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

High-efficiency electrosynthesis of urea over bacterial cellulose regulated Pd–Cu bimetallic catalyst DOI Creative Commons

Shengbo Zhang,

Jing Geng, Zhong Zhao

et al.

EES Catalysis, Journal Year: 2022, Volume and Issue: 1(1), P. 45 - 53

Published: Oct. 28, 2022

PdCu/CBC exhibited a remarkable R urea of 763.8 ± 42.8 μg h −1 mg cat. at −0.50 V ( vs. RHE) and an exceptional FE 69.1 3.8% −0.40 RHE). Taking advantage operando spectroscopy characterization, the C–N coupling mechanism was verified.

Language: Английский

Citations

95
Designing Efficient Nitrate Reduction Electrocatalysts by Identifying and Optimizing Active Sites of Co-Based Spinels DOI
Qi Hu,

Qi Shuai,

Qihua Huo

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(5), P. 2967 - 2976

Published: Dec. 29, 2023

Cobalt-based spinel oxides (i.e., Co

Language: Английский

Citations

94
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

92
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
Electrocatalytic Urea Synthesis with 63.5 % Faradaic Efficiency and 100 % N‐Selectivity via One‐step C−N coupling DOI
Xiaoran Zhang, Xiaorong Zhu,

Shuowen Bo

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(33)

Published: June 20, 2023

Electrocatalytic urea synthesis via coupling N2 and CO2 provides an effective route to mitigate energy crisis close carbon footprint. However, the difficulty on breaking N≡N is main reason that caused low efficiencies for both electrocatalytic NH3 synthesis, which bottleneck restricting their industrial applications. Herein, a new mechanism overcome inert of nitrogen molecule was proposed by elongating instead realize one-step C-N in process production. We constructed Zn-Mn diatomic catalyst with axial chloride coordination, sites display high tolerance CO poisoning Faradaic efficiency can even be increased 63.5 %, highest value has ever been reported. More importantly, negligible bond breakage effectively avoids generation ammonia as intermediates, therefore, N-selectivity co-electrocatalytic system reaches100 % synthesis. The previous cognition electrocatalysts must possess activity broken. Isotope-labelled measurements Operando synchrotron-radiation Fourier transform infrared spectroscopy validate activation N-N triple fixation arise from species adsorbed molecules.

Language: Английский

Citations

83
Copper with an atomic-scale spacing for efficient electrocatalytic co-reduction of carbon dioxide and nitrate to urea DOI
Seokmin Shin, Siraj Sultan,

Zong-Xian Chen

et al.

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(5), P. 2003 - 2013

Published: Jan. 1, 2023

This work presents that Cu with atomic-scale spacings ( d s ) efficiently catalyses the electrochemical co-reduction of CO 2 and NO 3 − to urea. Specifically, near 6 Å (6 Å-Cu) produces urea a high yield rate partial current density.

Language: Английский

Citations

81
C‐Bound or O‐Bound Surface: Which One Boosts Electrocatalytic Urea Synthesis? DOI
Yingying Liu,

Xiaojin Tu,

Xiaoxiao Wei

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(19)

Published: March 9, 2023

Abstract The electrocatalytic C−N coupling from carbon dioxide and nitrate under ambient conditions is kind of sustainable promising alternative method for urea synthesis. To date, the influence catalyst surface properties on molecular adsorption configuration synthesis activity unclear. In this work, we proposed that closely linked with localized charge bimetallic electrocatalysts, it found a negatively charged induces C‐bound path boosts yield rate can reach 13.1 mmol g −1 h Cu 97 3 ‐C, which about 13 times positively 30 70 ‐C counterpart O‐bound surface. This conclusion also applies to Cu−Bi Cu−Sn systems. modification shifts state, leads sharp decline in performance. We demonstrated more favorable than one boost

Language: Английский

Citations

79
Emerging p-Block-Element-Based Electrocatalysts for Sustainable Nitrogen Conversion DOI
Chade Lv, Jiawei Liu, Carmen Lee

et al.

ACS Nano, Journal Year: 2022, Volume and Issue: 16(10), P. 15512 - 15527

Published: Oct. 14, 2022

Artificial nitrogen conversion reactions, such as the production of ammonia via dinitrogen or nitrate reduction and synthesis organonitrogen compounds C–N coupling, play a pivotal role in modern life. As alternatives to traditional industrial processes that are energy- carbon-emission-intensive, electrocatalytic reactions under mild conditions have attracted significant research interests. However, electrosynthesis process still suffers from low product yield Faradaic efficiency, which highlight importance developing efficient catalysts. In contrast transition-metal-based catalysts been widely studied, p-block-element-based recently shown promising performance because their intriguing physiochemical properties intrinsically poor hydrogen adsorption ability. this Perspective, we summarize latest breakthroughs development electrocatalysts toward applications, including N2 urea using nitrogen-containing feedstocks carbon dioxide. The catalyst design strategies underlying reaction mechanisms discussed. Finally, major challenges opportunities future directions also proposed.

Language: Английский

Citations

78
Carbon‐Anchored Molybdenum Oxide Nanoclusters as Efficient Catalysts for the Electrosynthesis of Ammonia and Urea DOI

Mengmiao Sun,

Guanzheng Wu,

Jiadi Jiang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(19)

Published: March 13, 2023

Abstract The electrochemical NO 3 − reduction and its coupling with CO 2 can provide novel clean routes to synthesize NH urea, respectively. However, their practical application is still impeded by the lack of efficient catalysts desirable Faradaic efficiency (FE) yield rate. Herein, we report synthesis molybdenum oxide nanoclusters anchored on carbon black (MoO x /C) as electrocatalyst. It affords an outstanding FE 98.14 % rate 91.63 mg h −1 cat. in reduction. Besides, highest 27.7 a maximum urea 1431.5 μg toward also achieved. formation electron‐rich MoO highly unsaturated metal sites /C heterostructure beneficial for enhanced catalytic performance. Studies mechanism reveal that stabilization *NO *CO NOOH intermediates are critical synthesis,

Language: Английский

Citations

76
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