Zhu, Suqin Liu, Kuangmin Zhao

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(38)

Published: April 10, 2024

Abstract Many non‐precious metal‐nitrogen (M–N x )‐containing catalysts are highly efficient for electrochemical reduction of CO 2 to and yet encounter challenges in further converting more valuable two‐carbon products (C2), such as ethanol acetic acid. The ambiguous structure‐activity relationship the M–N moieties toward reaction (CO RR) results difficulties regulating RR product selectivity on ‐containing catalysts. Herein, by using fluorinated iron phthalocyanines with axial‐coordinated ligands (L–FePc–F) an 4 ‐based model electrocatalyst RR, a correlation between electronic structure C2 Fe–N is revealed comprehensive descriptor based Fe–CO π‐backbonding proposed guiding regulation higher selectivity. Based principle, Br‐axial‐coordinated FePc–F (Br–FePc–F) remarkably increases Faradic efficiency (FE) from 0% (i.e., FE FePc–F) 34% due strengthened stemming elevated 3 d xz / yz orbital energy enhanced electron‐donating ability Fe centers . This work provides strategy mechanism insights moieties, which may be inspiring precise construction specific products.

Language: Английский

Citations

12
Value‐Added Cascade Synthesis Mediated by Paired‐Electrolysis Using an Ultrathin Microenvironment‐Inbuilt Metalized Covalent Organic Framework Heterojunction DOI
Qing Li, Dong‐Dong Ma,

Wenbo Wei

et al.

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(27)

Published: April 25, 2024

Abstract Energy‐saving and value‐added management in advanced catalysis is highly desirable but challenged by the limitations of multifunctional catalysts catalytic modules. Herein, an azo‐linked phthalocyanine‐porphyrin covalent organic framework (COF) with ultrathin layered nanostructure grown on carbon nanotubes (NiPc‐azo‐H2Pp@CNTs) has been designed synthesized, which can serve as a active stable bifunctional heterojunction electrocatalyst for selective paired‐electrosynthesis through coupling anodic iodide oxidation reaction cathodic CO 2 conversion. Particularly, inbuilt local microenvironment conferred dihydroporphyrin moieties COF act proton reservoir to promote relay at interface during electrocatalytic process. Moreover, cascade construction dual electrocatalytic/organocatalytic modules, cathode‐generated be further converted dimethyl carbonate yield 6.21 mmol L −1 h , while anode‐produced iodine derived into iodoform hundred‐milligram scale. It worth noting that synthesis mediated paired‐electrolysis using distinctive high‐powered electrocatalysts will help advance sustainable development industrial intelligent manufacturing.

Language: Английский

Citations

11
Microenvironment Engineering of Heterogeneous Catalysts for Liquid-Phase Environmental Catalysis DOI

Zhong‐Shuai Zhu,

Shuang Zhong, Cheng Cheng

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(20), P. 11348 - 11434

Published: Oct. 9, 2024

Environmental catalysis has emerged as a scientific frontier in mitigating water pollution and advancing circular chemistry reaction microenvironment significantly influences the catalytic performance efficiency. This review delves into engineering within liquid-phase environmental catalysis, categorizing microenvironments four scales: atom/molecule-level modulation, nano/microscale-confined structures, interface surface regulation, external field effects. Each category is analyzed for its unique characteristics merits, emphasizing potential to enhance efficiency selectivity. Following this overview, we introduced recent advancements advanced material system design promote (e.g., purification, transformation value-added products, green synthesis), leveraging state-of-the-art technologies. These discussions showcase was applied different reactions fine-tune regimes improve from both thermodynamics kinetics perspectives. Lastly, discussed challenges future directions engineering. underscores of intelligent materials drive development more effective sustainable solutions decontamination.

Language: Английский

Citations

11
CuNiZn vs CuZn Electrodes: Electrochemical CO2 Reduction, Role of Metal Elements, and Insights for C–C Coupling Chemistry DOI
Yunji Gwon, Seon Young Hwang,

Go Eun Park

et al.

ACS Applied Energy Materials, Journal Year: 2024, Volume and Issue: 7(2), P. 614 - 628

Published: Jan. 3, 2024

Exploring bi- and trimetallic catalysts in electrochemical CO2 reduction (EC CO2R) has been a focal point for discovering products. This study investigates the distinct roles of metal elements CO2R using CuNiZn CuZn electrodes. Bimetallic exhibits superior activity, yielding substantial amounts CO, CH4, C2H4, various liquid products, including formate, ethanol, acetate, propanol, isopropanol. The on suggests potential connections to Fischer–Tropsch (FT) synthesis, indicating their capability produce long-chain hydrocarbons (CnH2n CnH2n+2, n = 2–7) from CO2. EC CO validated FT process over catalysts. discussion explores mechanisms formation C–C coupled C2+ considering potential- concentration-dependent Faradaic efficiencies (FEs). Recycling tests emphasize influence composition FEs. Surface analyses reveal oxidation states compositional changes, while dissolution metals during electrochemistry highlights dynamic surface characteristics. work provides insights into catalysts, states, conditions, advancing our understanding these electrodes role recycling through electrochemistry.

Language: Английский

Citations

10
Restructuring multi-phase interfaces from Cu-based metal–organic frameworks for selective electroreduction of CO2 to C2H4 DOI Creative Commons

Jiye Feng,

Wenbiao Zhang, Danni Shi

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(24), P. 9173 - 9182

Published: Jan. 1, 2024

Directional in situ reconfiguration of Ag incorporating HKUST-1 frameworks was introduced to restructure multi-phase Ag/Cu/Cu 2 O electrocatalysts for the selective electro-reduction CO C H 4 .

Language: Английский

Citations

10
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
Electrocatalysis in deep eutectic solvents: from fundamental properties to applications DOI Creative Commons

Hengan Wang,

Xinchen Kang, Buxing Han

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(26), P. 9949 - 9976

Published: Jan. 1, 2024

Electrocatalysis stands out as a promising avenue for synthesizing high-value products with minimal environmental footprint, aligning the imperative sustainable energy solutions. Deep eutectic solvents (DESs), renowned their eco-friendly, safe, and cost-effective nature, present myriad advantages, including extensive opportunities material innovation utilization reaction media in electrocatalysis. This review initiates an exposition on distinctive features of DESs, progressing to explore applications electrocatalyst synthesis Additionally, it offers insightful analysis challenges prospects inherent electrocatalysis within DESs. By delving into these aspects comprehensively, this aims furnish nuanced understanding thus broadening horizons realm facilitating expanded application.

Language: Английский

Citations

9
Optimal Electrocatalyst Design Strategies for Acidic Oxygen Evolution DOI Creative Commons
Dongdong Zhang, Qilong Wu, Liyun Wu

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 11(38)

Published: Aug. 9, 2024

Abstract Hydrogen, a clean resource with high energy density, is one of the most promising alternatives to fossil. Proton exchange membrane water electrolyzers are beneficial for hydrogen production because their current facile operation, and gas purity. However, large‐scale application electrochemical splitting acidic electrolytes severely limited by sluggish kinetics anodic reaction inadequate development corrosion‐ highly oxidation‐resistant anode catalysts. Therefore, catalysts excellent performance long‐term durability must be developed oxygen evolution reactions (OER) in media. This review comprehensively outlines three commonly employed strategies, namely, defect, phase, structure engineering, address challenges within OER, while also identifying existing limitations. Accordingly, correlation between material design strategies catalytic discussed terms contribution activity stability. In addition, various nanostructures that can effectively enhance catalyst at mesoscale summarized from perspective engineering technology, thus providing suitable satisfy industrial requirements. Finally, future outlook area OER presented.

Language: Английский

Citations

9