Urea stands as a vital industrial material with notable applications in energy and agriculture. However, the Haber-Bosch synthesis process, characterized by high energy consumption and emissions, poses significant challenges. Electrocatalytic C-N coupling offers a promising alternative but is constrained by the scarcity of efficient catalysts. In this work, Cr4/Ti2CO2 is emerged as an optimal candidate with a remarkable low overpotential of 0.29 V and a kinetic energy barrier of 0.40 eV. A comprehensive investigation into the influence of electrochemical potential on C-N coupling revealed that the d orbitals of active sites in different chemical environments within the clusters led to distinct hybridization mechanisms with the π* orbitals of adsorbed N2, which is defined as Mixed Cooperative Orbital Hybridization Mechanism. Specifically, the synergistic activation of the N≡N bond by the d(x2-y2) of top atom and the d-band center of bottom atoms determined the critical step C-N coupling energy barrier under electrode potential regulation. Additionally, Cr4/Ti2CO2 demonstrated optimal catalytic activity at a potential of 0.40 V versus the reversible hydrogen electrode (RHE) under acidic conditions (pH 0). These findings not only rationalize the design of an efficient electrocatalyst for urea synthesis but also elucidates the electronic mechanisms underlying potential-dependent catalytic activity.

Center for Integrated Computational Materials Engineering Beihang University Beijing 100191 P R China

Department of Condensed Matter Physics Faculty of Mathematics and Physics Charles University Ke Karlovu 3 Prague 2 121 16 Czech Republic

Department of Earth and Environmental Science and Department of Chemistry University of Pennsylvania Philadelphia Pennsylvania 19104 USA

IT4Innovations VSB Technical University of Ostrava 17 listopadu 2172 15 Ostrava CZ 70800 Czech Republic

School of Materials Science and Engineering Beihang University Beijing 100191 P R China

Zobrazit více v PubMed

G.‐L. Yang, C.‐T. Hsieh, Y.‐S. Ho, T.‐C. Kuo, Y. Kwon, Q. Lu, M.‐J. Cheng, ACS Catal. 2022, 12, 11494.

W.‐Y. Lin, Z.‐X. Chen, H. Xiong, H.‐C. Li, Y.‐S. Ho, C.‐T. Hsieh, Q. Lu, M.‐J. Cheng, ACS Catal. 2023, 13, 11697.

J. Cao, F. Zhao, C. Li, Q. Zhao, L. Gao, T. Ma, H. Xu, X. Ren, A. Liu, Small 2024, 20, 2403412.

C. S. Gerke, M. Klenk, P. Zapol, V. S. Thoi, ACS Catal. 2023, 13, 14540.

M. Jiang, M. Zhu, M. Wang, Y. He, X. Luo, C. Wu, L. Zhang, Z. Jin, ACS Nano 2023, 17, 3209.

R. Ge, J. Huo, P. Lu, Y. Dou, Z. Bai, W. Li, H. Liu, B. Fei, S. Dou, Adv. Mater. 2024, 36, 2412031.

J. Liu, S. C. Smith, Y. Gu, L. Kou, Adv. Funct. Mater. 2023, 33, 2305894.

C. Liu, H. Tong, P. Wang, R. Huang, P. Huang, G. Zhou, L. Liu, Appl. Catal., B 2023, 336, 122917.

P. Li, Y. Wei, X. Yang, Y. Zhu, Z. Zhang, X. Yang, Y. Shen, M. Wang, ACS Catal. 2024, 14, 7967.

A. Kumar, X. Liu, J. Lee, B. Debnath, A. R. Jadhav, X. Shao, V. Q. Bui, Y. Hwang, Y. Liu, M. G. Kim, H. Lee, Energy Environ. Sci. 2021, 14, 6494.

Z. Xiong, Y. Xiao, C. Shen, Chem. Mater. 2022, 34, 9402.

S. Shin, S. Sultan, Z.‐X. Chen, H. Lee, H. Choi, T.‐U. Wi, C. Park, T. Kim, C. Lee, J. Jeong, H. Shin, T.‐H. Kim, H. Ju, H. C. Yoon, H.‐K. Song, H.‐W. Lee, M.‐J. Cheng, Y. Kwon, Energy Environ. Sci. 2003, 16, 2023.

X. Wei, X. Wen, Y. Liu, C. Chen, C. Xie, D. Wang, M. Qiu, N. He, P. Zhou, W. Chen, J. Cheng, H. Lin, J. Jia, X.‐Z. Fu, S. Wang, J. Am. Chem. Soc. 2022, 144, 11530.

M. Jouny, J. J. Lv, T. Cheng, B. H. Ko, J. J. Zhu, W. A. Goddard 3rd, F. Jiao, Nat. Chem. 2019, 11, 846.

C. Chen, X. Zhu, X. Wen, Y. Zhou, L. Zhou, H. Li, L. Tao, Q. Li, S. Du, T. Liu, D. Yan, C. Xie, Y. Zou, Y. Wang, R. Chen, J. Huo, Y. Li, J. Cheng, H. Su, X. Zhao, W. Cheng, Q. Liu, H. Lin, J. Luo, J. Chen, M. Dong, K. Cheng, C. Li, S. Wang, Nat. Chem. 2020, 12, 717.

Y. Zhang, L. Lu, T. Zhao, J. Zhao, Q. Cai, Z. Chen, J. Mater. Chem. A 2024, 12, 16704.

Z. Li, M. Xu, J. Wang, Y. Zhang, W. Liu, X. Gu, Z. K. Han, W. Ye, G. Li, Small 2024, 20, 2400036.

W. Yang, L. Xiao, W. Dai, S. Mou, F. Dong, Adv. Energy Mater. 2024, 14, 2303806.

M. Yuan, J. Chen, Y. Bai, Z. Liu, J. Zhang, T. Zhao, Q. Wang, S. Li, H. He, G. Zhang, Angew. Chem., Int. Ed. 2021, 60, 10910.

B. Govindan, K. Annamalai, A. Kumar, S. Palanisamy, M. Abu Haija, F. Banat, ACS Sustainable Chem. Eng. 2024, 12, 8174.

X. Song, X. Ma, T. Chen, L. Xu, J. Feng, L. Wu, S. Jia, L. Zhang, X. Tan, R. Wang, C. Chen, J. Ma, Q. Zhu, X. Kang, X. Sun, B. Han, J. Am. Chem. Soc. 2024, 146, 25813.

W. E. Kaden, T. Wu, W. A. Kunkel, S. L. Anderson, Science 2009, 326, 826.

Y. Du, H. Sheng, D. Astruc, M. Zhu, Chem. Rev. 2020, 120, 526.

X. Li, S. Mitchell, Y. Fang, J. Li, J. Perez‐Ramirez, J. Lu, Nat. Rev. Chem. 2023, 7, 754.

X. Wei, Y. Liu, X. Zhu, S. Bo, L. Xiao, C. Chen, T. T. T. Nga, Y. He, M. Qiu, C. Xie, D. Wang, Q. Liu, F. Dong, C. L. Dong, X. Z. Fu, S. Wang, Adv. Mater. 2023, 35, 2300020.

L. J. Liu, Z. Y. Wang, Z. Y. Wang, R. Wang, S. Q. Zang, T. C. W. Mak, Angew. Chem., Int. Ed. 2022, 134, 202205626.

J. Zhang, Y. Zhang, Z. Qin, Z. Li, Z. Tong, Z. Zhao, J. A. Gascón, G. Li, Angew. Chem., Int. Ed. 2024, 137, 202420993.

J. C. Liu, X. L. Ma, Y. Li, Y. G. Wang, H. Xiao, J. Li, Nat. Commun. 2018, 9, 1610.

Y. Wu, W. Wei, R. Yu, L. Xia, X. Hong, J. Zhu, J. Li, L. Lv, W. Chen, Y. Zhao, L. Zhou, L. Mai, Adv. Funct. Mater. 2022, 32, 2110910.

W. Peng, M. Luo, X. Xu, K. Jiang, M. Peng, D. Chen, T. S. Chan, Y. Tan, Adv. Energy Mater. 2020, 10, 2001364.

Y. Wu, L. Wang, T. Bo, Z. Chai, J. K. Gibson, W. Shi, Adv. Funct. Mater. 2023, 33, 2214375.

G. Kresse, J. Furthmuller, Phys. Rev. B 1996, 54, 11169.

P. E. Blochl, Phys. Rev. B 1994, 50, 17953.

J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 1996, 77, 3865.

J. P. Perdew, Y. Wang, Phys. Rev. B 1992, 45, 13244.

S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys. 2010, 132, 154104.

Y. Gu, B. Wei, D. Legut, Z. Fu, S. Du, H. Zhang, J. S. Francisco, R. Zhang, Adv. Funct. Mater. 2021, 31, 2104285.

K. Mathew, R. Sundararaman, K. Letchworth‐Weaver, T. A. Arias, R. G. Hennig, J. Chem. Phys. 2014, 140, 084106.

Z. Duan, G. Henkelman, ACS Catal. 2020, 10, 12148.

D. Jiao, D. Zhang, D. Wang, J. Fan, X. Ma, J. Zhao, W. Zheng, X. Cui, Nano Res. 2023, 16, 11511.

A. Hagopian, M.‐L. Doublet, J.‐S. Filhol, T. Binninger, J. Chem. Theory Comput. 2022, 18, 1883.

J.‐C. Liu, F. Luo, J. Li, J. Am. Chem. Soc. 2023, 145, 25264.

Z. Duan, G. Henkelman, ACS Catal. 2019, 9, 5567.

G. Henkelman, B. P. Uberuaga, H. Jónsson, J. Chem. Phys. 2000, 113, 9901.

R. Yu, Z. Liu, D. Legut, J. Sun, Q. Zhang, J. S. Francisco, R. Zhang, ACS Catal. 2024, 14, 10568.

Z. C. Pan, Z. R. Liu, T. F. Xu, D. Legut, R. F. Zhang, Comput. Mater. Sci. 2024, 233, 112707.

A. Vojvodic, J. K. Nørskov, F. Abild‐Pedersen, Top. Catal. 2013, 57, 25.

Z. R. Liu, B. N. Yao, R. F. Zhang, Comput. Mater. Sci. 2022, 210, 111027.

K. Momma, F. Izumi, J. Appl. Crystallogr. 2008, 41, 653.

S. Maintz, V. L. Deringer, A. L. Tchougreeff, R. Dronskowski, J. Comput. Chem. 2016, 37, 1030.

X. Zhang, Y. Zhang, C. Cheng, Z. Yang, K. Hermansson, Nanoscale 2020, 12, 12497.

C. Cheng, X. Zhang, Z. Yang, Z. Zhou, ACS Appl. Mater. Interfaces 2018, 10, 32903.

J. Engel, S. Francis, A. Roldan, Phys. Chem. Chem. Phys. 2019, 21, 19011.

Y. Shi, B. Wei, D. Legut, S. Du, J. S. Francisco, R. Zhang, Adv. Funct. Mater. 2022, 32, 2210218.

M. Yuan, J. Chen, Y. Xu, R. Liu, T. Zhao, J. Zhang, Z. Ren, Z. Liu, C. Streb, H. He, C. Yang, S. Zhang, G. Zhang, Energy Environ. Sci. 2021, 14, 6605.

U. Mondal, P. Ghosh, Catal. Today 2021, 370, 93.

H. Tao, Y. Li, X. Cai, H. Zhou, Y. Li, W. Lin, S. Huang, K. Ding, W. Chen, Y. Zhang, J. Phys. Chem. C 2019, 123, 24118.

B. Yang, C. Liu, A. Halder, E. C. Tyo, A. B. F. Martinson, S. Seifert, P. Zapol, L. A. Curtiss, S. Vajda, J. Phys. Chem. C 2017, 121, 10406.

X. Zhu, X. Zhou, Y. Jing, Y. Li, Nat. Commun. 2021, 12, 4080.

X. Guo, J. Gu, S. Lin, S. Zhang, Z. Chen, S. Huang, J. Am. Chem. Soc. 2020, 142, 5709.

D.‐K. Seo, G. Papoian, R. Hoffmann, Int. J. Quantum Chem. 1999, 77, 408.

Z. Fu, B. Yang, R. Wu, Phys. Rev. Lett. 2020, 125, 156001.

C. He, C.‐H. Lee, L. Meng, H.‐Y. T. Chen, Z. Li, J. Am. Chem. Soc. 2024, 146, 12395.

S. Ringe, N. G. Hörmann, H. Oberhofer, K. Reuter, Chem. Rev. 2021, 122, 10777.

J. Zhang, H. Zhang, T. Wu, Q. Wang, D. van der Spoel, J. Chem. Theory Comput. 2017, 13, 1034.

S.‐J. Qian, H. Cao, J.‐W. Chen, J.‐C. Chen, Y.‐G. Wang, J. Li, ACS Catal. 2022, 12, 11530.

H. Xiao, T. Cheng, W. A. Goddard, R. Sundararaman, J. Am. Chem. Soc. 2016, 138, 483.