In summary, we have performed an in-depth theoretical investigation on GaN monolayer supported TM-SACs and elucidated various mechanistic pathways towards CO2RR. Using stability descriptors (Estab and Udiss), we implied that the proposed catalysts are thermodynamically and electrochemically stable. Through Bader charge analysis, we show that a well-defined active site and directional charge transfer from surface to adsorbate is imperative for achieving a high catalytic performance. A comparative mechanistic analysis further revealed that CO2RR on Ti/V/Cr/Mn/Zr/Nb/Mo/Ru/Rh/Hf/
Ta/W/Re embedded SACs proceeds via two-electron pathway and yield HCOOH, rather than CO, while the Os- and Ir-SACs follow *COOH route to generate *CO, which leads to a more facile reaction pathway to produce CH4. By calculating the energy barrier at each step, we find that the Mn- and Rh- SACs have the best catalytic activity towards the formation of HCOOH with the lowest UL(s) of -0.50 V and -0.42 V, respectively, while the Ir-SAC exhibits a better catalytic activity for CH4 production with a UL of -0.48 V and a selectivity of 97% against the competing HER process, credited to its moderate binding with various CO2RR intermediates. We envision that the mechanistic insights demonstrated in this work stimulate further interest to design new high-performance CO2RR catalysts.
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Acknowledgements
All praise is due to Allah, the Creator and Sustainer of the universe, for His showers of blessings throughout my research work to complete the research successfully, and may His peace and blessings be upon our Holy Prophet, the ever-shining torch of guidance, knowledge, love and peace for entire humanity.
I would first and foremost like to thank my supervisor Prof. Geunsik Lee who trusted in my skills. The knowledge I have gained under his leadership is invaluable and I will be forever grateful to him as one of his research students. I am deeply thankful to Prof. Kwang Soo Kim, for his support at every step.
This study would have not been possible without his continuous rigorous critique, scholarly comments, suggestions, and inspiring guidance.
I wish to thank my committee member Prof. Myung Jong Kim who was more than generous with his expertise and precious time.
I appreciate and thank all my lab fellows for their constant support and encouragement. I appreciate and specially thank, Muhammad Umer who guided me at every step of the research - from planning to completion.
I dedicate this work to my parents, sisters, and brother for their endless love, support and encouragement throughout my life.
Thank you all for the incredible support.