Hydrogenation reactions are fundamental in the fine chemical, pharmaceutical, and petrochemical industries, however heavily relying on H2 gas at high temperatures and pressures, incurring large energy and carbon costs. Photocatalytic transfer hydrogenation, using water as a proton source, offers a greener alternative, but existing photocatalysts often suffer from modest yields, limited selectivity, and narrow substrate scope. Additionally, they often require co-activation, such as Mg-activated water or non-sustainable hydrogen feeds. Here, a photocatalyst is introduced that offers high yields and selectivities across a broad spectrum of organic compounds. The developed photocatalyst is a multivalence palladium superstructure with ultrasmall Pd0 nanoparticles enveloped by isolated Pd2+/Pd4+ atoms within a carbon-nitride matrix. Mechanistic studies reveal that the redox-flexible Pd single atoms, with triethylamine as an electronic modulator, attract photogenerated holes for water oxidation, while Pd0 nanoparticles facilitate hydrogen transfer to the unsaturated bonds of the organic molecules. The cooperative and dynamic behavior of Pd centers during catalysis, involving transitions among Pd+2, Pd+3, and Pd+4 states, is validated using operando electron paramagnetic resonance spectroscopy. This multivalent palladium catalyst represents a conceptual advance in photocatalytic transfer hydrogenation with water as a hydrogen source, holding promise for sustainable hydrogenation processes in the chemical industry.

Leibniz Institute for Catalysis Albert Einstein Straβe 29a 18059 Rostock Germany

Nanotechnology Centre Centre for Energy and Environmental Technologies VSB Technical University of Ostrava 17 listopadu 2172 15 Ostrava Poruba 708 00 Czech Republic

National Key Laboratory for the Development and Utilization of Forest Food Resources Jiangsu Co Innovation Center of Efficient Processing and Utilization of Forest Resources International Innovation Center for Forest Chemicals and Materials Nanjing Forestry University Longpan Road 159 Nanjing 210037 China

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

School of Physical Science and Technology Shanghai Tech University Shanghai 201210 P R China

Shanghai Synchrotron Radiation Facility Shanghai Advanced Research Institute Zhangheng Road 293 Shanghai 201204 P R China

See more in PubMed

Luneau M., Lim J. S., Patel D. A., Sykes E. C. H., Friend C. M., Sautet P., Chem. Rev. 2020, 120, 12834. PubMed

Wang X., Liang X., Geng P., Li Q., ACS Catal. 2020, 10, 2395.

Arcudi F., Ethordevic L., Schweitzer N., Stupp S. I., Weiss E. A., Nat. Chem. 2022, 14, 1007. PubMed

Biosca M., Diéguez M., Zanotti‐Gerosa A., Adv. Catal. 2021, 68, 341.

Stoffels M. A., Klauck F. J. R., Hamadi T., Glorius F., Leker J., Adv. Synth. Catal. 2020, 362, 1258. PubMed PMC

Zhao D., Li X., Zhang K., Guo J., Huang X., Wang G., Coord. Chem. Rev. 2023, 487, 215159.

Zhang L., Zhou M., Wang A., Zhang T., Chem. Rev. 2019, 120, 683. PubMed

Wang D., Astruc D., Chem. Rev. 2015, 115, 6621. PubMed

Wu D., Baaziz W., Gu B., Marinova M., Hernández W. Y., Zhou W., Vovk E. I., Ersen O., Safonova O. V., Addad A., Nuns N., Khodakov A. Y., Ordomsky V. V., Nat. Catal. 2021, 4, 595.

Zhao M., Yuan K., Wang Y., Li G., Guo J., Gu L., Hu W., Zhao H., Tang Z., Nature 2016, 539, 76. PubMed

Sheldon R. A., Woodley J. M., Chem. Rev. 2018, 118, 801. PubMed

Kar S., Sanderson H., Roy K., Benfenati E., Leszczynski J., Chem. Rev. 2022, 122, 3637. PubMed

Poulose A. C., Zoppellaro G., Konidakis I., Serpetzoglou E., Stratakis E., Tomanec O., Beller M., Bakandritsos A., Zbořil R., Nat. Nanotechnol. 2022, 17, 485. PubMed PMC

Chandrashekhar V. G., Senthamarai T., Kadam R. G., Malina O., Kašlík J., Zbořil R., Gawande M. B., Jagadeesh R. V., Beller M., Nat. Catal. 2022, 5, 20.

Obata K., Schwarze M., Thiel T. A., Zhang X., Radhakrishnan B., Ahmet I. Y., van de Krol R., Schomäcker R., Abdi F. F., Nat. Commun. 2023, 14, 6017. PubMed PMC

Lee K., Jing Y., Wang Y., Yan N., Nat. Rev. Chem. 2022, 6, 635. PubMed PMC

Poulose A. C., Medveď M., Bakuru V. R., Sharma A., Singh D., Kalidindi S. B., Bares H., Otyepka M., Jayaramulu K., Bakandritsos A., Zbořil R., Nat. Commun. 2023, 14, 1373. PubMed PMC

Nie R., Tao Y., Nie Y., Lu T., Wang J., Zhang Y., Lu X., Xu C. C., ACS Catal. 2021, 11, 1071.

Yang H., Cui X., Dai X., Deng Y., Shi F., Nat. Commun. 2015, 6, 6478. PubMed

Sharma D., Choudhary P., Mittal P., Kumar S., Gouda A., Krishnan V., ACS Catal. 2024, 14, 4211.

Wakizaka M., Matsumoto T., Tanaka R., Chang H.‐C., Nat. Commun. 2016, 7, 12333. PubMed PMC

Xu C., Paon E., Rodríguez‐Padrón D., Luque R., Mauriello F., Chem. Soc. Rev. 2020, 49, 4273. PubMed

Hill C. K., Hartwig J. F., Nat. Chem. 2017, 9, 1213. PubMed PMC

Zhao E., Li M., Xu B., Wang X. L., Jing Y., Ma D., Mitchell S., Pérez‐Ramírez J., Chen Z., Angew. Chem., Int. Ed. 2022, 61, 202207410. PubMed

Wang T., Xin Y., Chen B., Zhang B., Luan S., Dong M., Wu Y., Cheng X., Liu Y., Liu H., Han B., Nat. Commun. 2024, 15, 2166. PubMed PMC

Liu C., Chen F., Zhao B.‐H., Wu Y., Zhang B., Nat. Rev. Chem. 2024, 8, 277. PubMed

Hao C. H., Guo X. N., Pan Y. T., Chen S., Jiao Z. F., Yang H., Guo X. Y., J. Am. Chem. Soc. 2016, 138, 9361. PubMed

Wang H., Shi Y., Wang Z., Song Y., Shen M., Guo B., Wu L., J. Catal. 2021, 396, 374.

Sharma P., Sasson Y., Green Chem. 2019, 21, 261.

Wang X., Maeda K., Chen X., Takanabe K., Domen K., Hou Y., Fu X., Antonietti M., J. Am. Chem. Soc. 2009, 131, 1680. PubMed

Goettmann F., Fischer A., Antonietti M., Thomas A., Angew. Chem., Int. Ed. 2006, 45, 4467. PubMed

Kim T. W., Choi K.‐S., Science 2014, 343, 990. PubMed

Risse T., Hollmann D., Brückner A., Catalysis 2015, 27, 1.

Hu C., Zhang Y., Hu A., Wang Y., Wei X., Shen K., Chen L., Li Y., Adv. Mater. 2023, 35, 2209298. PubMed

Bennati M., in EPR Spectroscopy: Fundamentals and Methods, (Eds: Goldfarb D., Stoll S.), Wiley, New York/Chichester, UK: 2018, pp. 81–94.

Takata T., Jiang J., Sakata Y., Nakabayashi M., Shibata N., Nandal V., Seki K., Hisatomi T., Domen K., Nature 2020, 581, 411. PubMed