A Universal Approach for Sustainable Urea Synthesis via Intermediate Assembly at the Electrode/Electrolyte Interface DOI

Xiaojin Tu,

Xiaorong Zhu,

Shuowen Bo

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(3)

Published: Dec. 7, 2023

Abstract Electrocatalytic C−N coupling process is indeed a sustainable alternative for direct urea synthesis and co‐upgrading of carbon dioxide nitrate wastes. However, the main challenge lies in unactivated process. Here, we proposed strategy intermediate assembly with alkali metal cations to activate at electrode/electrolyte interface. Urea activity follows trend Li + <Na <Cs <K . In presence K , world‐record performance was achieved yield rate 212.8±10.6 mmol h −1 g on single‐atom Co supported TiO 2 catalyst −0.80 V versus reversible hydrogen electrode. Theoretical calculations operando synchrotron‐radiation Fourier transform infrared measurements revealed that energy barriers were significantly decreased via mediated assembly. By applying this various catalysts, demonstrate interface universal approach boost synthesis.

Language: Английский

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
Kinetically matched C–N coupling toward efficient urea electrosynthesis enabled on copper single-atom alloy DOI Creative Commons

Mengqiu Xu,

Fangfang Wu, Ye Zhang

et al.

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

Published: Nov. 1, 2023

Chemical C-N coupling from CO2 and NO3-, driven by renewable electricity, toward urea synthesis is an appealing alternative for Bosch-Meiser production. However, the unmatched kinetics in NO3- reduction reactions complexity of C- N-species involved co-reduction render challenge coupling, leading to low yield rate Faradaic efficiency. Here, we report a single-atom copper-alloyed Pd catalyst (Pd4Cu1) that can achieve highly efficient electrosynthesis. The regulated matched steering Cu doping level Pd4Cu1/FeNi(OH)2 interface. Charge-polarized Pdδ--Cuδ+ dual-sites stabilize key *CO *NH2 intermediates promote coupling. synthesized Pd4Cu1-FeNi(OH)2 composite achieves 436.9 mmol gcat.-1 h-1 efficiency 66.4%, as well long cycling stability 1000 h. In-situ spectroscopic results theoretical calculation reveal atomically dispersed lattice promotes deep *NH2, Pd-Cu lower energy barrier pivotal between *CO.

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
Review on strategies for improving the added value and expanding the scope of CO2 electroreduction products DOI
Minghang Jiang, Huaizhu Wang, Mengfei Zhu

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(10), P. 5149 - 5189

Published: Jan. 1, 2024

This review summarizes promising strategies including the design of catalysts and construction coupled electrocatalytic reaction systems, aimed at achieving selective production various products from CO 2 electroreduction.

Language: Английский

Citations

75
Pulsed co-electrolysis of carbon dioxide and nitrate for sustainable urea synthesis DOI
Qi Hu,

Weiliang Zhou,

Qi Shuai

et al.

Nature Sustainability, Journal Year: 2024, Volume and Issue: 7(4), P. 442 - 451

Published: Feb. 26, 2024

Language: Английский

Citations

69
Efficient Electrochemical Co‐Reduction of Carbon Dioxide and Nitrate to Urea with High Faradaic Efficiency on Cobalt‐Based Dual‐Sites DOI

Xiaoya Fan,

Chaozhen Liu,

Xun He

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(25)

Published: April 2, 2024

Abstract Renewable electricity‐powered nitrate/carbon dioxide co‐reduction reaction toward urea production paves an attractive alternative to industrial processes and offers a clean on‐site approach closing the global nitrogen cycle. However, its large‐scale implantation is severely impeded by challenging C–N coupling requires electrocatalysts with high activity/selectivity. Here, cobalt‐nanoparticles anchored on carbon nanosheet (Co NPs@C) are proposed as catalyst electrode boost yield Faradaic efficiency (FE) electrosynthesis enhanced coupling. Such Co NPs@C renders superb urea‐producing activity FE reaching 54.3% of 2217.5 µg h −1 mg cat. , much superior NPs C counterparts, meanwhile shows strong stability. The affords rich catalytically active sites, fast reactant diffusion, sufficient catalytic surfaces‐electrolyte contacts favored charge ion transfer efficiencies. theoretical calculations reveal that high‐rate formation *CO *NH 2 intermediates crucial for facilitating synthesis.

Language: Английский

Citations

47
Palladium-Copper bimetallic catalysts for electroreduction of CO2 and nitrogenous species DOI

Fengchen Zhou,

Junjun Zhang, Yifan Zhang

et al.

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 509, P. 215802 - 215802

Published: March 26, 2024

Language: Английский

Citations

46
Potential and electric double-layer effect in electrocatalytic urea synthesis DOI Creative Commons
Qian Wu, Chencheng Dai, Fanxu Meng

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 6, 2024

Abstract Electrochemical synthesis is a promising way for sustainable urea production, yet the exact mechanism has not been fully revealed. Herein, we explore of electrochemical coupling nitrite and carbon dioxide on Cu surfaces towards basis constant-potential method combined with an implicit solvent model. The working electrode potential, which normally overlooked, found influential both reaction activity. further computational study pathways reveals that *CO-NH *NH-CO-NH as key intermediates. In addition, through analysis turnover frequencies under various potentials, pressures, temperatures within microkinetic model, demonstrate activity increases temperature, Cu(100) shows highest efficiency among all three surfaces. electric double-layer capacitance also plays role in synthesis. Based these findings, propose two essential strategies to promote electrodes: increasing surface ratio elevating temperature.

Language: Английский

Citations

44
Electrocatalytic synthesis of C–N coupling compounds from CO2 and nitrogenous species DOI Creative Commons
Zheng Zhang, Danyang Li, Yunchuan Tu

et al.

SusMat, Journal Year: 2024, Volume and Issue: 4(2)

Published: March 12, 2024

Abstract The electrocatalytic synthesis of C–N coupling compounds from CO 2 and nitrogenous species not only offers an effective avenue to achieve carbon neutrality reduce environmental pollution, but also establishes a route synthesize valuable chemicals, such as urea, amide, amine. This innovative approach expands the application range product categories beyond simple carbonaceous in reduction, which is becoming rapidly advancing field. review summarizes research progress urea synthesis, using N , NO − 3 species, explores emerging trends electrosynthesis amide amine nitrogen species. Additionally, future opportunities this field are highlighted, including amino acids other containing bonds, anodic reactions water oxidation, catalytic mechanism corresponding reactions. critical captures insights aimed at accelerating development electrochemical reactions, confirming superiority method over traditional techniques.

Language: Английский

Citations

42
Dynamic Reconstruction of Two‐Dimensional Defective Bi Nanosheets for Efficient Electrocatalytic Urea Synthesis DOI
Yan Wang,

Shuai Xia,

Rui Cai

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(16)

Published: Feb. 22, 2024

Abstract Abstract:Catalyst surface dynamics drive the generation of active species for electrocatalytic reactions. Yet, understanding dominant site formation and reaction mechanisms is limited. In this study, we thoroughly investigate dynamic reconstruction two‐dimensional defective Bi nanosheets from exfoliated 2 Se 3 under electrochemical CO nitrate (NO − ) reduction conditions. The ultrathin obtained by NaBH 4 ‐assisted cryo‐mediated liquid‐phase exfoliation are more easily reduced reconstructed to with high‐density grain boundaries (GBs; GB‐rich Bi). catalyst affords a remarkable yield rate 4.6 mmol h −1 mg cat. Faradaic efficiency 32 % urea production at −0.40 V vs. RHE. Notably, 8.2 times higher than those low‐GB bulk catalysts, respectively. Theoretical analysis demonstrates that GB sites significantly reduce *CO *NH intermediate energy C−N coupling barrier, enabling selective electrosynthesis on catalyst. This work will trigger further research into structure‐activity interplay in processes using situ techniques.

Language: Английский

Citations

38