Lulu Sun,Shiyang Liu,Taifeng Liu,Dongqiang Lei,Nengchao Luo,Feng Wang
ABSTRACT Photocatalytic decomposition of sugars is a promising way of providing H 2 , CO, and HCOOH as sustainable energy vectors. However, the production of C 1 chemicals requires the cleavage of robust C−C bonds in sugars with concurrent production of H 2 , which remains challenging. Here, the photocatalytic activity for glucose decomposition to HCOOH, CO (C 1 chemicals), and H 2 on Cu/TiO 2 was enhanced by nitrogen doping. Owing to nitrogen doping, atomically dispersed and stable Cu sites resistant to light irradiation are formed on Cu/TiO 2 . The electronic interaction between Cu and nitrogen ions originates valence band structure and defect levels composed of N 2 p orbit, distinct from undoped Cu/TiO 2 . Therefore, the lifetime of charge carriers is prolonged, resulting in the production of C 1 chemicals and H 2 with productivities 1.7 and 2.1 folds that of Cu/TiO 2 . This work provides a strategy to design coordinatively stable Cu ions for photocatalytic biomass conversion.
The production of C 2 H 3 Cl from CH 3 Cl (MCTV) represents a promising non-petroleum route for synthesizing C 2 alkenes from C 1 molecules. Exploration of new MCTV catalysts is crucial for advancing sustainable chemical production. In this study, we present NaVO 3 as a surface-confined coupling center for • CH 2 Cl radicals, demonstrating its superior performance in the selective coupling of methyl chloride to synthesize vinyl chloride. By incorporating NaVO 3 onto the surface of CeO 2 , the catalyst enables effective capture of • CH 2 Cl radicals during the CH 3 Cl oxidative pyrolysis and their subsequent conversion into C 2 H 3 Cl. We experimentally validate the capability of highly dispersed NaVO 3 to controllably couple • CH 2 Cl radicals through in-situ synchrotron-based vacuum ultraviolet photoionization mass spectrometry. The results demonstrate that the dispersion of NaVO 3 on the catalyst surface has a considerable impact on the reaction efficiency of • CH 2 Cl radicals and the overall MCTV performance. This discovery holds substantial implications for the controlled C 1 radical transformation and provides a guidance for the design of catalysts for sustainable production of C 2 H 3 Cl.
The direct methane (CH 4 ) oxidation to high value-added C1 chemicals is a great promising strategy to explore the CH 4 resource utilization. However, the low activity and selectivity of catalytic performance remains a great conundrum due to the difficulty to activate the C H bond and the unmanageable over oxidation. Herein, Pd x Au y nanowires (NWs) with various Pd/Au atomic ratios are presented as ideal models to explore the atomic-level effect of PdAu atoms for the direct CH 4 oxidation. The influence of reaction parameters are systematically investigated, and Pd 9 Au 1 NWs display a maximum yield of 2890.3 μmol g −1 h −1 with 99% selectivity for the liquid C1 oxygenated products. This enhanced performance is attributed to the combination of one-dimensional structure and the synergistic effect from the suitable portion of Au on Pd sites, which regulates bond strength between adsorbed radicals (•OH, •OOH, •CH 3 ) and PdAu atoms, confirmed by the density function theory calculations.
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