Epoxy Group-tuned Co-N₄ Active Sites on Graphyne for High-efficiency Hydrogen Peroxide Production

Abstract

The green electrochemical synthesis of hydrogen peroxide (H₂O₂) through two-electron oxygen reduction reaction (2e⁻ ORR) urgently requires catalysts with high selectivity and stability. Regulating the electronic structure and stable anchoring of molecular catalysts is an effective strategy to achieve this goal. Based on this, this research focuses on the anchoring effect of oxidized graphyne (GYO) on cobalt phthalocyanine (CoPc) and the regulation mechanism of its epoxy group on the electronic structure of active sites, and proposes a novel GYO-CoPc composite catalyst. Through a nitric acid oxidation strategy, the GYO substrate constructs a three-dimensional porous network and abundant epoxy groups. It firmly anchors CoPc through π-π interactions and induces an electron-deficient state at the Co-N₄ center via an electron coupling effect. Characterization of morphology and physical phase confirm the precise regulation of the active site by epoxy groups, which significantly weakens the adsorption strength of the *OOH intermediate. Electrochemical tests show that GYO-CoPc achieves a H₂O₂ selectivity of 99% at 0.65 V vs. RHE, with a high yield of 7.15 mol·g⁻¹·h⁻¹ and a stability of over 30 h. This work reveals new strategy for the design of carbon-based molecular catalysts and provides important references for the development of efficient 2e⁻ ORR catalytic systems.

Keywords

Oxygen reduction reaction / Hydrogen peroxide / Molecular catalyst / Oxidized graphyne

References

[1] Zhou W, Xie L, Gao J H, Nazari R, Zhao H Q, Meng X X, Sun F, Zhao G B, Ma J. Chem. Eng. J., 2021, 410: 128368

[2] Zhang H Y, Wang H, Duan P Y, Lei Q, Li B B, Zhu D M, Tian M, Sun J Y, Sun J H, Wang Y F. Adv. Funct. Mater., 2025, 35: 2417090

[3] Perry S C, Pangotra D, Vieira L, Csepei L I, Sieber V, Wang L, Ponce De León C, Walsh F C. Nat. Rev. Chem., 2019, 3: 442

[4] Shi X J, Back S, Gill T M, Siahrostami S, Zheng X L. Chem, 2021, 7: 38

[5] Lu Z Y, Chen G X, Siahrostami S, Chen Z H, Liu K, Xie J, Liao L, Wu T, Lin D C, Liu Y Y, Jaramillo T F, Nørskov J K, Cui Y. Nat. Catal., 2018, 1: 156

[6] Li B Y, Ou H H, Chen S H, Su Y Q, Wang D S. Chem. Res. Chinese Universities, 2023, 39: 527

[7] Siahrostami S, Villegas S J, Bagherzadeh Mostaghimi A H, Back S, Farimani A B, Wang H T, Persson K A, Montoya J. ACS Catal., 2020, 10: 7495

[8] Campos Martin J M, Blanco Brieva G, Fierro J L G. Angew. Chem. Int. Ed., 2006, 45: 6962

[9] Bu Y F, Wang Y B, Han G, Zhao Y X, Ge X L, Li F, Zhang Z H, Zhong Q, Baek J. Adv. Mater., 2021, 33: 2103266

[10] Nazir A, Pathak A, Hamal D, Awadallah O, Motevalian S, Claus A, Drozd V, El-Zahab B. Energy Environ. Mater., 2025, 8: e12844

[11] Tang J Y, Zhao T S, Solanki D, Miao X B, Zhou W G, Hu S. Joule, 2021, 5: 1432

[12] He J, Chen C, Yu H L, Zhao Y, Xu M, Xiong T, Lu Q H, Yu Z, Tai K P, Tan J, Liu C. J. Mater. Sci. Technol, 2025, 212: 139

[13] Wang N, Ma S B, Zuo P J, Duan J Z, Hou B R. Adv. Sci., 2021, 8: 2100076

[14] Jiang K, Zhao J J, Wang H T. Adv. Funct. Mater., 2020, 30: 2003321

[15] Liu X Y, Liu J W, Li G, Zhao J X. Rare Met., 2024, 43: 3107

[16] Li B, Zhao C, Liu J, Zhang Q. Adv. Mater., 2019, 31: 1808173

[17] Chen B, Jiang Y F, Xiao H, Li J. Chin. J. Catal., 2023, 50: 306

[18] Yang X X, Zeng Y C, Alnoush W, Hou Y, Higgins D, Wu G. Adv. Mater., 2022, 34: 2107954

[19] Ren X F, Dong X M, Liu L F, Hao J, Zhu H D, Liu A M, Wu G. SusMat, 2023, 3: 442

[20] Zhang C C, Liu X P, Li X F, Liu Y P, Wei G Y, Yang T F, Zhang J, Chen Y, Gao S Y. Sci. China Mater., 2023, 66: 2689

[21] Xu S R, Wu Q, Lu B A, Tang T, Zhang J N, Hu J S. Acta Phys. Chim. Sin., 2022, 39: 2209001

[22] Wu J, Mehmood A, Zhang G H, Wu S, Ali G, Kucernak A. ACS Catal., 2021, 11: 5035

[23] Ma Z C, Yang T F, Huang J R, Hu S X, Ge B C, Liu Y, Gao S Y. J. Mater. Sci. Technol., 2025, 233: 193

[24] Wu Z K, Wang T Z, Zou J J, Li Y D, Zhang C J. ACS Catal., 2022, 12: 5911

[25] Pu C, Deng D J, Li H N, Xu L. Acta Phys. Chim. Sin., 2024, 40: 2304021

[26] Zhou Z, Kong Y, Tan H, Huang Q W, Wang C, Pei Z X, Wang H Z, Liu Y Y, Wang Y H, Li S, Liao X Z, Yan W S, Zhao S L. Adv. Mater., 2022, 34: 2106541

[27] Zhang X, Su X Z, Zheng Y, Hu S, Shi L, Gao F, Yang P, Niu Z, Wu Z, Qin S, Wu R, Duan Y, Gu C, Zheng X, Zhu J, Gao M. Angew. Chem. Int. Ed., 2021, 60: 26922

[28] Liu M R, Liu C Y, Yang T F, Hu S X, Li S Y, Liu S Z, Liu Y, Chen Y, Ge B C, Gao S Y. Chin. J. Catal., 2024, 66: 212

[29] Yu Y H, Rao P, Feng S Y, Chen M, Deng P L, Li J, Miao Z P, Kang Z Y, Shen Y J, Tian X L. Acta Phys. Chim. Sin., 2022, 39: 2210039

[30] Xia T, Wan J W, Zhou X, He Y L, Su F M, Ji B F, Zheng Y P, Wang D, Yu R B. Nano Res., 2025, 18: 94907311

[31] Zhu Q Y, Zhou J, Li L. Int. J. Hydrog. Energy, 2025, 125: 86

[32] Gong H S, Wei Z X, Gong Z C, Liu J J, Ye G L, Yan M M, Dong J C, Allen C, Liu J B, Huang K, Liu R, He G C, Zhao S L, Fei H L. Adv. Funct. Mater., 2022, 32: 2106886

[33] Mao Y X, Chen S, Jia Z H, Dong X F, Mao Q. Chem. Res. Chinese Universities, 2023, 39: 1031

[34] Fan W J, Duan Z Y, Liu W, Mehmood R, Qu J T, Cao Y C, Guo X Y, Zhong J, Zhang F X. Nat. Commun., 2023, 14: 1426

[35] Lin L, Sun Z M, Chen H T, Zhao L, Sun M Y, Yang Y T, Liao Z S, Wu X Y, Li X X, Tang C. Acta Phys. Chim. Sin., 2024, 40: 2305019

[36] Sun L B, Jin X D, Su T, Fisher A C, Wang X. Adv. Mater., 2024, 36: 2306336

[37] Liu W, Chen R, Sang Z Y, Li Z X, Nie J H, Yin L C, Hou F, Liang J. Adv. Mater., 2024, 36: 2406403

[38] Wang S F, Li L F, Zheng Y, Xu C H, Zhuang Z W, Sun K A, Yan W, Zhang J J. Appl. Catal. B Environ. Energy, 2025, 377: 125493

[39] Xu S Y, Cen J H, Yang G, Si L P, Xiao X Y, Liu H Y. Chem. Res. Chinese Universities, 2024, 40: 1106

[40] Hu J W, Shang W Z, Xin C C, Guo J Y, Cheng X S, Zhang S L, Song S C, Liu W, Ju F, Hou J G, Shi Y T. Angew. Chem. Int. Ed., 2023, 62: e202304754

[41] Ge W J, Chen X C, Ma R Z, Zheng S Y, Shang N Z, Zhao X X. Chem. Res. Chinese Universities, 2024, 40: 437

[42] Huang X, Liu W, Zhang J J, Song M, Zhang C, Li J W, Zhang J, Wang D L. ACS Appl. Mater. Interfaces, 2022, 14: 11350

[43] Wen Z Y, Han N, Li Y G. Acta Phys. Chim. Sin., 2024, 40: 2304001

[44] Lee B H, Shin H, Rasouli A S, Choubisa H, Ou P F, Dorakhan R, Grigioni I, Lee G, Shirzadi E, Miao R K, Wicks J, Park S, Lee H S, Zhang J Q, Chen Y J, Chen Z, Sinton D, Hyeon T, Sung Y-E, Sargent E H. Nat. Catal., 2023, 6: 234

[45] Liu Y Y, Liu S L, Jiang J C, Wei X N, Zhao K K, Shen R F, Wang X P, Wei M, Wang Y F, Pang H, Li B J. Adv. Mater., 2025, 37: 2502197

[46] Lei Z Y, Sun H L, Dong Z H, Sun S S, Bi C Y, Zhan J L, Wu L, Jia M J. Chem. Res. Chinese Universities, 2024, 40: 1116

[47] Fan Y W, Wang Y, Wang H J, Chen Y Z, Li Z B. Chem. Res. Chinese Universities, 2024, 40: 1141

[48] Wang C B, Li P, Chen D H, Zhang R Y, Wang L, Zong L B. Chem. Res. Chinese Universities, 2024, 40: 462

[49] Gu H L, Zhong L X, Shi G S, Li J Q, Yu K, Li J, Zhang S, Zhu C Y, Chen S H, Yang C L, Kong Y, Chen C, Li S Z, Zhang J, Zhang L M. J. Am. Chem. Soc., 2021, 143: 8679

[50] Li X H, Li X D, Sun Q H, He J J, Yang Z, Xiao J C, Huang C S. Acta Phys. Chim. Sin., 2022, 39: 2206029

[51] Zhang C, Li Y Q, Xie Y, Yu Z J, Wan X, Wang X Z, He J A, Li J L, Chen Z G, Li X Y, Y X H, Wang Z L, Ying G-G, Dionysiou D D, Huang M Z. ACS Catal., 2023, 13: 12425

[52] La W G, Jung M J, Yoon J K, Bhang S H, Jang H K, Lee T J, Yoon H H, Shin J Y, Kim B S. Carbon, 2014, 78: 428

[53] Liu Y Y, Zhou L M, Liu S L, Li S Q, Zhou J J, Li X, Chen X M, Sun K, Li B J, Jiang J C, Pang H. Angew. Chem. Int. Ed., 2024, 63: e202319983

[54] Yuan L, Du P Y, Zhang C Q, Xi Y M, Zou Y Y, Li J X, Bi Y, Bao T, Liu C, Yu C Z. Appl. Catal. B: Environ. Energy, 2025, 364: 124855

[55] Fisseha G, Yu Y, Lu S J, Hu Y P, Zhou Y, Yue Q. Chin. J. Catal., 2024, 56: 81

[56] Zhang W J, Li J, Wei Z D. Chin. J. Catal., 2023, 48: 15

[57] Jiang H R, Wang Z C, Chen S H, Xiao Y, Zhu Y, Wu W, Chen R Z, Cheng N C. J. Mater. Sci. Technol., 2025, 205: 212

[58] Cao P K, Quan X, Nie X W, Zhao K, Liu Y M, Chen S, Yu H T, Chen J G. Nat. Commun., 2023, 14: 172

[59] Zhang L, Li J F, Wei G Y, Yang H F, Bai H, Xi G C. Angew. Chem. Int. Ed., 2024, 63: e202316936

[60] Feng X, Bai Y, Liu M Q, Li Y, Yang H Y, Wang X R, Wu C. Energy Environ. Sci., 2021, 14: 2036

[61] Liu Y Y, Liu S L, Zhang P X, Zhou J J, Liu H, Li S Q, Li X, Wang X P, Han D D, Chen Y, Wang Y F, Jiang J C, Li B J. Adv. Funct. Mater., 2024, 34: 2400522

[62] Gong L Y, Wang Y, Liu J, Wang X, Li Y, Hou S, Wu Z J, Jin Z, Liu C P, Xing W, Ge J J. Chin. J. Catal., 2023, 50: 352

[63] Aljabour A, Awada H, Song L Y, Sun H, Offenthaler S, Yari F, Bechmann M, Scharber M C, Schöfberger W. Angew. Chem. Int. Ed., 2023, 62: e202302208

[64] Liu B W, Feng R H, Busch M, Wang S H, Wu H F, Liu P, Gu J J, Bahadoran A, Matsumura D, Tsuji T, Zhang D, Song F, Liu Q L. ACS Nano, 2022, 16: 14121

RIGHTS & PERMISSIONS

Jilin University, The Editorial Department of Chemical Research in Chinese Universities and Springer-Verlag GmbH