Boosting Electrochemical Urea Synthesis via Constructing Ordered Pd–Zn Active Pair

Weiliang Zhou; Chao Feng; Xuan Li; Xingxing Jiang; Lingyan Jing; Shuai Qi; Qihua Huo; Miaoyuan Lv; Xinbao Chen; Tianchi Huang; Jingwen Zhao; Na Meng; Hengpan Yang; Qi Hu; Chuanxin He

doi:10.1007/s40820-024-01462-w

[1] C. Chen, X. Zhu, X. Wen, Y. Zhou, L. Zhou et al., Coupling N2 and CO2 in H2O to synthesize urea under ambient conditions. Nat. Chem. 12, 717–724 (2020).

[2] J. Li, Y. Zhang, K. Kuruvinashetti, N. Kornienko, Construction of C–N bonds from small-molecule precursors through heterogeneous electrocatalysis. Nat. Rev. Chem. 6, 303–319 (2022).

[3] X. Peng, L. Zeng, D. Wang, Z. Liu, Y. Li et al., Electrochemical C–N coupling of CO2 and nitrogenous small molecules for the electrosynthesis of organonitrogen compounds. Chem. Soc. Rev. 52, 2193–2237 (2023).

[4] A.J. Martín, T. Shinagawa, J. Pérez-Ramírez, Electrocatalytic reduction of nitrogen: from Haber-Bosch to ammonia artificial leaf. Chem 5, 263–283 (2019).

[5] Y. Zhao, Y. Ding, W. Li, C. Liu, Y. Li et al., Efficient urea electrosynthesis from carbon dioxide and nitrate via alternating Cu-W bimetallic C–N coupling sites. Nat. Commun. 14, 4491 (2023).

[6] Y. Wang, S. Xia, J. Zhang, Z. Li, R. Cai et al., Spatial management of CO diffusion on tandem electrode promotes NH2 intermediate formation for efficient urea electrosynthesis. ACS Energy Lett. 8, 3373–3380 (2023).

[7] C. Lv, L. Zhong, H. Liu, Z. Fang, C. Yan et al., Selective electrocatalytic synthesis of urea with nitrate and carbon dioxide. Nat. Sustain. 4, 868–876 (2021).

[8] M. Yuan, J. Chen, H. Zhang, Q. Li, L. Zhou et al., Host–guest molecular interaction promoted urea electrosynthesis over a precisely designed conductive metal–organic framework. Energy Environ. Sci. 15, 2084–2095 (2022).

[9] D. Wang, C. Chen, S. Wang, Defect engineering for advanced electrocatalytic conversion of nitrogen-containing molecules. Sci. China Chem. 66, 1052–1072 (2023).

[10] X. Zhang, X. Zhu, S. Bo, C. Chen, K. Cheng et al., Electrocatalytic urea synthesis with 63.5% faradaic efficiency and 100% N-Selectivity via one-step C–N coupling. Angew. Chem. Int. Ed. 62, e202305447 (2023).

[11] Y. Gao, J. Wang, Y. Yang, J. Wang, C. Zhang et al., Engineering spin states of isolated copper species in a metal-organic framework improves urea electrosynthesis. Nano-Micro Lett. 15, 158 (2023).

[12] J. Leverett, T. Tran-Phu, J.A. Yuwono, P. Kumar, C. Kim et al., Tuning the coordination structure of Cu–N–C single atom catalysts for simultaneous electrochemical reduction of CO2 and NO3– to urea. Adv. Energy Mater. 12, 2201500 (2022).

[13] X. Wei, X. Wen, Y. Liu, C. Chen, C. Xie et al., Oxygen vacancy-mediated selective C–N coupling toward electrocatalytic urea synthesis. J. Am. Chem. Soc. 144, 11530–11535 (2022).

[14] Q. Zhao, X. Lu, Y. Wang, S. Zhu, Y. Liu et al., Sustainable and high-rate electrosynthesis of nitrogen fertilizer. Angew. Chem. Int. Ed. 62, e20230712310 (2023).

[15] T. Hou, J. Ding, H. Zhang, S. Chen, Q. Liu et al., FeNi3 nanoparticles for electrocatalytic synthesis of urea from carbon dioxide and nitrate. Mater. Chem. Front. 7, 4952–4960 (2023).

[16] M. Yuan, J. Chen, Y. Bai, Z. Liu, J. Zhang et al., Unveiling electrochemical urea synthesis by co-activation of CO2 and N2 with Mott-Schottky heterostructure catalysts. Angew. Chem. Int. Ed. 60, 10910–10918 (2021).

[17] Y. Liu, X. Tu, X. Wei, D. Wang, X. Zhang et al., C-bound or O-bound surface: which one boosts electrocatalytic urea synthesis? Angew. Chem. Int. Ed. 62, e202300387 (2023).

[18] C. Lv, C. Lee, L. Zhong, H. Liu, J. Liu et al., A defect engineered electrocatalyst that promotes high-efficiency urea synthesis under ambient conditions. Nano Lett. 16, 8213–8222 (2022).

[19] D. Wu, R. Feng, C. Xu, P.-F. Sui, J. Zhang et al., Regulating the electron localization of metallic bismuth for boosting CO2 electroreduction. Nano-Micro Lett. 14, 38 (2021).

[20] B. Rhimi, M. Zhou, Z. Yan, X. Cai, Z. Jiang, Cu-based materials for enhanced C2+ product selectivity in photo-/ electro-catalytic CO2 reduction: challenges and prospects. Nano-Micro Lett. 16, 64 (2024).

[21] X.-Y. Ji, K. Sun, Z.-K. Liu, X. Liu, W. Dong et al., Identification of dynamic active sites among Cu species derived from MOFs@CuPc for electrocatalytic nitrate reduction reaction to ammonia. Nano-Micro Lett. 15, 110 (2023).

[22] C.S. Gerke, Y. Xu, Y. Yang, G.D. Foley, B. Zhang et al., Electrochemical C–N bond formation within boron imidazolate cages featuring single copper sites. J. Am. Chem. Soc. 145, 26144–26151 (2023).

[23] S. Chen, G. Qi, R. Yin, Q. Liu, L. Feng et al., Electrocatalytic nitrate-to-ammonia conversion on CoO/CuO nanoarrays using Zn-nitrate batteries. Nanoscale 15, 19577–19585 (2023).

[24] R. He, N. Xu, I.M.U. Hasan, L. Peng, L. Li et al., Advances in electrolyzer design and development for electrochemical CO2 reduction. EcoMat. 5, e12346 (2023).

[25] S. Zhang, J. Geng, Z. Zhao, M. Jin, W. Li et al., High-efficiency electrosynthesis of urea over bacterial cellulose regulated Pd–Cu bimetallic catalyst. EES. Catal. 1, 45–53 (2023).

[26] N. Meng, X. Ma, C. Wang, Y. Wang, R. Yang et al., Oxide-derived core-shell Cu@Zn nanowires for urea electrosynthesis from carbon dioxide and nitrate in water. Nano lett. 16, 9095–9104 (2022).

[27] H. Wang, Y. Jiang, S. Li, F. Gou, X. Liu et al., Realizing efficient C–N coupling via electrochemical co-reduction of CO2 and NO3- on AuPd nanoalloy to form urea: key C–N coupling intermediates. Appl. Catal. B Environ. 318, 121819 (2022).

[28] H. Wan, X. Wang, L. Tan, M. Filippi, P. Strasser et al., Electrochemical synthesis of urea: co-reduction of nitric oxide and carbon monoxide. ACS Catal. 13, 1926–1933 (2023).

[29] X. Liu, Y. Jiao, Y. Zheng, M. Jaroniec, S.-Z. Qiao, Mechanism of C–N bonds formation in electrocatalytic urea production revealed by ab initio molecular dynamics simulation. Nat. Commun. 13, 5471 (2022).

[30] X. Zhang, X. Zhu, S. Bo, C. Chen, M. Qiu et al., Identifying and tailoring C–N coupling site for efficient urea synthesis over diatomic Fe–Ni catalyst. Nat. Commun. 13, 5337 (2022).

[31] S. Zhang, Y. Zha, Y. Ye, K. Li, Y. Lin et al., Oxygen-coordinated single Mn sites for efficient electrocatalytic nitrate reduction to ammonia. Nano-Micro Lett. 16, 9 (2023).

[32] X. Rao, J. Yan, K. Yokoyama, X. Shao, C. Inoue et al., A porous Co3O4-carbon paper electrode enabling nearly 100% electrocatalytic reduction of nitrate to ammonia. Mater. Rep. Energy 3, 100216 (2023).

[33] B. Xu, I.M.U. Hasan, L. Peng, J. Liu, N. Xu et al., Anion-regulation engineering toward Cu/In/MOF bimetallic electrocatalysts for selective electrochemical reduction of CO2 to CO/formate. Mater Rep Energy. 2, 100139 (2022).

[34] L. Peng, C. Chen, R. He, N. Xu, J. Qiao et al., Tin-doped bismuth dendrites for highly efficient electrocatalytic reduction of CO2 by using bipolar membrane in ultrathin liquid reactor. EcoMat 4, e12260 (2022).

[35] L. Peng, Y. Zhang, R. He, N. Xu, J. Qiao, Research advances in electrocatalysts, electrolytes, reactors and membranes for the electrocatalytic carbon dioxide reduction reaction. Acta Phys. Chim. Sin. (2023).

[36] J. Yan, Y. Guan, B. Marchetti, Y. Liu, F. Ning et al., Bi-Eu bimetallic catalysts enabling ultrastable electroreduction of CO2 with a ∼ 100% formate Faradaic efficiency. Chem. Eng. J. 467, 143531 (2023).

[37] M. Yang, G. Meng, H. Li, T. Wei, Q. Liu et al., Bifunctional bimetallic oxide nanowires for high-efficiency electrosynthesis of 2, 5-furandicarboxylic acid and ammonia. J. Colloid Interface Sci. 652, 155–163 (2023).

[38] Y. Ji, Z. Chen, R. Wei, C. Yang, Y. Wang et al., Selective CO-to-acetate electroreduction via intermediate adsorption tuning on ordered Cu–Pd sites. Nat. Catal. 5, 251–258 (2022).

[39] J. Geng, S. Ji, M. Jin, C. Zhang, M. Xu et al., Ambient electrosynthesis of urea with nitrate and carbon dioxide over iron-based dual-sites. Angew. Chem. Int. Ed. 62, e202210958 (2023).

[40] Y. Li, Y. Li, H. Sun, L. Gao, X. Jin et al., Current status and perspectives of dual-atom catalysts towards sustainable energy utilization. Nano-Micro Lett. 16, 139 (2024).

[41] C.-L. Yang, L.-N. Wang, P. Yin, J. Liu, M.-X. Chen et al., Sulfur-anchoring synthesis of platinum intermetallic nanoparticle catalysts for fuel cells. Science 374, 459–464 (2021).

[42] Y. Yang, W. Xiao, X. Feng, Y. Xiong, M. Gong et al., Golden palladium zinc ordered intermetallics as oxygen reduction electrocatalysts. Nano Lett. 13, 5968–5974 (2019).

[43] W. Xiao, M.A.L. Cordeiro, G. Gao, A. Zheng, J. Wang et al., Atomic rearrangement from disordered to ordered Pd–Fe nanocatalysts with trace amount of Pt decoration for efficient electrocatalysis. Nano Energy 50, 70–78 (2018).

[44] Q. Gao, B. Yao, H.S. Pillai, W. Zang, X. Han et al., Synthesis of core/shell nanocrystals with ordered intermetallic single-atom alloy layers for nitrate electroreduction to ammonia. Nat. Synth. 2, 624–634 (2023).

[45] J. Lim, C.-Y. Liu, J. Park, Y.-H. Liu, T.P. Senftle et al., Structure sensitivity of Pd facets for enhanced electrochemical nitrate reduction to ammonia. ACS Catal. 11, 7568–7577 (2021).

[46] W. Luo, J. Zhang, M. Li, A. Züttel, Boosting CO production in electrocatalytic CO2 reduction on highly porous Zn catalysts. ACS Catal. 9, 3783–3791 (2019).

[47] J. Rosen, G.S. Hutchings, Q. Lu, R.V. Forest, A. Moore et al., Electrodeposited Zn dendrites with enhanced CO selectivity for electrocatalytic CO2 reduction. ACS Catal. 5, 4586–4591 (2015).

[48] Y. Guo, R. Zhang, S. Zhang, Y. Zhao, Q. Yang et al., Pd doping-weakened intermediate adsorption to promote electrocatalytic nitrate reduction on TiO2 nanoarrays for ammonia production and energy supply with zinc–nitrate batteries. Energy Environ. Sci. 14, 3938–3944 (2021).

[49] M. Hu, S. Zhao, S. Liu, C. Chen, W. Chen et al., MOF-confined sub-2 nm atomically ordered intermetallic PdZn nanoparticles as high-performance catalysts for selective hydrogenation of acetylene. Adv. Mater. 30, e1801878 (2018).

[50] X. Tu, X. Zhu, S. Bo, X. Zhang, R. Miao et al., A universal approach for sustainable urea synthesis via intermediate assembly at the electrode/electrolyte interface. Angew. Chem. Int. Ed. 63, e202317087 (2024).

[51] Y. Huang, Y. Wang, Y. Liu, A. Ma, J. Gui et al., Unveiling the quantification minefield in electrocatalytic urea synthesis. Chem. Eng. J. 453, 139836 (2023).

[52] Q. Hu, K. Gao, X. Wang, H. Zheng, J. Cao et al., Subnanometric Ru clusters with upshifted D band center improve performance for alkaline hydrogen evolution reaction. Nat. Commun. 13, 3958 (2022).

[53] D. Zhang, Y. Xue, X. Zheng, C. Zhang, Y. Li, Multi-heterointerfaces for selective and efficient urea production. Natl. Sci. Rev. 10, nwac209 (2022).

[54] S. Zhu, B. Jiang, W.-B. Cai, M. Shao, Direct observation on reaction intermediates and the role of bicarbonate anions in CO2 electrochemical reduction reaction on Cu surfaces. J. Am. Chem. Soc. 139, 15664–15667 (2017).

[55] Y. Huang, R. Yang, C. Wang, N. Meng, Y. Shi et al., Direct electrosynthesis of urea from carbon dioxide and nitric oxide. ACS Energy Lett. 7, 284–291 (2022).

[56] N. Meng, Y. Huang, Y. Liu, Y. Yu, B. Zhang, Electrosynthesis of urea from nitrite and CO2 over oxygen vacancy-rich ZnO porous nanosheets. Cell Rep. Phys. Sci. 2, 100378 (2021).

[57] M. Sun, G. Wu, J. Jiang, Y. Yang, A. Du et al., Carbon-anchored molybdenum oxide nanoclusters as efficient catalysts for the electrosynthesis of ammonia and urea. Angew. Chem. Int. Ed. 62, e202301 957 (2023).

[58] M. Yuan, H. Zhang, Y. Xu, R. Liu, R. Wang et al., Artificial frustrated Lewis pairs facilitating the electrochemical N2 and CO2 conversion to urea. Chem Catal. 2, 309–320 (2022).

[59] X. Liu, P.V. Kumar, Q. Chen, L. Zhao, F. Ye et al., Carbon nanotubes with fluorine-rich surface as metal-free electrocatalyst for effective synthesis of urea from nitrate and CO2. Appl. Catal. B Environ. 316, 121618 (2022).

[60] M. Yuan, J. Chen, Y. Bai, Z. Liu, J. Zhang et al., Electrochemical C–N coupling with perovskite hybrids toward efficient urea synthesis. Chem. Sci. 12, 6048–6058 (2021).

[61] Q. Hu, Y. Qin, X. Wang, Z. Wang, X. Huang et al., Reaction intermediate-mediated electrocatalyst synthesis favors specified facet and defect exposure for efficient nitrate–ammonia conversion. Energy Environ. Sci. 14, 4989–4997 (2021).

[62] Z. Chen, T. Wang, B. Liu, D. Cheng, C. Hu et al., Grain-boundary-rich copper for efficient solar-driven electrochemical CO2 reduction to ethylene and ethanol. J. Am. Chem. Soc. 142, 6878–6883 (2020).

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