Hydrogen spillover is a phenomenon in which hydrogen atoms generated on metal catalysts diffuse onto catalyst supports. This phenomenon offers reaction routes for functional materials. However, due to difficulties in visualizing hydrogen, the fundamental nature of the phenomenon, such as how far hydrogen diffuses, has not been well understood. Here, in this study, we fabricated catalytic model systems based on Pd-loaded SrFeO ( ∼ 2.8) epitaxial films and investigated hydrogen spillover. We show that hydrogen spillover on the SrFeO support extends over long distances (∼600 μm). Furthermore, the hydrogen-spillover-induced reduction of Fe in the support yields large energies (as large as 200 kJ/mol), leading to the spontaneous hydrogen transfer and driving the surprisingly ultralong hydrogen diffusion. These results show that the valence changes in the supports' surfaces are the primary factor determining the hydrogen spillover distance. Our study leads to a deeper understanding of the long-debated issue of hydrogen spillover and provides insight into designing catalyst systems with enhanced properties.
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http://dx.doi.org/10.1021/jacs.2c09729 | DOI Listing |
Mater Horiz
January 2025
School of Materials Science and Engineering, National Institute for Advanced Materials, Nankai University, Tianjin, 300350, China.
The semi-hydrogenation of alkynes into alkenes rather than alkanes is of great importance in the chemical industry, and palladium-based metallic catalysts are currently employed. Unfortunately, a fairly high cost and uncontrollable over-hydrogenation impeded the application of Pd-based catalysts on a large scale. Herein, a sandwich structure single atom Pd catalyst, Z@Pd@Z, was prepared impregnation exchange and epitaxial growth methods (Z stands for ZIF-8), in which Pd single atoms were stabilized by pyrrolic N in a zeolitic imidazolate framework (ZIF-8).
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), State Key Laboratory of Chemical Engineering, Haihe Laboratory of Sustainable Chemical Transformations, Tianjin Key Laboratory of Applied Catalysis Science and Engineering, School of Chemical Engineering & Technology, Tianjin University, Tianjin, 300072, P. R. China.
CO hydrogenation to methanol using green hydrogen derived from renewable resources provides a promising method for sustainable carbon cycle but suffers from high selectivity towards byproduct CO. Here, we develop an efficient PdZn-ZnO/TiO catalyst by engineering lattice dislocation structures of TiO support. We discover that this modification orders irregularly arranged atoms in TiO to stabilize crystal lattice, and consequently weakens electronic interactions with supported active phases.
View Article and Find Full Text PDFAdv Mater
January 2025
State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing, 100084, China.
Nitrate electroreduction is promising for achieving effluent waste-water treatment and ammonia production with respect to the global nitrogen balance. However, due to the impeded hydrogenation process, high overpotentials need to be surmounted during nitrate electroreduction, causing intensive energy consumption. Herein, a hydroxide regulation strategy is developed to optimize the interfacial HO behavior for accelerating the hydrogenation conversion of nitrate to ammonia at ultralow overpotentials.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Shandong university, School of Chemistry and Chemical Engineering, No 27, Shandananlu,, 250100, Jinan, CHINA.
Rational regulation of active hydrogen (*H) behavior is crucial for advancing electrocatalytic nitrate reduction reaction (NO3RR) to ammonia (NH3), yet in-depth understanding of the *H generation, transfer, and utilization remains ambiguous, and explorations for *H dynamic optimization are urgently needed. Herein we engineer a Ni3N nanosheet array intimately decorated with Cu nanoclusters (NF/Ni3N-Cu) for remarkably boosted NO3RR. From comprehensive experimental and theoretical investigations, the Ni3N moieties favors water dissociation to generate *H, and then *H can rapidly transfer to the Cu via unique reverse hydrogen spillover mediating interfacial Ni-N-Cu bridge bond, thus increasing *H coverage on the Cu site for subsequent deoxygenation/hydrogenation.
View Article and Find Full Text PDFSmall
January 2025
State Key Laboratory of Bio-Fibers and Eco-Textiles, College of Materials Science and Engineering, College of Environmental Science and Engineering, Qingdao University, Qingdao, 266071, P. R. China.
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