Activity and Selectivity Roadmap for C–N Electro-Coupling on MXenes DOI
Yiran Jiao, Haobo Li, Yan Jiao

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(28), P. 15572 - 15580

Published: July 6, 2023

Electrochemical coupling between carbon and nitrogen species to generate high-value C-N products, including urea, presents significant economic environmental potentials for addressing the energy crisis. However, this electrocatalysis process still suffers from limited mechanism understanding due complex reaction networks, which restricts development of electrocatalysts beyond trial-and-error practices. In work, we aim improve mechanism. This goal was achieved by constructing activity selectivity landscape on 54 MXene surfaces density functional theory (DFT) calculations. Our results show that step is largely determined *CO adsorption strength (Ead-CO), while relies more co-adsorption *N (Ead-CO Ead-N). Based these findings, propose an ideal catalyst should satisfy moderate stable adsorption. Through machine learning-based approach, data-driven formulas describing relationship Ead-CO Ead-N with atomic physical chemistry features were further identified. identified formula, 162 materials screened without time-consuming DFT Several potential catalysts predicted good performance, such as Ta2W2C3. The candidate then verified study has incorporated learning methods first time provide efficient high-throughput screening method selective electrocatalysts, could be extended a wider range electrocatalytic reactions facilitate green chemical production.

Language: Английский

Identifying and tailoring C–N coupling site for efficient urea synthesis over diatomic Fe–Ni catalyst DOI Creative Commons
Xiaoran Zhang, Xiaorong Zhu,

Shuowen Bo

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Sept. 10, 2022

Electrocatalytic urea synthesis emerged as the promising alternative of Haber-Bosch process and industrial synthetic protocol. Here, we report that a diatomic catalyst with bonded Fe-Ni pairs can significantly improve efficiency electrochemical synthesis. Compared isolated single-atom catalysts, act efficient sites for coordinated adsorption activation multiple reactants, enhancing crucial C-N coupling thermodynamically kinetically. The performance up to an order magnitude higher than those electrocatalysts, high yield rate 20.2 mmol h-1 g-1 corresponding Faradaic 17.8% has been successfully achieved. A total about 100% formation value-added urea, CO, NH3 was realized. This work presents insight into synergistic catalysis towards sustainable via identifying tailoring atomic site configurations.

Language: Английский

Citations

291
Electrochemical Nitrate Reduction: Ammonia Synthesis and the Beyond DOI
Yuecheng Xiong, Yunhao Wang, Jingwen Zhou

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(17)

Published: June 9, 2023

Natural nitrogen cycle has been severely disrupted by anthropogenic activities. The overuse of N-containing fertilizers induces the increase nitrate level in surface and ground waters, substantial emission oxides causes heavy air pollution. Nitrogen gas, as main component air, used for mass ammonia production over a century, providing enough nutrition agriculture to support world population increase. In last decade, researchers have made great efforts develop processes under ambient conditions combat intensive energy consumption high carbon associated with Haber-Bosch process. Among different techniques, electrochemical reduction reaction (NO

Language: Английский

Citations

214
Dynamic Reconstitution Between Copper Single Atoms and Clusters for Electrocatalytic Urea Synthesis DOI
Xiaoxiao Wei, Yingying Liu, Xiaorong Zhu

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(18)

Published: Feb. 6, 2023

Electrocatalytic CN coupling between carbon dioxide and nitrate has emerged to meet the comprehensive demands of footprint closing, valorization waste, sustainable manufacture urea. However, identification catalytic active sites design efficient electrocatalysts remain a challenge. Herein, synthesis urea catalyzed by copper single atoms decorated on CeO2 support (denoted as Cu1 -CeO2 ) is reported. The catalyst exhibits an average yield rate 52.84 mmol h-1 gcat.-1 at -1.6 V versus reversible hydrogen electrode. Operando X-ray absorption spectra demonstrate reconstitution (Cu1 clusters (Cu4 during electrolysis. These electrochemically reconstituted Cu4 are real for electrocatalytic synthesis. Favorable reactions formation validated using operando synchrotron-radiation Fourier transform infrared spectroscopy theoretical calculations. Dynamic transformations single-atom configurations occur when applied potential switched open-circuit potential, endowing with superior structural electrochemical stabilities.

Language: Английский

Citations

203
Ambient Electrosynthesis of Urea with Nitrate and Carbon Dioxide over Iron‐Based Dual‐Sites DOI Creative Commons
Jing Geng, Sihan Ji, Jin Meng

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(6)

Published: Oct. 20, 2022

The development of efficient electrocatalysts to generate key *NH2 and *CO intermediates is crucial for ambient urea electrosynthesis with nitrate (NO3- ) carbon dioxide (CO2 ). Here we report a liquid-phase laser irradiation method fabricate symbiotic graphitic encapsulated amorphous iron oxide nanoparticles on nanotubes (Fe(a)@C-Fe3 O4 /CNTs). Fe(a)@C-Fe3 /CNTs exhibits superior electrocatalytic activity toward synthesis using NO3- CO2 , affording yield 1341.3±112.6 μg h-1 mgcat-1 faradic efficiency 16.5±6.1 % at conditions. Both experimental theoretical results indicate that the formed Fe(a)@C Fe3 CNTs provide dual active sites adsorption activation thus generating lower energy barriers formation. This work would be helpful design high-efficiency dual-site synthesis.

Language: Английский

Citations

190
Electrochemical C–N coupling of CO2and nitrogenous small molecules for the electrosynthesis of organonitrogen compounds DOI
Xianyun Peng, Libin Zeng, Dashuai Wang

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(6), P. 2193 - 2237

Published: Jan. 1, 2023

Electrochemical C–N coupling reaction by renewable electricity for the electrosynthesis of organonitrogen compounds with abundant CO 2 and nitrogenous small molecules as carbon nitrogen sources, respectively, is a promising sustainable synthetic strategy.

Language: Английский

Citations

160
Interfacial polarization in metal-organic framework reconstructed Cu/Pd/CuOx multi-phase heterostructures for electrocatalytic nitrate reduction to ammonia DOI

Tianlun Ren,

Zuan Yu,

Hongjie Yu

et al.

Applied Catalysis B Environment and Energy, Journal Year: 2022, Volume and Issue: 318, P. 121805 - 121805

Published: July 28, 2022

Language: Английский

Citations

154
Efficient urea electrosynthesis from carbon dioxide and nitrate via alternating Cu–W bimetallic C–N coupling sites DOI Creative Commons
Yilong Zhao,

Yunxuan Ding,

Wenlong Li

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: July 26, 2023

Electrocatalytic urea synthesis is an emerging alternative technology to the traditional energy-intensive industrial protocol. Novel strategies are urgently needed promote electrocatalytic C-N coupling process and inhibit side reactions. Here, we report a CuWO4 catalyst with native bimetallic sites that achieves high production rate (98.5 ± 3.2 μg h-1 mg-1cat) for co-reduction of CO2 NO3- Faradaic efficiency (70.1 2.4%) at -0.2 V versus reversible hydrogen electrode. Mechanistic studies demonstrated combination stable intermediates *NO2 *CO increases probability reduces potential barrier, resulting in low overpotential. This study provides new perspective on achieving efficient electrosynthesis by stabilizing key reaction intermediates, which may guide design other electrochemical systems high-value bond-containing chemicals.

Language: Английский

Citations

154
Review on Electrocatalytic Coreduction of Carbon Dioxide and Nitrogenous Species for Urea Synthesis DOI
Minghang Jiang, Mengfei Zhu, Mengjun Wang

et al.

ACS Nano, Journal Year: 2023, Volume and Issue: 17(4), P. 3209 - 3224

Published: Feb. 14, 2023

The electrochemical coreduction of carbon dioxide (CO2) and nitrogenous species (such as NO3–, NO2–, N2, NO) for urea synthesis under ambient conditions provides a promising solution to realize carbon/nitrogen neutrality mitigate environmental pollution. Although an increasing number studies have made some breakthroughs in synthesis, the unsatisfactory Faradaic efficiency, low yield rate, ambiguous C–N coupling reaction mechanisms remain major obstacles its large-scale applications. In this review, we present recent progress on based CO2 aqueous solutions conditions, providing useful guidance discussion rational design metal nanocatalyst, understanding mechanism, existing challenges prospects synthesis. We hope that review can stimulate more insights inspiration toward development electrocatalytic technology.

Language: Английский

Citations

147
Turning Waste into Wealth: Sustainable Production of High-Value-Added Chemicals from Catalytic Coupling of Carbon Dioxide and Nitrogenous Small Molecules DOI
Sisi Liu, Mengfan Wang,

Qiyang Cheng

et al.

ACS Nano, Journal Year: 2022, Volume and Issue: 16(11), P. 17911 - 17930

Published: Oct. 31, 2022

Carbon neutrality is one of the central topics not only scientific community but also majority human society. The development highly efficient carbon dioxide (CO2) capture and utilization (CCU) techniques expected to stimulate routes concepts go beyond fossil fuels provide more economic benefits for a carbon-neutral economy. While various single-carbon (C1) multi-carbon (C2+) products have been selectively produced date, scope CCU can be further expanded valuable chemicals simple species by integration nitrogenous reactants into CO2 reduction. In this Review, research progress toward sustainable production high-value-added (urea, methylamine, ethylamine, formamide, acetamide, glycine) from catalytic coupling small molecules (NH3, N2, NO3–, NO2–) highlighted. C–N bond formation key mechanistic step in N-integrated reduction, so we focus on possible pathways starting reduction processes as well attributes that enable coupling. We propose directions prospects field, aiming inspire future investigations achieve comprehensive improvement performance product systems.

Language: Английский

Citations

106
Single‐Atom or Dual‐Atom in TiO2Nanosheet: Which is the Better Choice for Electrocatalytic Urea Synthesis? DOI
Lu Pan, Jingnan Wang, Fei Lu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(8)

Published: Nov. 30, 2022

As rising star materials, single-atom and dual-atom catalysts have been widely reported in the electro-catalysis area. To answer key question: catalysts, which is better for electrocatalytic urea synthesis? we design two types of via a vacancy-anchorage strategy: Pd1 -TiO2 Cu1 nanosheets. An ultrahigh activity 166.67 molurea molPd-1 h1 with corresponding 22.54 % Faradaic efficiency at -0.5 V vs. reversible hydrogen electrode (RHE) achieved over , much higher than that . Various characterization including an situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) theoretical calculations demonstrate site more favorable producing urea, experiences C-N coupling pathway lower energy barrier compared

Language: Английский

Citations

99