Periodic Reporting for period 1 - C[Au]PSULE (Crystal phase engineering of Au nanoparticles for enhanced solar fuel generation)
Periodo di rendicontazione: 2020-04-01 al 2022-03-31
In the grant proposal, I focus on the development of novel photocatalysts to convert solar energy into chemicals and fuels, mainly including photocatalytic CO2 reduction into CO fuel and organic synthesis. Different photocatalysts such as twin-Au modified TiO2, and metal Pd cube decorated perovskites are designed to achieve this goal. The following text introduces some typic examples about the addressed issue in scientific area and shows how we can obtain higher and better solar to energy conversion efficiency.
The efficient utilization of sunlight to activate CO2 provides a renewable route to offset CO2 emissions and support a more sustainable global carbon cycle. More importantly, the direct photoreduction of CO2 into CO, rather than CH4, is arguably the technologically and economically preferred approach. In the grant proposal, I reported a strategy for depositing phase-modified Au nanoparticles abundant with stable twinned crystal planes as a co-catalyst on TiO2 for the effective photocatalytic reduction of CO2 to CO. Compared to pristine TiO2, the addition of twinned Au nanoparticles raise photocatalytic CO production activity by nearly 40-fold and establishes near unity CO selectivity (99%). (Angewandte Chemie - International Edition, 2022, 10.1002/anie.202204563)
The Suzuki coupling reaction is one of the most important organic synthetic methods for C–C bond formation. Recent research has shown the possibility to enhance the Suzuki coupling reaction under light irradiation through the use of photocatalytic supports in combination with Pd NPs. Yet, the temperature-dependent photocatalytic activity of Pd-photocatalytic support hybrids is seldom investigated. Therefore, I try to introducte Pd cube onto perovskite to synthesize highly efficient photocatalyst for organic transformation.The Pd/CsPbBr3 catalyst exhibits 11 times higher activity than pure CsPbBr3 at 30 °C due to reduced activation barrier and facilitated charge carrier dynamics. This work has been published: ACS Applied Materials & Interfaces 2022, 14, 15, 17185–17194.
Recently, metal halide perovskites (MHPs) have emerged as efficient H2 evolution photocatalysts. However, most of the H2 evolution reaction (HER) experiments are performed in saturated aqueous hydrohalic acid HX (X = Br and I) solutions. Based on the above work, I have prepared crystalline-amorphous core@shell Pd (APd) cube decorated Cs3Bi2Br9 photocatalyst, to further improve the photocatalytic performance of H2 evolution coupled with organic synthesis. Such a dual-purpose photocatalytic reaction offers an excellent alternative for H2 evolution over MHP photocatalysts avoiding concentrated hydrohalic acid solutions. As a result, the optimized APd/Cs3Bi2Br9 photocatalyst exhibits over 4-fold higher photoactivity that the pure Cs3Bi2Br9 counterpart toward H2 and benzaldehyde production.
Photocatalytic conversion of light to the chemical fuel appears to be an ideal green approach and the above mentioned works clearly exhibit how to improve the photocatalytic performance towards solar to energy conversion, i.e. engineering the phase, morphology and structure of cocatalysts.
The efficient utilization of sunlight to activate CO2 provides a renewable route to offset CO2 emissions and support a more sustainable global carbon cycle. More importantly, the direct photoreduction of CO2 into CO, rather than CH4, is arguably the technologically and economically preferred approach. In the grant proposal, I reported a strategy for depositing phase-modified Au nanoparticles abundant with stable twinned crystal planes as a co-catalyst on TiO2 for the effective photocatalytic reduction of CO2 to CO. Compared to pristine TiO2, the addition of twinned Au nanoparticles raise photocatalytic CO production activity by nearly 40-fold and establishes near unity CO selectivity (99%). (Angewandte Chemie - International Edition, 2022, 10.1002/anie.202204563)
The Suzuki coupling reaction is one of the most important organic synthetic methods for C–C bond formation. Recent research has shown the possibility to enhance the Suzuki coupling reaction under light irradiation through the use of photocatalytic supports in combination with Pd NPs. Yet, the temperature-dependent photocatalytic activity of Pd-photocatalytic support hybrids is seldom investigated. Therefore, I try to introducte Pd cube onto perovskite to synthesize highly efficient photocatalyst for organic transformation.The Pd/CsPbBr3 catalyst exhibits 11 times higher activity than pure CsPbBr3 at 30 °C due to reduced activation barrier and facilitated charge carrier dynamics. This work has been published: ACS Applied Materials & Interfaces 2022, 14, 15, 17185–17194.
Recently, metal halide perovskites (MHPs) have emerged as efficient H2 evolution photocatalysts. However, most of the H2 evolution reaction (HER) experiments are performed in saturated aqueous hydrohalic acid HX (X = Br and I) solutions. Based on the above work, I have prepared crystalline-amorphous core@shell Pd (APd) cube decorated Cs3Bi2Br9 photocatalyst, to further improve the photocatalytic performance of H2 evolution coupled with organic synthesis. Such a dual-purpose photocatalytic reaction offers an excellent alternative for H2 evolution over MHP photocatalysts avoiding concentrated hydrohalic acid solutions. As a result, the optimized APd/Cs3Bi2Br9 photocatalyst exhibits over 4-fold higher photoactivity that the pure Cs3Bi2Br9 counterpart toward H2 and benzaldehyde production.
Photocatalytic conversion of light to the chemical fuel appears to be an ideal green approach and the above mentioned works clearly exhibit how to improve the photocatalytic performance towards solar to energy conversion, i.e. engineering the phase, morphology and structure of cocatalysts.
Some typic examples and results are introduced briefly in the following text.
1. I have reported a strategy for depositing phase-modified Au nanoparticles abundant with stable twinned crystal planes as a co-catalyst on TiO2 for the photocatalytic reduction of CO2 to CO. Compared to pristine TiO2, the addition of twinned Au nanoparticles boost the activity by nearly 40-fold and establishes near unity CO selectivity (99%). This enhancement is due to a beneficial shift in the surface reactive site energetics arising at the twinned stacking fault, whereby both the CO reaction energy and desorption energy are significantly reduced – a physio-chemical response confirmed by ab initio thermodynamic modelling.
2. I have also reported introduction of Pd onto perovskite to synthesize highly efficient photocatalyst for organic transformation.The Pd/CsPbBr3 catalyst exhibits 11 times higher activity than pure CsPbBr3 at 30 °C due to reduced activation barrier and facilitated charge carrier dynamics. Furthermore, the alkoxide radicals (R–O–) for the Suzuki reaction are experimentally and theoretically confirmed, and photogenerated holes are proven to be crucial for cleaving C–B bonds of phenylboronic acids to drive the reaction. This work prescribes a general strategy to study photothermal catalysis and offers a mechanistic guideline for photothermal Suzuki reactions.
3. Based on the above work, I have expanded the concept of Schottky junction by using a phase-engineered crystalline-amorphous core@shell Pd (APd) cube decorated Cs3Bi2Br9 photocatalyst, to further improve the photocatalytic performance of H2 evolution coupled with organic synthesis, through a photocatalytic dual-functional reaction system. The optimized APd/Cs3Bi2Br9 photocatalyst exhibits over 4-fold higher photoactivity that the pure Cs3Bi2Br9 counterpart toward H2 and benzaldehyde production. In addition, compared to the widely used precipitation-solubility dynamic equilibrium technology for H2 evolution over MHPs, this dual-functional reaction can be easily carried out under mild conditions, which get rid of the haloacid solutions and additional reducing agents.
Overview of the results and exploitation and dissemination:
The results of MSCA project have been disseminated via specialized peer-reviewed journals with high visibility within the community. 7 peer-reviewed research work have been published in different journals with high impact. Further, general results could be promoted via the website: www.roeffaers-lab.org and www.roeffaers-lab.org/publications/. On this website, we (will) share news on the general research aspects, highlights such as, e.g. publications and awards, but the site can also explain the capabilities of the tools available in the labs, and that can be of interest to users in academia and industry. Moreover, our published work are also list and share by researchgate (https://www.researchgate.net/profile/Bo-Weng(si apre in una nuova finestra)) google scholar (https://scholar.google.com.hk/citations?hl=zh-CN&user=uo6X3KYAAAAJ&view_op=list_works&sortby=pubdate#(si apre in una nuova finestra)) and Twitter (https://twitter.com/BoWeng24154463(si apre in una nuova finestra)) via my own profile.
1. I have reported a strategy for depositing phase-modified Au nanoparticles abundant with stable twinned crystal planes as a co-catalyst on TiO2 for the photocatalytic reduction of CO2 to CO. Compared to pristine TiO2, the addition of twinned Au nanoparticles boost the activity by nearly 40-fold and establishes near unity CO selectivity (99%). This enhancement is due to a beneficial shift in the surface reactive site energetics arising at the twinned stacking fault, whereby both the CO reaction energy and desorption energy are significantly reduced – a physio-chemical response confirmed by ab initio thermodynamic modelling.
2. I have also reported introduction of Pd onto perovskite to synthesize highly efficient photocatalyst for organic transformation.The Pd/CsPbBr3 catalyst exhibits 11 times higher activity than pure CsPbBr3 at 30 °C due to reduced activation barrier and facilitated charge carrier dynamics. Furthermore, the alkoxide radicals (R–O–) for the Suzuki reaction are experimentally and theoretically confirmed, and photogenerated holes are proven to be crucial for cleaving C–B bonds of phenylboronic acids to drive the reaction. This work prescribes a general strategy to study photothermal catalysis and offers a mechanistic guideline for photothermal Suzuki reactions.
3. Based on the above work, I have expanded the concept of Schottky junction by using a phase-engineered crystalline-amorphous core@shell Pd (APd) cube decorated Cs3Bi2Br9 photocatalyst, to further improve the photocatalytic performance of H2 evolution coupled with organic synthesis, through a photocatalytic dual-functional reaction system. The optimized APd/Cs3Bi2Br9 photocatalyst exhibits over 4-fold higher photoactivity that the pure Cs3Bi2Br9 counterpart toward H2 and benzaldehyde production. In addition, compared to the widely used precipitation-solubility dynamic equilibrium technology for H2 evolution over MHPs, this dual-functional reaction can be easily carried out under mild conditions, which get rid of the haloacid solutions and additional reducing agents.
Overview of the results and exploitation and dissemination:
The results of MSCA project have been disseminated via specialized peer-reviewed journals with high visibility within the community. 7 peer-reviewed research work have been published in different journals with high impact. Further, general results could be promoted via the website: www.roeffaers-lab.org and www.roeffaers-lab.org/publications/. On this website, we (will) share news on the general research aspects, highlights such as, e.g. publications and awards, but the site can also explain the capabilities of the tools available in the labs, and that can be of interest to users in academia and industry. Moreover, our published work are also list and share by researchgate (https://www.researchgate.net/profile/Bo-Weng(si apre in una nuova finestra)) google scholar (https://scholar.google.com.hk/citations?hl=zh-CN&user=uo6X3KYAAAAJ&view_op=list_works&sortby=pubdate#(si apre in una nuova finestra)) and Twitter (https://twitter.com/BoWeng24154463(si apre in una nuova finestra)) via my own profile.
I started my MSCA postdoctoral research work from 1st April 2020 under the supervision of Prof. Roeffaers. The successful completion of Marie Curie IF is not only prestigious for my career but also helped me to demonstrate my capability to obtain funding, managing project and successfully completing it on time in a new country and different work environment, a valuable quality in a scientific field. This demonstration also helped me to apply for the FWO junior postdoc and I also own this project. In the next 10 years, I foresee myself establishing my lab in a world-renowned institution, focusing on the development of a comprehensive understanding of metal Au-based and perovskite-based photocatalysts for solar fuel generation. During the fellowship, I was also able to make many scientific contacts with pioneers in the field that is always an added advantage. The results were obtained during the fellowship that could be further extrapolated for applying grants such as ERC starting or to other European funding opportunities.