Interface engineering of cerium dioxide enables CO 2 photoreduction to green methanol Subhajit Chakraborty a,b , Mohd Riyaz a,b , Harishankar Kopperi c,d , Sathyapal R Churipard a,b , Risov Das a,b , Mohammed Jasil a,b , Nilutpal Dutta a,b , C. P. Vinod e , S. Venkata Mohan c,d and Sebastian C. Peter a,b * a New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore-560064, India, b School of Advanced Materials, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore-560064, India, c Bioengineering and Environmental Sciences Lab, Department of Energy and Environmental Engineering (DEEE), CSIR-Indian Institute of Chemical Technology (CSIR-IICT), Hyderabad 500007, India, d Academy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India, e Catalysis and Inorganic Chemistry Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune, 410008, India *Email: sebastiancp@jncasr.ac.in, sebastiancp@gmail.com Harnessing solar energy for CO 2 conversion into carbonaceous products is a growing research focus but suffers from low efficiency due to multielectron transfer and sluggish kinetics. 1 With multiple CO 2 reduction products, green METHANOL stands out as a key industrial product. 2 However, its formation requires stabilizing the *CO 2 - intermediate, posing a significant challenge for catalyst design. Here, we obtain a new scientific concept, EXSOLUTION, for catalyst design, where we modify the surface of CeO 2 with the exsolution of the metal (here, Bismuth) originating from the host lattice. 3 The exsolved metallic Bi nanoparticles were well socketed on the CeO 2 support, experiencing metal-support interactions, leading to the well dispersity facilitating selective conversion of CO 2 to methanol. The catalyst efficiently converts CO 2 to CH 3 OH with 87.1% selectivity and 723.2 µmol g -1 h -1 evolution rate without using any sacrificial agent, which is comparatively higher than all of the methanol-generated photocatalysts, as per our knowledge. The strong interactions between metal and support enhance the stability of *CO 2 - over the surface by the electronic interaction with Bi d + . The unusual electron transfer kinetics is feasible by the generation of ‘partial Ohmic contact’ at the metal-semiconductor interface. The exsolved metallic Bi on the CeO 2 support has been mapped using a combination of in-situ and ex-situ spectroscopic and microscopic techniques. Density Functional Theory (DFT) corroborates with in-situ Diffuse Reflectance infrared Fourier- transform spectroscopy (DRIFTs) and surface-enhanced in situ RAMAN spectroscopy, giving an implicit idea about the reaction pathway of methanol production from CO 2 . Life Cycle Assessment indicates negative emission impacts with the use of a hydropower grid for the production of 1 Kg of green methanol by photocatalytic CO 2 reduction route and thus guardrails beyond Green House Gas (GHG) emissions for the transformative actions of decarbonization. Acknowledgements: Financial support from the Department of Science and Technology (DST/TMD/(EWO)/IC#5- 2018/02 and DST/TMDEWO/CCUS/CoE/2020/JNCASR(c)) is gratefully acknowledged. SCP thanks DST for the Swarna Jayanti Fellowship (DST/SJF/CSA-02/2017-18) and Sheikh Saud Laboratory for Career Fellowship.. SC, RD, and DB thank CSIR, KD thank DST, and AKS thank JNCASR for the research fellowship. ‘The National Supercomputing Mission (Param Yukti)‘ at JNCASR for computational resources. Parts of this research were also carried out at the light source PETRA III at DESY, a member of the Helmholtz Association (HGF), and we thank Dr. Wolfgang Caliebe for assistance in using PETRA III beamline P64 at DESY, Germany. Thankful to DST for the financial assistance for the measurement at DESY. References 1. S. Fang, M. Rahaman, J. Bharti, E. Reisner, M. Robert, G. A. Ozin et al., Nat Rev Methods Primers , 2023, 3 , 61. 2. P. Ganji, R. K. Chowdari and B. Likozar, Energy Fuels , 2023, 37 , 7577-7602. 3. D. Neagu, G. et al., Nat. Chem. , 2013, 5 , 916-923.
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