Journal
ACS CATALYSIS
Volume -, Issue -, Pages -Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.2c04951
Keywords
PdmPn; sulfur tolerance; hydrogenation; sulfur-containing substrates; mechanism
Categories
Funding
- Natural Science of Foundation China [21576140]
- Fundamental Research Funds for the Central Universities (Nankai University) [63201039]
- Fundamental Research Funds for the Central Universities (111 project) [B12015]
- MOE Innovation Team of China [IRT13R30, IRT13022]
- Tianjin Normal University Innovation Plan [135202XC1601]
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This study synthesized PdmPn/CNF catalysts with different crystal phases and systematically studied their sulfur resistance. The results showed that Pd5P2/CNFs exhibited the best hydrogenation activity under sulfur poisoning conditions, and the weakening of sulfur-related bonds led to the difficulty in forming palladium sulfide.
The development of sulfur-tolerant heterogeneous noble metal catalysts with high activity and stability has always been a major challenge. Herein, PdmPn/carbon nanofiber (CNF) catalysts with tunable crystal phases (Pd6P, Pd3P, Pd5P2, and PdP2) were synthesized by a simple impregnation-pyrolysis method, and their sulfur resistance was systematically studied in hydrogenation of sulfur-containing substrates and hydrogenation of aromatic compounds in a sulfur-containing system. Structural analysis showed that all PdmPn/CNF catalysts with phase-pure phosphides exhibited a similar morphology and physicochemical properties. However, the obvious differences in hydrogenation activity (Pd > Pd6P > Pd3P > Pd5P2 > PdP2) and anti-sulfur (Pd < Pd6P < Pd3P < Pd5P2 < PdP2) performance are presented. Overall, Pd5P2/CNFs exhibited the optimal catalytic hydrogenation activity of sulfur-containing substrates and aromatic compounds in sulfur-containing systems, and its turnover frequency (1043.9 h(-1)) was 20 times higher than that of Pd/CNFs (51.8 h(-1)) in 4-nitrothioanisole hydrogenation. Combining systematical characterizations with density functional theory calculation, the enhanced resistance to sulfur poisoning of PdmPn/CNFs is attributed to the reduced adsorption strength and adsorption energy of the sulfur-containing molecules. Meanwhile, when sulfur-containing molecules are adsorbed on PdmPn/CNFs, the weakened Pd-S and enhanced C-S bond suggest that it is more difficult to form palladium sulfide from being poisoned. This work was valuable for guiding the design and manipulation of noble metal-based anti-sulfur catalysts.
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