Atomic Scale Engineering of Multivalence‐State Palladium Photocatalyst for Transfer Hydrogenation with Water as a Proton Source
Abstract
AbstractHydrogenation 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.
Article Details
Authors (13)
En Zhao
Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, Jiangsu Province Key Laboratory of Green Biomass-Based Fuels and Chemicals, College of Chemical Engineering, Nanjing Forestry University, Longpan Road 159, Nanjing 210037, People’s Republic of China
Wenjing Kong
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
Giorgio Zoppellaro
Yue Yang
Bing Nan
Lina Li
Wengjun Zhang
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
Zhaohui Chen
Laboratory of Tropical Veterinary Medicine and Vector Biology, School of Life and Health Sciences, Hainan Province Key Laboratory of One Health, Collaborative Innovation Center of One Health, Hainan University
Aristides Bakandritsos
Regional Centre of Advanced Technologies and Materials, Czech Advanced Technology and Research Institute (CATRIN), Palacký University Olomouc, Šlechtitelů 241/27, 783 71 Olomouc-Holice, Czech Republic
Zhu‐Jun Wang
School of Physical Science and Technology Shanghai Tech University Shanghai 201210 P. R. China
Matthias Beller
Leibniz-Institut für Katalyse
Radek Zbořil
Nanotechnology Centre, Centre for Energy and Environmental Technologies (CEET), VŠB−Technical University of Ostrava, 17. listopadu 2172/15, Ostrava-Poruba 708 00, Czech Republic
Zupeng Chen
Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, Jiangsu Province Key Laboratory of Green Biomass-Based Fuels and Chemicals, College of Chemical Engineering, Nanjing Forestry University, Longpan Road 159, Nanjing 210037, People’s Republic of China