Metal Single Atom Strategy Greatly Boosts Photocatalytic Methyl Activation and C–C Coupling for the Coproduction of High-Value-Added Multicarbon Compounds and Hydrogen

No Thumbnail Available
File version
Author(s)
Zhou, Peng
Chao, Yuguang
Lv, Fan
Wang, Kai
Zhang, Weiyu
Zhou, Jinhui
Chen, Hui
Wang, Liang
Li, Yiju
Zhang, Qinghua
Gu, Lin
Guo, Shaojun
Griffith University Author(s)
Primary Supervisor
Other Supervisors
Editor(s)
Date
2020
Size
File type(s)
Location
License
Abstract

Photocatalytic reforming of renewable and low-cost biomass is an alternative approach to synthesize high-value-added multicarbon compounds and hydrogen. However, the difficulty in activating the methyl group of biomass and simultaneously promoting the C–C coupling makes photocatalytic reforming still a great challenge. Herein, through the first-principles simulation calculation of the energy barrier of acetone dehydrogenation and conversion over a series of noble metal single atom (Ru, Rh, Pd, Ag, Os, Ir, Pt, and Au)-loaded TiO2 (MSA-TiO2) photocatalysts, we predict a Pt single atom-loaded TiO2 (PtSA-TiO2) photocatalyst that can enable methyl activation, CH3COCH2• radical formation, and hydrogen production most effectively from acetone, which is very significant for the synthesis of high-value-added multicarbon compounds by C–C coupling. This is well confirmed by our photocatalytic experiments, revealing that PtSA-loaded commercial P25-TiO2 exhibits the best photocatalytic activity of 3.87 mmol g–1 h–1 for the direct coproduction of high-value-added 2,5-hexanedione (HDN) and hydrogen from acetone with a selectivity of 93%, at least 13-fold higher activity than other noble metal (Ru, Rh, and Ir) single atoms or Pt nanoparticle-loaded ones. In situ attenuated total reflection infrared spectroscopy reveals that the PtSAs contribute to the effective methyl activation and simultaneously promote the formation of more intermediate CH3COCH2• radicals, which are further confirmed by in situ electron spin resonance spectroscopy.

Journal Title

ACS Catalysis

Conference Title
Book Title
Edition
Volume

10

Issue

16

Thesis Type
Degree Program
School
Publisher link
Patent number
Funder(s)
Grant identifier(s)
Rights Statement
Rights Statement
Item Access Status
Note
Access the data
Related item(s)
Subject

Inorganic Chemistry

Organic Chemistry

Chemical Engineering

Persistent link to this record
Citation

Zhou, P; Chao, Y; Lv, F; Wang, K; Zhang, W; Zhou, J; Chen, H; Wang, L; Li, Y; Zhang, Q; Gu, L; Guo, S, Metal Single Atom Strategy Greatly Boosts Photocatalytic Methyl Activation and C–C Coupling for the Coproduction of High-Value-Added Multicarbon Compounds and Hydrogen, ACS Catalysis, 2020, 10 (16), pp. 9109-9114

Collections