With increasing concerns for global warming, the solar-driven photocatalytic reduction of CO2 into chemical fuels like methanol is a propitious route to enrich energy supplies, with concomitant reduction of the abundant CO2 stockpiles. Herein, a novel single atom-confinement and a strategy are reported toward single ruthenium atoms dispersion over porous carbon nitride surface. Ruthenium single atom character is well confirmed by EXAFS absorption spectrometric analysis unveiling the cationic coordination environment for the single-atomic-site ruthenium center, that is formed by Ru-N/C intercalation in the first coordination shell, attaining synergism in N-Ru-N connection and interfacial carrier transfer. From time resolved fluorescence decay spectra, the average carrier lifetime of the RuSA-mC3 N4 system is found to be higher compared to m-C3 N4 ; the fact uncovering the crucial role of single Ru atoms in promoting photocatalytic reaction system. A high yield of methanol (1500 µmol g-1 cat. after 6 h of the reaction) using water as an electron donor and the reusability of the developed catalyst without any significant change in the efficiency represent the superior aspects for its potential application in real industrial technologies.

Davidson School of Chemical Engineering Purdue University 480 Stadium Mall Drive West Lafayette IN 47907 USA

Department of Industrial and Engineering Chemistry Institute of Chemical Technology Mumbai Marathwada Campus Jalna Maharashtra 431213 India

Nanotechnology Centre CEET VŠB Technical University 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

Zobrazit více v PubMed

U. Ulmer, T. Dingle, P. N. Duchesne, R. H. Morris, A. Tavasoli, T. Wood, G. A. Ozin, Nat. Commun. 2019, 10, 3169.

Q. Liu, L. Wu, R. Jackstell, M. Beller, Nat. Commun. 2015, 6, 5933.

X. Liu, S. Inagaki, J. Gong, Angew. Chem., Int. Ed. 2016, 55, 14924.

S. N. Habisreutinger, L. Schmidt-Mende, J. K. Stolarczyk, Angew. Chem., Int. Ed. 2013, 52, 7372.

M. Parry, M. L. Parry, O. Canziani, J. Palutikof, P. Van der Linden, C. Hanson, Climate Change 2007-Impacts, Adaptation and Vulnerability: Working Group II Contribution to the Fourth Assessment Report of the IPCC, Cambridge University Press, Cambridge 2007.

A. White, M. G. R. Cannell, A. D. Friend, Global Change Biol. 2000, 6, 817.

C. Costentin, M. Robert, J.-M. Savéant, Chem. Soc. Rev. 2013, 42, 2423.

X. Jiao, K. Zheng, Z. Hu, Y. Sun, Y. Xie, ACS Cent. Sci. 2020, 6, 653.

B. Kumar, M. Llorente, J. Froehlich, T. Dang, A. Sathrum, C. P. Kubiak, Annu. Rev. Phys. Chem. 2012, 63, 541.

J. Zhong, X. Yang, Z. Wu, B. Liang, Y. Huang, T. Zhang, Chem. Soc. Rev. 2020, 49, 1385.

P. R. Yaashikaa, P. Senthil Kumar, S. J. Varjani, A. Saravanan, J. CO2 Util. 2019, 33, 131.

S. Kumar, M. B. Gawande, J. Kopp, S. Kment, R. S. Varma, R. Zbořil, ChemSusChem 2020, 13, 5231.

K. Sekizawa, K. Maeda, K. Domen, K. Koike, O. Ishitani, J. Am. Chem. Soc. 2013, 135, 4596.

A. Kumar, P. Kumar, R. Borkar, A. Bansiwal, N. Labhsetwar, S. L. Jain, Carbon 2017, 123, 371.

B. Duan, L. Mei, J. Colloid Interface Sci. 2020, 575, 265.

Y. N. Kavil, Y. A. Shaban, R. Kh. Al Farawati, M. I. Orif, M. Zobidi, S. U. M. Khan, J. Photochem. Photobiol. Chem. 2017, 347, 244.

B. AlOtaibi, X. Kong, S. Vanka, S. Y. Woo, A. Pofelski, F. Oudjedi, S. Fan, M. G. Kibria, G. A. Botton, W. Ji, H. Guo, Z. Mi, ACS Energy Lett. 2016, 1, 246.

T. Billo, F.-Y. Fu, P. Raghunath, I. Shown, W.-F. Chen, H.-T. Lien, T.-H. Shen, J.-F. Lee, T.-S. Chan, K.-Y. Huang, C.-I. Wu, M. C. Lin, J.-S. Hwang, C.-H. Lee, L.-C. Chen, K.-H. Chen, Small 2018, 14, 1702928.

H. Cheng, B. Huang, Y. Liu, Z. Wang, X. Qin, X. Zhang, Y. Dai, Chem. Commun. 2012, 48, 9729.

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

Z. Chen, E. Vorobyeva, S. Mitchell, E. Fako, N. López, S. M. Collins, R. K. Leary, P. A. Midgley, R. Hauert, J. Pérez-Ramírez, Natl. Sci. Rev. 2018, 5, 642.

X. Su, X.-F. Yang, Y. Huang, B. Liu, T. Zhang, Acc. Chem. Res. 2019, 52, 656.

L. Cao, W. Liu, Q. Luo, R. Yin, B. Wang, J. Weissenrieder, M. Soldemo, H. Yan, Y. Lin, Z. Sun, C. Ma, W. Zhang, S. Chen, H. Wang, Q. Guan, T. Yao, S. Wei, J. Yang, J. Lu, Nature 2019, 565, 631.

H. Wang, J.-X. Liu, L. F. Allard, S. Lee, J. Liu, H. Li, J. Wang, J. Wang, S. H. Oh, W. Li, M. Flytzani-Stephanopoulos, M. Shen, B. R. Goldsmith, M. Yang, Nat. Commun. 2019, 10, 3808.

G. Vilé, D. Albani, M. Nachtegaal, Z. Chen, D. Dontsova, M. Antonietti, N. López, J. Pérez-Ramírez, Angew. Chem., Int. Ed. 2015, 54, 11265.

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.

B. Ma, G. Chen, C. Fave, L. Chen, R. Kuriki, K. Maeda, O. Ishitani, T.-C. Lau, J. Bonin, M. Robert, J. Am. Chem. Soc. 2020, 142, 6188.

J. Fu, S. Wang, Z. Wang, K. Liu, H. Li, H. Liu, J. Hu, X. Xu, H. Li, M. Liu, Front. Phys. 2020, 15, 33201.

W. Yu, D. Xu, T. Peng, J. Mater. Chem. A 2015, 3, 19936.

M. S. Jeletic, M. T. Mock, A. M. Appel, J. C. Linehan, J. Am. Chem. Soc. 2013, 135, 11533.

Q. Liu, Y. Zhou, J. Kou, X. Chen, Z. Tian, J. Gao, S. Yan, Z. Zou, J. Am. Chem. Soc. 2010, 132, 14385.

C. Federsel, A. Boddien, R. Jackstell, R. Jennerjahn, P. J. Dyson, R. Scopelliti, G. Laurenczy, M. Beller, Angew. Chem., Int. Ed. 2010, 49, 9777.

S. Cao, M. Yang, A. O. Elnabawy, A. Trimpalis, S. Li, C. Wang, F. Göltl, Z. Chen, J. Liu, J. Shan, M. Li, T. Haas, K. W. Chapman, S. Lee, L. F. Allard, M. Mavrikakis, M. Flytzani-Stephanopoulos, Nat. Chem. 2019, 11, 1098.

L. Liang, F. Lei, S. Gao, Y. Sun, X. Jiao, J. Wu, S. Qamar, Y. Xie, Angew. Chem., Int. Ed. 2015, 54, 13971.

P. Huang, J. Huang, S. A. Pantovich, A. D. Carl, T. G. Fenton, C. A. Caputo, R. L. Grimm, A. I. Frenkel, G. Li, J. Am. Chem. Soc. 2018, 140, 16042.

X. Cui, W. Li, P. Ryabchuk, K. Junge, M. Beller, Nat. Catal. 2018, 1, 385.

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.

K. Li, B. Peng, T. Peng, ACS Catal. 2016, 6, 7485.

D. Zhao, J. Feng, Q. Huo, N. Melosh, G. H. Fredrickson, B. F. Chmelka, G. D. Stucky, Science 1998, 279, 548.

M. Wu, Y. Gong, T. Nie, J. Zhang, R. Wang, H. Wang, B. He, J. Mater. Chem. A 2019, 7, 5324.

Q. Lin, Y. Huang, Y. Wang, L. Li, X. Y. Liu, F. Lv, A. Wang, W.-C. Li, T. Zhang, J. Mater. Chem. A 2014, 2, 5178.

R. E. Shepherd, A. Proctor, W. W. Henderson, T. K. Myser, Inorg. Chem. 1987, 26, 2440.

L. Chen, P. Hu, C. P. Deming, N. Wang, J. E. Lu, S. Chen, J. Phys. Chem. C 2016, 120, 13303.

C. Creutz, N. Sutin, Proc. Natl. Acad. Sci. USA 1975, 72, 2858.

Y.-T. Li, S.-H. Zhang, G.-P. Zheng, P. Liu, Z.-K. Peng, X.-C. Zheng, Appl. Catal., A 2020, 595, 117511.

S. Yang, Y. Gong, J. Zhang, L. Zhan, L. Ma, Z. Fang, R. Vajtai, X. Wang, P. M. Ajayan, Adv. Mater. 2013, 25, 2452.

T. Marshall-Roth, N. J. Libretto, A. T. Wrobel, K. J. Anderton, M. L. Pegis, N. D. Ricke, T. V. Voorhis, J. T. Miller, Y. Surendranath, Nat. Commun. 2020, 11, 5283.

T. Marshall-Roth, N. J. Libretto, A. T. Wrobel, K. Anderton, N. D. Ricke, T. Van Voorhis, J. T. Miller, Y. Surendranath, Nat. Commun. 2020, 11, 5283.

X. Li, H. Rong, J. Zhang, D. Wang, Y. Li, Nano Res. 2020, 13, 1842.

J. Yang, W. Li, D. Wang, Y. Li, Small Struct. 2021, 2, 2000051.

X. Wang, C. Liow, A. Bisht, X. Liu, T. C. Sum, X. Chen, S. Li, Adv. Mater. 2015, 27, 2207.

S. Mondal, L. Sahoo, Y. Vaishnav, S. Mishra, R. S. Roy, C. P. Vinod, A. K. De, U. K. Gautam, J. Mater. Chem. A 2020, 8, 20581.

Developing Benign Ni/g-C3N4 Catalysts for CO2 Hydrogenation: Activity and Toxicity Study

Silver nanomaterials: synthesis and (electro/photo) catalytic applications