4.6 Article

Improved Visible-Light Activities of Rutile Nanorod by Comodifying Highly Dispersed Surface Plasmon Resonance Au Nanoparticles and HF Groups for Aerobic Selective Alcohol Oxidation

Journal

ACS SUSTAINABLE CHEMISTRY & ENGINEERING
Volume 6, Issue 11, Pages 14652-14659

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acssuschemeng.8b03222

Keywords

Rutile nanorod; SPR Au; O-2 adsorption; Charge separation; Visible-light photocatalysis; Selective alcohol oxidation

Funding

  1. NSFC [U1401245, 21706044, 91622119]
  2. Research Project of Chinese Ministry of Education [213011A]
  3. China Postdoctoral Science Foundation [2017M621316]
  4. Natural Science Foundation of Heilongjiang Province, China [B2017006]

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In this work, rutile nanorod comodified by highly dispersed surface plasmon resonance (SPR) Au nanoparticles (NPs) and HF groups exhibits remarkable visible-light activities for the benzyl alcohol oxidation conversion of 90% compared to that (25%) of the unmodified one and the high selectivity (>99%) at room temperature with O-2 as the oxidant. Based on the time-resolved surface photovoltage responses and O-2-temperature-programmed desorption curves, it is confirmed that the outstanding activity of comodified rutile nanorod is synergistically attributed to the large surface area of and the favored charge separation of as-synthesized nanorod, to the extended visible-light response and the promoted charge separation of deposited SPR Au NPs, and then to the promoted O-2 adsorption of modified HF groups. Moreover, it is suggested that the produced superoxide-type species is the main active oxygen species to dominate the conversion of benzyl alcohol (BA). Especially, the comodified rutile nanorod is more active for the visible-light oxidation of alcohol with the electron-donating group like methyl. This work has provided feasible design strategy for highly effective visible-light photocatalysts for elective aerobic organic oxidation and pollutant degradation.

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