Strong p‐d Orbital Hybridization on Bismuth Nanosheets for High Performing CO2 Electroreduction DOI

Xueying Cao,

Yadong Tian,

Jizhen Ma

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(6)

Published: Nov. 27, 2023

Abstract Single‐atom alloys (SAAs) show great potential for a variety of electrocatalytic reactions. However, the atomic orbital hybridization effect SAAs on electrochemical reactions is unclear yet. Herein, in situ confinement vanadium/molybdenum/tungsten atoms bismuth nanosheet shown to create with rich grain boundaries, respectively. With detailed analysis microstructure and composition, strong p‐d between vanadium enables exceptional performance carbon dioxide (CO 2 ) reduction Faradaic efficiency nearly 100% C1 products wide range from −0.6 −1.4 V, long‐term electrolysis stability 90 h. In‐depth investigations theoretical computations reveal that electron delocalization toward via evokes active centers efficient CO activation σ‐donation O‐to‐Bi, thus reduces protonation energy barriers formate production. such fundamental understanding, SAA electrocatalyst employed fabricated solar‐driven electrolytic cell 5‐hydroxymethylfurfural oxidation, achieving an outstanding 2,5‐furandicarboxylic acid yield 90.5%. This study demonstrates feasible strategy rationally design advanced electrocatalysts basic principles hybridization.

Language: Английский

Self-Tandem Electrocatalytic NO Reduction to NH3 on a W Single-Atom Catalyst DOI
Kai Chen, Jiaxin Wang, Hu Zhang

et al.

Nano Letters, Journal Year: 2023, Volume and Issue: 23(5), P. 1735 - 1742

Published: Feb. 14, 2023

We design single-atom W confined in MoO3-x amorphous nanosheets (W1/MoO3-x) comprising W1-O5 motifs as a highly active and durable NORR catalyst. Theoretical operando spectroscopic investigations reveal the dual functions of to (1) facilitate activation protonation NO molecules (2) promote H2O dissociation while suppressing *H dimerization increase proton supply, eventually resulting self-tandem mechanism W1/MoO3-x greatly accelerate energetics NO-to-NH3 pathway. As result, exhibits highest NH3-Faradaic efficiency 91.2% NH3 yield rate 308.6 μmol h-1 cm-2, surpassing that most previously reported catalysts.

Language: Английский

Citations

96
Urea Electrosynthesis from Nitrate and CO2 on Diatomic Alloys DOI
Kai Chen, Danyang Ma, Ying Zhang

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(30)

Published: June 14, 2024

Abstract Urea electrosynthesis from co–electrolysis of NO 3 − and CO 2 (UENC) offers a promising technology for achieving sustainable efficient urea production. Herein, diatomic alloy catalyst (CuPd 1 Rh –DAA), with mutually isolated Pd atoms alloyed on Cu substrate, is theoretically designed experimentally confirmed to be highly active selective UENC catalyst. Combining theoretical computations operando spectroscopic characterizations reveals the synergistic effect –Cu sites promote via tandem catalysis mechanism, where site triggers early C–N coupling promotes *CO –to–*CO NH steps, while facilitates subsequent protonation step *COOHNH toward formation. Impressively, CuPd –DAA assembled in flow cell presents highest Faradaic efficiency 72.1% yield rate 53.2 mmol h −1 g cat at −0.5 V versus RHE, representing nearly performance among all reported catalysts.

Language: Английский

Citations

92
Ampere-Level Nitrate Electroreduction to Ammonia over Monodispersed Bi-Doped FeS2 DOI
Guike Zhang, Guohui Wang,

Yuying Wan

et al.

ACS Nano, Journal Year: 2023, Volume and Issue: 17(21), P. 21328 - 21336

Published: Oct. 23, 2023

Electrochemical conversion of NO3– into NH3 (NO3RR) holds an enormous prospect to simultaneously yield valuable and alleviate pollution. Herein, we report monodispersed Bi-doped FeS2 (Bi–FeS2) as a highly effective NO3RR catalyst. Atomic coordination characterizations Bi–FeS2 disclose that the isolated Bi dopant coordinates with its adjacent Fe atom create unconventional p–d hybridized Bi–Fe dinuclear sites. Operando spectroscopic measurements combined theoretical calculations sites can synergistically enhance hydrogenation energetics NO3–-to-NH3 pathway, while suppressing competitive hydrogen evolution, leading high selectivity activity. Consequently, specially designed flow cell equipped exhibits rate 83.7 mg h–1 cm–2 near-100% Faradaic efficiency at ampere-level current density 1023.2 mA cm–2, together excellent long-term stability for 100 h electrolysis, ranking almost highest performance among all reported catalysts.

Language: Английский

Citations

91
Controlling the Metal–Ligand Coordination Environment of Manganese Phthalocyanine in 1D–2D Heterostructure for Enhancing Nitrate Reduction to Ammonia DOI
Ashadul Adalder, Sourav Paul,

Narad Barman

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(20), P. 13516 - 13527

Published: Oct. 6, 2023

Eight-electron nitrate reduction (NO3RR) offers a cost-effective and environmentally friendly route of ammonia production wastewater remediation. However, identification reinforcement the metal–ligand interaction responsible for catalytic activity in transition-metal phthalocyanine-based heterostructures still remain unclear due to their complexity. Herein, directed by computation, we present heterostructure approach couple 2D graphene sheets with 1D manganese (II) phthalocyanine produce pyrrolic-N coordinated electron-deficient Mn center that interacts generate vital intermediates NO3RR process. The catalyst system delivers an yield rate 20,316 μg h–1 mgcat–1, faradaic efficiency (FE) 98.3%, electrocatalytic stability 50 h. Mechanistic investigations verified FTIR spectroscopy theoretical calculations identify as active sites MnPc RGO reinforce orbital enhancing charge transfer formation *NOH @ while suppressing competitive hydrogen evolution reaction (HER), resulting high selectivity FE.

Language: Английский

Citations

71
Pd1Cu Single-Atom Alloys for High-Current-Density and Durable NO-to-NH3 Electroreduction DOI
Kai Chen,

Jiaqi Xiang,

Yali Guo

et al.

Nano Letters, Journal Year: 2024, Volume and Issue: 24(2), P. 541 - 548

Published: Jan. 8, 2024

Electrochemical reduction of NO to NH3 (NORR) offers a prospective method for efficient electrosynthesis. Herein, we first design single-atom Pd-alloyed Cu (Pd1Cu) as an and robust NORR catalyst at industrial-level current densities (>0.2 A cm–2). Operando spectroscopic characterizations theoretical computations unveil that Pd1 strongly electronically couples its adjacent two atoms (Pd1Cu2) enhance the activation while promoting NO-to-NH3 protonation energetics suppressing competitive hydrogen evolution. Consequently, flow cell assembled with Pd1Cu exhibits unprecedented yield rate 1341.3 μmol h–1 cm–2 NH3–Faradaic efficiency 85.5% density 210.3 mA cm–2, together excellent long-term durability 200 h electrolysis, representing one highest performances on record.

Language: Английский

Citations

70
Atomic Co─P Catalytic Pair Drives Efficient Electrochemical Nitrate Reduction to Ammonia DOI Creative Commons
Jiaqi Ni,

Jing Yan,

Fuhua Li

et al.

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(28)

Published: March 3, 2024

Abstract Electrochemically reducing nitrate (NO 3 − ), a common water pollutant, to valuable ammonia (NH ) offers green, sustainable, and decentralized route for synthesis. Electrochemical reduction reaction RR) involves two crucial steps: deoxygenation followed by nitrite hydrogenation; in particular, the hydrogenation is rate‐determining step (RDS) NO RR. In this work, an atomically dispersed cobalt‐phosphorus (Co─P) catalytic pair (CP) with strong electronic coupling reported. The Co site Co─P CP effectively activates , while P facilitates dissociation release H + synergistically enhancing thermodynamic kinetic performance of electrochemical ammonia.

Language: Английский

Citations

66
Tandem Electrocatalytic Nitrate Reduction to Ammonia on MBenes DOI
Guike Zhang, Xiaotian Li, Kai Chen

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(13)

Published: Feb. 3, 2023

Abstract We demonstrate the great feasibility of MBenes as a new class tandem catalysts for electrocatalytic nitrate reduction to ammonia (NO 3 RR). As proof concept, FeB 2 is first employed model MBene catalyst NO RR, showing maximum NH ‐Faradaic efficiency 96.8 % with corresponding yield 25.5 mg h −1 cm −2 at −0.6 V vs. RHE. Mechanistic studies reveal that exceptional RR activity arises from catalysis mechanism, is, B sites activate − form intermediates, while Fe dissociate H O and increase *H supply on promote intermediate hydrogenation enhance ‐to‐NH conversion.

Language: Английский

Citations

65
Electrocatalytic nitrate-to-ammonia conversion on CoO/CuO nanoarrays using Zn–nitrate batteries DOI
Shanshan Chen, Gaocan Qi,

Ruilian Yin

et al.

Nanoscale, Journal Year: 2023, Volume and Issue: 15(48), P. 19577 - 19585

Published: Jan. 1, 2023

Zn-NO3- batteries can generate electricity while producing NH3 in an environmentally friendly manner, making them a very promising device. However, the conversion of NO3- to involves proton-assisted 8-electron (8e-) transfer process with high kinetic barrier, requiring high-performance catalysts realize potential applications this technology. Herein, we propose heterostructured CoO/CuO nanoarray electrocatalyst prepared on copper foam (CoO/CuO-NA/CF) that electrocatalytically and efficiently convert at low achieves maximum yield 296.9 μmol h-1 cm-2 Faraday efficiency (FE) 92.9% -0.2 V vs. reversible hydrogen electrode (RHE). Impressively, battery based monolithic CoO/CuO-NA/CF delivers 60.3 cm-2, FENH3 82.0%, power density 4.3 mW cm-2. This study provides paradigm for catalyst preparation energy-efficient production simultaneously generating electrical energy.

Language: Английский

Citations

64
Tandem Electrocatalytic Reduction of Nitrite to Ammonia on Rhodium–Copper Single Atom Alloys DOI

Jiaqi Xiang,

Chaofan Qiang,

Shiyao Shang

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(36)

Published: April 23, 2024

Abstract Electrocatalytic reduction of NO 2 − to NH 3 (NO RR) presents a fascinating approach for simultaneously migrating pollutants and producing valuable . In this study, single‐atom Rh‐alloyed copper (CuRh 1 ) is explored as highly active selective catalyst toward the RR. Combined theoretical calculations in situ FTIR/EPR spectroscopic experiments uncover synergistic effect Rh Cu promote RR energetics CuRh through tandem catalysis pathway, which activates preliminary adsorption hydrogenation → *NO *NOOH *NO), while generated on then transferred substrate promotes rate‐determining step *NHO synthesis. As result, equipped flow cell an unprecedented yield rate 2191.6 µmol h −1 cm −2 ‐Faradaic efficiency 98.9% at high current density 322.5 mA , well long‐term stability 100 electrolysis.

Language: Английский

Citations

60
Electrochemical Co-Production of Ammonia and Biodegradable Polymer Monomer Glycolic Acid via the Co-Electrolysis of Nitrate Wastewater and Waste Plastic DOI

Tianlun Ren,

Zhongyao Duan,

Huizhen Wang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(15), P. 10394 - 10404

Published: July 25, 2023

Electrochemical reformation of nitrate wastewater and poly(ethylene terephthalate) (PET) plastic waste into ammonia (NH3) fine chemicals is a sustainable strategy for resource utilization. Herein, co-production system glycolic acid (GA, degradable polymer monomer) constructed by coupling reduction ethylene glycol (EG, in PET hydrolysate) oxidation. Low-crystalline CoOOH (LC-CoOOH/CF) Pd nanothorns (Pd NTs/NF) grown situ on the metal foam substrates are employed as cathode anode, respectively. The high density amorphous regions LC-CoOOH/CF enables enhanced adsorption provides abundant active sites, ultimately leading to an Faradic efficiency (FE) 97.38 ± 1.0% at −0.25 V vs reversible hydrogen electrode (RHE). Meanwhile, unique nanothorn morphology endows NTs/NF with high-curvature tip, triggering tip effect (TE) promote highly selective oxidation EG GA. Furthermore, two-electrode system, NH3 GA operated low energy consumption (onset voltage: 0.5 V), much lower than traditional electrolysis process (1.4 V). This study method utilization co-produce value-added chemicals.

Language: Английский

Citations

59