Lattice distortion induced enhanced activity of W-doped Bi 2 MoO 6 nanosheets for efficient photocatalytic nitrogen fixation Manisha Sharma 1 , Ashish Kumar 1# , Shilpi Jaiswal 2 , Abhijit Patra 2 and Venkata Krishnan 1* 1 School of Basic Sciences and Advanced Materials Research Center, Indian Institute of Technology Mandi, Kamand, Mandi 175075, Himachal Pradesh, India, 2 Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Madhya Pradesh 462066, India # Present Address: Department of Chemistry, Sardar Patel University Mandi, Mandi 175001, Himachal Pradesh, India. NH 3 , being the raw material for various fertilizers and pharmaceutical products holds great importance in chemical industries. 1 The conventional way of producing NH 3 which is the Haber-Bosch process is neither green nor sustainable because of its high energy demands. This process consumes about 1-3% of global annual energy. 2 In recent years, the photocatalytic reduction of N 2 into NH 3 has become a hot topic due to its green, sustainable, and cost-effective approach. 3 However, photocatalysts suffer from the fast recombination of charge carriers which can hinder the photocatalytic activity. Defect engineering has proven to increase the surface active sites as well as decrease the recombination. 4 In this work, we have synthesized W-doped Bi 2 MoO 6 nanosheets in various molar ratios and compared their photocatalytic activity to produce NH 3 . It was found that the photocatalytic activity for the BMWO 0.4 was increased 13 times more than pristine Bi 2 MoO 6 . The production of NH 3 was increased to 71 µmol for BMWO 0.4 in 120 min. The increased photocatalytic activity could be attributed to the lattice distortions because of Mo substitution by the W atom. Also, the presence of oxygen vacancies in BMWO 0.4 led to more absorption of visible light as well as decreased the recombination of charge carriers. The stability and recyclability of the photocatalyst makes it a promising material for photocatalytic nitrogen fixation and provides an insight into the structurally induced activity of the photocatalysts. References 1. Liu, Q.-Y.; Wang, H.-D.; Tang, R.; Cheng, Q.; Yuan, Y.-J., Rutile TiO2 nanoparticles with oxygen vacancy for photocatalytic nitrogen fixation. ACS Applied Nano Materials 2021, 4 (9), 8674-8679. 2. Kumar, A.; Krishnan, V., Vacancy engineering in semiconductor photocatalysts: Implications in hydrogen evolution and nitrogen fixation applications. Advanced Functional Materials 2021, 31 (28), 2009807. 3. Kumar, A.; Kumar, M.; Rao, V. N.; Shankar, M. V.; Bhattacharya, S.; Krishnan, V., Unraveling the structural and morphological stability of oxygen vacancy engineered leaf-templated CaTiO 3 towards photocatalytic H 2 evolution and N 2 fixation reactions. Journal of Materials Chemistry A 2021, 9 (31), 17006-17018. 4. Sharma, M.; Kumar, A.; Krishnan, V., Influence of oxygen vacancy defects on Aurivillius phase layered perovskite oxides of bismuth towards photocatalytic environmental remediation. Nanotechnology 2022, 33 (27), 275702.
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