Boosting Electrocatalytic Urea Production via Promoting Asymmetric C–N Coupling

Qiu, Mengyi; Zhu, Xiaoyan; Bo, Shuowen; Cheng, Kai; He, Nihan; Gu, Kaizhi; Song, Dezhong; Chen, Chen; Wei, Xiaoxiao; Wang, Dongdong; Liu, Yingying; Li, Shuang; Tu, Xiaojin; Li, Yafei; Liu, Qinghua; Li, Conggang; Wang, Shuangyin

doi:10.31635/ccschem.023.202202408

Cited by 33 publications

(27 citation statements)

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“…Therefore, we selected five typical urea synthesis electrocatalysts that have been reported, as research objects to investigate the cation effect on their urea synthesis performances. Cuprous oxide with multi‐hole morphology (m‐Cu 2 O), single‐atom copper anchored on cerium dioxide nanorods (Cu‐CeO 2 ), oxygen‐vacancy enriched CeO 2 nanorods (Vo‐CeO 2 ), copper‐indium alloy decorated on carbon support (Cu 97 In 3 ‐C), and diatomic Fe−Ni decorated carbon spheres (B‐FeNi‐DASC) were successfully fabricated according to the reports [9,10a,b,c,23a] . These structures are shown in Figure S41 and S42.…”

Section: Resultsmentioning

confidence: 99%

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

Tu,

Zhu,

et al. 2023

Angew Chem Int Ed

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Electrocatalytic C−N coupling process is indeed a sustainable alternative for direct urea synthesis and co‐upgrading of carbon dioxide and nitrate wastes. However, the main challenge lies in the unactivated C−N coupling process. Here, we proposed a strategy of intermediate assembly with alkali metal cations to activate C−N coupling at the electrode/electrolyte interface. Urea synthesis activity follows the trend of Li+<Na+<Cs+<K+. In the presence of K+, a world‐record performance was achieved with a urea yield rate of 212.8±10.6 mmol h−1 g−1 on a single‐atom Co supported TiO2 catalyst at −0.80 V versus reversible hydrogen electrode. Theoretical calculations and operando synchrotron‐radiation Fourier transform infrared measurements revealed that the energy barriers of C−N coupling were significantly decreased via K+ mediated intermediate assembly. By applying this strategy to various catalysts, we demonstrate that intermediate assembly at the electrode/electrolyte interface is a universal approach to boost sustainable urea synthesis.

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Section: Resultsmentioning

confidence: 99%

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

Tu,

Zhu,

et al. 2023

Angew Chem Int Ed

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“…38 The C−N coupling between *CO and *NO is thermodynamically promoted on the electrochemically constructed Cu 0 −Cu + pair sites with a low energy of +0.36 eV, whereas a free-energy change of +1.35 eV is needed on Cu 0 sites, which is conducive to the boosted urea production. 39 3.2.2. Reversible Reconstruction.…”

Section: Irreversible Reconstructionmentioning

confidence: 99%

“…On the contrary, the preservation of the Cu + component is observed on m-Cu 2 O, which can be attributed to the unique multihole structure of m-Cu 2 O (Figure a) . The C–N coupling between *CO and *NO is thermodynamically promoted on the electrochemically constructed Cu 0 –Cu + pair sites with a low energy of +0.36 eV, whereas a free-energy change of +1.35 eV is needed on Cu 0 sites, which is conducive to the boosted urea production …”

Section: Electrocatalytic Urea Synthesis From Nitrate and Co2mentioning

confidence: 99%

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Electrocatalytic Urea Synthesis via C–N Coupling from CO₂ and Nitrogenous Species

Wang,

Chen,

Chen

et al. 2023

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS: Industrial urea synthesis consists of the Haber− Bosch process to produce ammonia and the subsequent Bosch− Meiser process to produce urea. Compared to the conventional energy-intensive urea synthetic protocol, electrocatalytic C−N coupling from CO 2 and nitrogenous species emerges as a promising alternative to construct a C−N bond under ambient conditions and to realize the direct synthesis of high-value urea products via skipping the intermediate step of ammonia production. The main challenges for electrocatalytic C−N coupling lie in the intrinsic inertness of molecules and the competition with parallel side reactions. In this Account, we give an overview of our recent progress toward electrocatalytic C−N coupling from CO 2 and nitrogenous species toward urea synthesis.To begin, we present the direct transformation of dinitrogen (N 2 ) to the C−N bond by coelectrolysis, verifying the feasibility of direct urea synthesis from N 2 and CO 2 under ambient conditions. In contrast to the highly endothermic step of proton coupling in conventional N 2 reduction, the N 2 activation and construction of the C−N bond arise from a thermodynamic spontaneous reaction between CO (derived from CO 2 reduction) and *N�N* (the asterisks represent the adsorption sites), and the crucial *NCON* species mediates the interconversion of N 2 , CO 2 , and urea. Based on theoretical guidance, the effect of N 2 adsorption configurations on C−N coupling is investigated on the model catalysts with defined active site structure, revealing that the side-on adsorption rather than the end-on one favors C−N coupling and urea synthesis. Electrocatalytic C−N coupling of CO 2 and nitrate (NO 3 − ) is also an effective pathway to achieve direct urea synthesis. We summarize our progress in the C−N coupling of CO 2 and NO 3 − , from the aspects of modulating intermediate species adsorption and reaction paths, monitoring irreversible and reversible reconstruction of active sites, and precisely constructing active sites to match activities and to boost the electrocatalytic urea synthesis. In each case, in situ electrochemical technologies and density functional theory (DFT) calculations are carried out to unveil the microscopic mechanisms for the promotion of C−N coupling and the enhancement of urea synthesis activity. In the last section, we put forward the limitations, challenges, and perspectives in these two coupling systems for further development of electrocatalytic urea synthesis.

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“…[11,12] Currently, the strategy of electrocatalytic synthesis of urea is coupling the electrocatalytic CO 2 reduction reaction (CO 2 RR) with electrocatalytic nitrogen-containing molecule (such as N 2 , NO 2 À , or NO 3 À ) reduction reaction, which results in the in-situ formation of CÀ N bonds between carbon and nitrogen intermediates and ultimately the desired products. [13][14][15][16][17][18][19] The CO 2 RR has become a widely researched technology that can effectively break the C=O double bond of CO 2 or HCO 3 À to generate CO and other high-value-added products. [20][21][22][23] Notable progresses have been made to address the issues of immediate synthesizing CÀ N bonds after C=O double-bond breakage during the synthesis of urea.…”

Section: Introductionmentioning

confidence: 99%

A New Method for Urea Synthesis under Environmental Conditions Based on Nucleophilic Addition Reaction During Electrochemical CO₂ Reduction

Li,

Zhang,

Yang

et al. 2023

ChemCatChem

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Urea (H2NCONH2) is a commercially indispensable chemical as a fertilizer and starting material for the manufacture of many other products. Currently, commercial urea can be prepared with an energy‐consuming process by combining liquid ammonia (NH3) and liquid carbon dioxide (CO2) under high‐temperature and high‐pressure conditions. An alternative approach for synthesis of urea may involve electrochemical synthesis reactions that occur under aqueous and ambient conditions. Here, we propose synthesis of urea via nucleophilic addition reaction during an electrochemical CO2 reduction process in NH4HCO3‐containing electrolytes. The urea formation at a rate of 0.11 mmol g−1 h−1 was achieved on a polycrystalline Au electrode (area: 1 cm2) at a potential of −1.4 V (vs. saturated calomel electrode). Furthermore, the detailed investigations including in‐situ spectroscopic analysis and isotopic labeling characterization reveal the capability of producing urea could be mainly attributed to a spontaneous reaction between the NH3 molecule and the CO2⋅− intermediate. This study promotes the exploration of electrochemical synthesis of high‐value‐added products.

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Boosting Electrocatalytic Urea Production via Promoting Asymmetric C–N Coupling

Cited by 33 publications

References 0 publications

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

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

Electrocatalytic Urea Synthesis via C–N Coupling from CO₂ and Nitrogenous Species

A New Method for Urea Synthesis under Environmental Conditions Based on Nucleophilic Addition Reaction During Electrochemical CO₂ Reduction

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Boosting Electrocatalytic Urea Production via Promoting Asymmetric C–N Coupling

Cited by 33 publications

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

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

Electrocatalytic Urea Synthesis via C–N Coupling from CO2 and Nitrogenous Species

A New Method for Urea Synthesis under Environmental Conditions Based on Nucleophilic Addition Reaction During Electrochemical CO2 Reduction

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Product

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Electrocatalytic Urea Synthesis via C–N Coupling from CO₂ and Nitrogenous Species

A New Method for Urea Synthesis under Environmental Conditions Based on Nucleophilic Addition Reaction During Electrochemical CO₂ Reduction