Modulating Hydrogen Adsorption by Unconventional p–d Orbital Hybridization over Porous High‐entropy Alloy Metallene for Efficient Electrosynthesis of Nylon‐6 Precursor DOI

Youwei Sheng,

Jiangwei Xie,

Ruidong Yang

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(44)

Published: July 12, 2024

Abstract Renewable electricity driven electrosynthesis of cyclohexanone oxime (C 6 H 11 NO) from 10 O) and nitrogen oxide (NO x ) is a promising alternative to traditional environment‐unfriendly industrial technologies for green synthesis C NO. Precisely controlling the reaction pathway O/NO ‐involved electrochemical reductive coupling crucial selectively producing NO, which yet still challenging. Herein, we report porous high‐entropy alloy PdCuAgBiIn metallene (HEA‐PdCuAgBiInene) boost NO O nitrite, achieving high Faradaic efficiency (47.6 %) almost 100 % yield under ambient conditions. In situ Fourier transform infrared spectroscopy theoretical calculations demonstrate that unconventional orbital hybridization between d‐block metals p‐block could regulate local electronic structure active sites induce electron localization electron‐rich Pd sites, tunes hydrogen supply, facilitates generation enrichment key intermediates NH 2 OH* O*, efficiently promotes their C−N produce

Language: Английский

Electrocatalytic selective synthesis and tandem utilization of hydroxylamine DOI Creative Commons
Yuxuan Lu, Hengquan Yang

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

Language: Английский

Citations

0
Theoretical study on the synthesis of glycine via electrocatalytic reduction over tandem catalysts based on two-dimensional carbon-rich conjugated metalloporphyrin frameworks DOI

Xuan Niu,

Ling Guo

New Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

FeY-Cr(Zr)-BPor COF catalysts not only maintain the advantages of bimetallic but also utilize role B atoms to fully activate NO and CO 2 , thereby exhibiting good catalytic activity with a very low limiting potential (−0.20 V).

Language: Английский

Citations

0
Theoretical Insights into the Selectivity of Single-Atom Fe–N–C Catalysts for Electrochemical NOx Reduction DOI

Yao Tan,

Junwei Fu, Tao Luo

et al.

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

Published: Feb. 2, 2025

Single-atom Fe-N-C catalysts have attracted significant attention in the NOx reduction reaction (NOxRR). However, origin of their selectivity NOxRR remains unclear, impeding further advancements application. Herein, we investigate potential-driven competitive mechanism for NH3 and NH2OH production over single-atom pyridinic-FeN4 pyrrolic-FeN4 sites using constant-potential density functional theory calculations. The is linked to switching Fe 3d orbitals as they interact with intermediates. between determined by applied potentials. predominantly generates at higher potentials (-0.6 -1.2 V, vs SHE), while favored lower (0.6 -0.6 V). shows a similar potential-dependent product distribution, crossover potential -1.0 V. selectivity-determining intermediates (SDIs) are *NH2OH *NH2 + *OH. governed interacting SDIs, from dumbbell-shaped 3dz2 four-leaf clover-like 3dxz, 3dyz, 3dx2-y2, which plays crucial role controlling distribution based on These findings offer new insights into NOxRR.

Language: Английский

Citations

0
Unlocking Efficient Electrosynthesis of α‐Amino Acids: Adsorption Geometry Modulation and Electronic Structure Reconstruction in the Ag/Cu Bimetallic System DOI Open Access
Yujie Shi, Xiaowen Sun, Baokun Zhang

et al.

Small, Journal Year: 2025, Volume and Issue: 21(11)

Published: Feb. 5, 2025

Abstract Electrosynthesis of α‐amino acids from α‐keto is a promising strategy but faces challenges such as high reduction potential and limited efficiency due to sluggish reaction kinetics competitive side reactions. Here, this study presents bimetallic Ag/Cu nanowires (NWs) catalyst that effectively addresses these issues, demonstrating an exceptionally low onset‐potential −0.18 V versus RHE for alanine electrosynthesis achieving remarkable yield 690 µmol h −1 cm −2 . The reaches 94.71% conversion within 2.5 yields gram‐scale powder over ten cycles. Theoretical calculations reveal Ag incorporation exerts additional weak interactions with intermediates modulates their adsorption geometries. Simultaneously, electron transfer between Cu reconstructs the catalyst's electronic structure. These modifications enhance activation intermediates, significantly lowering energy barrier potential‐determining step. Additionally, presence suppresses hydrogen evolution reaction, thus improving selectivity production. This NWs also exhibits broad applicability synthesizing various acids. novel enhancing by modulating properties intermediate behaviors, providing valuable theoretical insights technical support sustainable chemical

Language: Английский

Citations

0
Interfacial Asymmetrically Coordinated Zn−MOF for High‐Efficiency Electrosynthetic Oxime DOI Open Access
Jiawei Kang, Peisen Liao,

Runan Xiang

et al.

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 21, 2025

Abstract Oximes are important intermediates for various chemicals synthesis such as pharmaceuticals, among which one vital precursor producing neurological disease, antimicrobial and anticancer agents is piperidone oxime (PDO). Compared with conventional thermocatalytic method, it's more attractive to synthesize PDO via green electrocatalytic technology especially utilizing waste nitrogen oxides gas source. However, there great challenges in catalyst design high‐efficiency electrosynthetic due the low electron transport rate multiple competing reactions. Herein, we propose an interfacial coordination strategy based on metal–organic frameworks (MOF) electrocatalyst first time promote electrosynthesis, by building Zn−O bridges between graphite felt (GF) zeolitic imidazolate framework (ZIF‐7/CGF). Specially, ZIF‐7/CGF delivers a Faraday efficiency (FE) of 75.9 % yield up 73.1 1‐methyl‐4‐piperidone oxime, far superior without (a FE 10.7 10.3 %). In‐depth mechanism study shows that introducing can transfer induce Zn sites transforming into distorted tetrahedron (Zn‐N 3 O) mode, benefits adsorption conversion. The developed presents wide universalities towards oximes electrosynthesis adapts other MOF materials (ZIF‐8, ZIF‐4). This work provides new insights organic upgrading cycle through rational surficial coordinated electrocatalysts.

Language: Английский

Citations

0
Interfacial Asymmetrically Coordinated Zn−MOF for High‐Efficiency Electrosynthetic Oxime DOI Open Access
Jiawei Kang, Peisen Liao,

Runan Xiang

et al.

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 21, 2025

Abstract Oximes are important intermediates for various chemicals synthesis such as pharmaceuticals, among which one vital precursor producing neurological disease, antimicrobial and anticancer agents is piperidone oxime (PDO). Compared with conventional thermocatalytic method, it's more attractive to synthesize PDO via green electrocatalytic technology especially utilizing waste nitrogen oxides gas source. However, there great challenges in catalyst design high‐efficiency electrosynthetic due the low electron transport rate multiple competing reactions. Herein, we propose an interfacial coordination strategy based on metal–organic frameworks (MOF) electrocatalyst first time promote electrosynthesis, by building Zn−O bridges between graphite felt (GF) zeolitic imidazolate framework (ZIF‐7/CGF). Specially, ZIF‐7/CGF delivers a Faraday efficiency (FE) of 75.9 % yield up 73.1 1‐methyl‐4‐piperidone oxime, far superior without (a FE 10.7 10.3 %). In‐depth mechanism study shows that introducing can transfer induce Zn sites transforming into distorted tetrahedron (Zn‐N 3 O) mode, benefits adsorption conversion. The developed presents wide universalities towards oximes electrosynthesis adapts other MOF materials (ZIF‐8, ZIF‐4). This work provides new insights organic upgrading cycle through rational surficial coordinated electrocatalysts.

Language: Английский

Citations

0
Single-atom catalysts for electrocatalytic conversion of biomass-derived small molecules DOI
Yulu Yang, Shengkai Li, Wenjie Wu

et al.

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 534, P. 216576 - 216576

Published: March 6, 2025

Language: Английский

Citations

0
Understanding the Selectivity Differences of NO Electroreduction on Ag and Au Electrodes DOI

Lin Li,

Dong Luan,

Jun Long

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 3447 - 3453

Published: March 28, 2025

Although noble metals Ag and Au have similar chemical reactivities, their catalytic selectivity for NO electroreduction is significantly different. Namely, hydroxylamine often considerably produced on while not observed the electrode. In this study, first-principles calculations electric field controlling constant potential (EFC-CP) method are adopted to unveil underlying reasons. We first reveal a distinct NO* adsorption configuration, vertical inclined Au, leading different reduction pathways NOH* HNO*, respectively. Via complete electrochemical barrier detailed kinetic analysis, we find difference between mainly induced by strength of NH2OH*. On Ag, obtained NH2OH* prefers desorb produce hydroxylamine, bonded strongly favors further ammonia. The study advances our understanding factors regulating product selectivity, providing crucial insights designing catalysts toward production.

Language: Английский

Citations

0
Lattice Hydrogen Involved Electrocatalytic Nitrate Reduction to Hydroxylamine DOI

Chengying Guo,

Minghao Guo,

Yuhan Zhang

et al.

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

Published: April 18, 2025

Electrocatalytic nitrate reduction to hydroxylamine (ENRH) provides a sustainable strategy for NH2OH synthesis under ambient conditions. At present, active hydrogen (*H) derived from water dissociation has been widely used as H-source hydrogenation, bringing big challenge ENRH. On the one hand, insufficient *H would lead accumulation of nitrite. other sufficient with high ability induce over-hydrogenation ammonia. To overcome this challenge, herein, we propose utilize lattice (Hlat) an appropriate We design and construct Cu-MnO2Hx electrocatalyst, in which Cu-triggered Jahn-Teller distortion [MnO6] octahedron significantly increases number Hlat. The Faradaic efficiency yield are 91.1% 396.6 mmol gcat.-1 h-1 over Cu-MnO2Hx, outperforming most reported catalysts. combined results isotopic tracking experiments theoretical calculations prove enrichment buffer functions Hlat, can provide abundant nitrate's selective hydroxylamine.

Language: Английский

Citations

0
Efficient electrochemical coupling of nitrate and biomass-derived acetone to acetoxime at a high current density over a Zn/Cu hexagonal nanosheet catalyst DOI
Jiang Shao, Yifei Zhang,

Sheng-Zhi Xue

et al.

Inorganic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(16), P. 5286 - 5298

Published: Jan. 1, 2024

Efficient electrosynthesis of acetoxime from nitrate and acetone at a high current density over novel Zn/Cu hexagonal nanosheet electrocatalyst.

Language: Английский

Citations

3