Photocatalytic Reforming of Ethanol in the Liquid Phase Using a Ternary Composite of Rh/TiO2/g-C3N4 as a Catalyst.

Photocatalytic reforming of ethanol provides an effective way to produce hydrogen energy using natural and nontoxic ethanol as raw material. Developing highly efficient catalysts is central to this field. Although traditional semiconductor/metal heterostructures (e.g., Rh/TiO2) can result in relatively high catalyst performance by promoting the separation of photoinduced hot carriers, it will still be highly promising to further improve the catalytic performance via a cost-effective and convenient method. In this study, we developed a highly efficient photocatalyst for ethanol reformation by preparing a ternary composite structure of Rh/TiO2/g-C3N4. Hydrogen is the main product, and the reaction rate could reach up to 27.5 mmol g-1 h-1, which is ∼1.41-fold higher than that of Rh/TiO2. The catalytic performance here is highly dependent on the wavelength of the light illumination. Moreover, the photocatalytic reforming of ethanol and production of hydrogen were also dependent on the Rh loading and g-C3N4:TiO2 ratio in Rh/TiO2/g-C3N4 composites as well as the ethanol content in the reaction system. The mechanism of the enhanced hydrogen production in Rh/TiO2/g-C3N4 is determined as the improvement in the separation of photoinduced hot carriers. This work provides an effective photocatalyst for ethanol reforming, largely expanding its application in the field of renewable energy and interface science.

Raman Monitoring of the Electro-Optical Synergy-Induced Enhancements in Carbon-Bromine Bond Cleavage, Reaction Rate, and Product Selectivity of p-Bromothiophenol.

Electro-optical synergy has recently been targeted to improve the separation of hot carriers and thereby further improve the efficiency of plasmon-mediated chemical reactions (PMCRs). However, the electro-optical synergy in PMCRs needs to be more deeply understood, and its contribution to bond dissociation and product selectivity needs to be clarified. Herein, the electro-optical synergy in plasmon-mediated reduction of p-bromothiophenol (PBTP) was studied on a plasmonic nanostructured silver electrode using in situ Raman spectroscopy and theoretical calculations. It was found that the electro-optical synergy-induced enhancements in the cleavage of carbon-bromine bonds, reaction rate, and product selectivity (4,4'-biphenyl dithiol vs thiophenol) were largely affected by the applied bias, laser wavelength, and laser power. The theoretical simulation further clarified that the strong electro-optical synergy is attributed to the matching of energy band diagrams of the plasmonic silver with those of the adsorbed PBTP molecules. A deep understanding of the electro-optical synergy in PBTP reduction and the clarification of the mechanism will be highly beneficial for the development of other highly efficient PMCRs.