Plasmon-Driven Catalysis on Bimetallic Nanostructures: Au-Pd for the Selective Oxygenation of Hydrocarbons

Project Information

PLACABIN

Grant agreement ID: 101022498

DOI

10.3030/101022498

Project closed

EC signature date 25 February 2021

Start date 5 January 2022

End date 4 January 2024

Funded under

• EXCELLENT SCIENCE - Marie Skłodowska-Curie Actions

Total cost

€ 224 933,76

EU contribution

€ 224 933,76

Coordinated by

CARDIFF UNIVERSITY
United Kingdom

Periodic Reporting for period 1 - PLACABIN (Plasmon-Driven Catalysis on Bimetallic Nanostructures: Au-Pd for the Selective Oxygenation of Hydrocarbons)

Reporting period: 2022-01-05 to 2024-01-04

Summary of the context and overall objectives of the project

The project PLACABIN aims to develop a universal principle guiding the design of bimetallic nanostructures for plasmonic-driven catalysis through an in-depth study of the intermetallic effects and the plasmon-driven selective mechanism. The partial oxidation of cyclohexane to cyclohexanone and cyclohexanol (KA oil) has been adopted as the representative reaction. KA oil is produced in millions of tonnes annually, mainly as a precursor to nylon. Due to the inertness of the C-H bond presents difficulties for selectivity, this reaction remains an important challenge for catalytic chemistry. We have developed Au-Pd bimetallic nanocatalysts supported by MgO micropowder and two graphitic carbon nitride based photocatalysts which were active in catalysing the solvent-free partial oxidation of cyclohexane to KA oil at mild conditions in the self-developed photocatalytic reaction systems. Through this project, we have developed a green and sustainable procedure for the production of industrially important KA oil.

Work performed from the beginning of the project to the end of the period covered by the report and main results achieved so far

Work performed through this project contains: (1) preparation of Au-Pd bimetallic photocatalysts and two graphitic carbon nitride based photocatalysts and structure-activity relationship study, (2) light-induced mechanism and kinetics studies, and (3) application potential evaluation for the developed photocatalysts and the photocatalytic reaction systems.
Results obtained from the above-mentioned work so far: Two photocatalytic reaction systems were developed for solid-liquid and solid-liquid-gas reactions. With the developed photocatalysts, the partial oxidation of cyclohexane to KA oil was achieved at mild conditions. These two graphitic carbon nitride based photocatalysts can be recycled for five times. The positive independence of activity on light intensity suggested a light induced reaction mechanism.
There is no exploitation/dissemination to report till now, because there are some tasks still under investigation, such as the intermetallic effects study for the Au-Pd bimetallic photocatalysts. However, we will continue to implement the plan for exploitation and dissemination of results as described in the DoA after the end of the final period.

Progress beyond the state of the art and expected potential impact (including the socio-economic impact and the wider societal implications of the project so far)

Partial oxidation of saturated C-H bonds of alkanes to value-added chemicals remains an important challenge for catalytic chemistry because the inertness of the C-H bond presents difficulties for selectivity. The partial oxidation of cyclohexane to KA oil catalysed by metals usually requires harsh conditions like high temperature and pressurised oxygen. Through this project, we have developed three photocatalysts which can catalyse this reaction at lower temperature and pressure conditions. Moreover, we have avoided the addition of radical initiators or other additives. This green and sustainable procedure holds the potential for the production of industrially important KA oil in the future.
The implementation of the fellowship has significantly enhanced my future career prospects, particularly in terms of my innovative research potential and soft skills. I have taken up a new role as an associate professor at a Chinese university in Beijing, where I am leading a Photocatalysis and Photobiocatalysis Group and initiating my independent research.

Au-Pd/MgO photocatalytic reaction