Single-atom catalysts (SACs) have aroused great attention due to their high atom efficiency and unprecedented catalytic properties. A remaining challenge is to anchor the single atoms individually on support materials via strong interactions. Herein, single atom Co sites have been developed on functionalized graphene by taking advantage of the strong interaction between Co2+ ions and the nitrile group of cyanographene. The potential of the material, which is named G(CN)Co, as a SAC is demonstrated using the electrocatalytic hydrazine oxidation reaction (HzOR). The material exhibits excellent catalytic activity for HzOR, driving the reaction with low overpotential and high current density while remaining stable during long reaction times. Thus, this material can be a promising alternative to conventional noble metal-based catalysts that are currently widely used in HzOR-based fuel cells. Density functional theory calculations of the reaction mechanism over the material reveal that the Co(II) sites on G(CN)Co can efficiently interact with hydrazine molecules and promote the NH bond-dissociation steps involved in the HzOR.

Davidson School of Chemical Engineering Purdue University 480 Stadium Mall Drive West Lafayette IN 47906 USA

Department of Chemical and Biochemical Engineering Rutgers The State University of New Jersey 98 Brett Road Piscataway NJ 08854 USA

Department of Chemistry and Chemical Biology Rutgers The State University of New Jersey 610 Taylor Road Piscataway NJ 08854 USA

Department of Industrial and Engineering Chemistry Institute of Chemical Technology Marathwada Campus Jalna Mumbai 431203 India

Nanotechnology Centre CEET VŠB Technical University of Ostrava 17 Listopadu 2172 15 Ostrava Poruba 708 00 Czech Republic

Regional Centre of Advanced Technologies and Materials Czech Advanced Technology and Research Institute Palacký University Olomouc 779 00 Czech Republic

Regional Centre of Advanced Technologies and Materials Palacký University Olomouc Šlechtitelů 27 Olomouc 783 71 Czech Republic

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T. Zhang, T. Asefa, Adv. Mater. 2019, 31, 1804394.

T. Zhang, J. Low, K. Koh, J. Yu, T. Asefa, ACS Sustainable Chem. Eng. 2018, 6, 531.

J. Sanabria-Chinchilla, K. Asazawa, T. Sakamoto, K. Yamada, H. Tanaka, P. Strasser, J. Am. Chem. Soc. 2011, 133, 5425.

A. Wang, J. Li, T. Zhang, Nat. Rev. Chem. 2018, 2, 65.

X. Li, X. Yang, Y. Huang, T. Zhang, B. Liu, Adv. Mater. 2019, 31, 1902031.

B. Singh, V. Sharma, R. P. Gaikwad, P. Fornasiero, R. Zbořil, M. B. Gawande, Small 2020, 2006473, https://doi.org/10.1002/smll.202006473.

X. F. Yang, A. Wang, B. Qiao, J. Li, J. Liu, T. Zhang, Acc. Chem. Res. 2013, 46, 1740.

M. B. Gawande, P. Fornasiero, R. Zbořil, ACS Catal. 2020, 10, 2231.

A. Bakandritsos, R. G. Kadam, P. Kumar, G. Zoppellaro, M. Medved, J. Tuček, T. Montini, O. Tomanec, P. Andrýsková, B. Drahoš, R. S. Varma, M. Otyepka, M. B. Gawande, P. Fornasiero, R. Zbořil, Adv. Mater. 2019, 31, 1900323.

H. Fei, J. Dong, D. Chen, T. Hu, X. Duan, I. Shakir, Y. Huang, X. Duan, Chem. Soc. Rev. 2019, 48, 5207.

Y. Wang, J. Mao, X. Meng, L. Yu, D. Deng, X. Bao, Chem. Rev. 2019, 119, 1806.

C. Zhang, J. Sha, H. Fei, M. Liu, S. Yazdi, J. Zhang, Q. Zhong, X. Zou, N. Zhao, H. Yu, Z. Jiang, E. Ringe, B. I. Yakobson, J. Dong, D. Chen, J. M. Tour, ACS Nano 2017, 11, 6930.

X. Zhang, J. Guo, P. Guan, C. Liu, H. Huang, F. Xue, X. Dong, S. J. Pennycook, M. F. Chisholm, Nat. Commun. 2013, 4, 1924.

K. C. Kwon, J. M. Suh, R. S. Varma, M. Shokouhimehr, H. W. Jang, Small Methods 2019, 3, 1800492.

J. Guo, J. Huo, Y. Liu, W. Wu, Y. Wang, M. Wu, H. Liu, G. Wang, Small Methods 2019, 3, 1900159.

Y. Cheng, S. Zhao, B. Johannessen, J. P. Veder, M. Saunders, M. R. Rowles, M. Cheng, C. Liu, M. F. Chisholm, R. De Marco, H. M. Cheng, S. Z. Yang, S. P. Jiang, Adv. Mater. 2018, 30, 1706287.

Y. Zhu, W. Peng, Y. Li, G. Zhang, F. Zhang, X. Fan, Small Methods 2019, 3, 1800438.

W. H. Lai, Z. Miao, Y. X. Wang, J. Z. Wang, S. L. Chou, Adv. Energy Mater. 2019, 9, 1900722.

M. D. Hossain, Z. Liu, M. Zhuang, X. Yan, G. L. Xu, C. A. Gadre, A. Tyagi, I. H. Abidi, C. J. Sun, H. Wong, A. Guda, Y. Hao, X. Pan, K. Amine, Z. Luo, Adv. Energy Mater. 2019, 9, 1803689.

Y. N. Chen, X. Zhang, Z. Zhou, Small Methods 2019, 3, 1900050.

R. R. Amirov, J. Shayimova, Z. Nasirova, A. Solodov, A. M. Dimiev, Phys. Chem. Chem. Phys. 2018, 20, 2320.

V. Georgakilas, M. Otyepka, A. B. Bourlinos, V. Chandra, N. Kim, K. C. Kemp, P. Hobza, R. Zbořil, K. S. Kim, Chem. Rev. 2012, 112, 6156.

K. Jiang, S. Siahrostami, T. Zheng, Y. Hu, S. Hwang, E. Stavitski, Y. Peng, J. Dynes, M. Gangisetty, D. Su, K. Attenkofer, H. Wang, Energy Environ. Sci. 2018, 11, 893.

S. Zhou, L. Shang, Y. Zhao, R. Shi, G. I. N. Waterhouse, Y.-C. Huang, L. Zheng, T. Zhang, Adv. Mater. 2019, 31, 1900509.

Z. Du, X. Chen, W. Hu, C. Chuang, S. Xie, A. Hu, W. Yan, X. Kong, X. Wu, H. Ji, L.-J. Wan, J. Am. Chem. Soc. 2019, 141, 3977.

H.-J. Qiu, Y. Ito, W. Cong, Y. Tan, P. Liu, A. Hirata, T. Fujita, Z. Tang, M. Chen, Angew. Chem., Int. Ed. 2015, 54, 14031.

H. Zhang, J. Li, S. Xi, Y. Du, X. Hai, J. Wang, H. Xu, G. Wu, J. Zhang, J. Lu, J. Wang, Angew. Chem., Int. Ed. 2019, 58, 14871.

D. D. Chronopoulos, A. Bakandritsos, M. Pykal, R. Zbořil, M. Otyepka, Appl. Mater. Today 2017, 9, 60.

X. Wei, D. Zheng, M. Zhao, H. Chen, X. Fan, B. Gao, L. Gu, Y. Guo, J. Qin, J. Wei, Y. Zhao, G. Zhang, Angew. Chem., Int. Ed. 2020, 59, 14639.

Y. Pan, R. Lin, Y. J. Chen, S. J. Liu, W. Zhu, X. Cao, W. X. Chen, K. L. Wu, W. C. Cheong, Y. Wang, L. R. Zheng, J. Luo, Y. Lin, Y. Q. Liu, C. G. Liu, J. Li, Q. Lu, X. Chen, D. S. Wang, Q. Peng, C. Chen, Y. D. Li, J. Am. Chem. Soc. 2018, 140, 4218.

H. Yang, L. Shang, Q. Zhang, R. Shi, G. I. N. Waterhouse, L. Gu, T. Zhang, Nat. Commun. 2019, 10, 4585.

K. Sohlberg, T. J. Pennycook, W. Zhou, S. J. Pennycook, Phys. Chem. Chem. Phys. 2015, 17, 3982.

A. Bakandritsos, M. Pykal, P. Błoński, P. Jakubec, D. D. Chronopoulos, K. Poláková, V. Georgakilas, K. Čépe, O. Tomanec, V. Ranc, A. B. Bourlinos, R. Zbořil, M. Otyepka, ACS Nano 2017, 11, 2982.

G. Zhang, C. Huang, X. Wang, Small 2015, 11, 1215.

J. P. Krogman, J. R. Gallagher, G. Zhang, A. S. Hock, J. T. Miller, C. M. Thomas, Dalton Trans. 2014, 43, 13852.

B. Hu, A. B. Getsoian, N. M. Schweitzer, U. Das, H. Kim, J. Niklas, O. Poluektov, L. A. Curtiss, P. C. Stair, J. T. Miller, A. S. Hock, J. Catal. 2015, 322, 24.

T. Zhang, T. Asefa, Front. Chem. Sci. Eng. 2018, 12, 329.

B. Dong, B. L. He, J. Huang, G. Y. Gao, Z. Yang, H. L. Li, J. Power Sources 2008, 175, 266.

Y. Meng, X. Zou, X. Huang, A. Goswami, Z. Liu, T. Asefa, Adv. Mater. 2014, 26, 6510.

A. L. Cazetta, T. Zhang, T. L. Silva, V. C. Almeida, T. Asefa, Appl. Catal., B 2018, 225, 30.

A. C. Martins, X. Huang, A. Goswami, K. Koh, Y. Meng, V. C. Almeida, T. Asefa, Carbon 2016, 102, 97.

A. V. Marenich, C. J. Cramer, D. G. Truhlar, J. Phys. Chem. B 2009, 113, 6378.

D. Zaoralová, R. Mach, P. Lazar, M. Medveď, M. Otyepka, Adv. Mater. Interfaces 2020, 2001392.

Coordination effects on the binding of late 3d single metal species to cyanographene

Emerging graphene derivatives as active 2D coordination platforms for single-atom catalysts