High Throughput DFT Calculations on Single Atom Catalysts for Solar Fuel Generation

Abstract

Fossil fuels have been the primary source of rising energy requirements for humankind. However, the extensive use of fossil fuels has led to an increase in Earth's surface temperature. To tackle rising energy demands and the increase in Earth's surface temperature, various organizations like Inter-governmental Panel for Climate Change and the European Environmental Agency have suggested the use of renewable energy as an alternative energy supply. E.g., the use of hydrogen as an alternative fuel in transportation will reduce greenhouse gas emissions. Besides, converting CO2 and N2 to fuels and industrial feedstock like CO or NH¬3 can curb the Earth's increasing surface temperature. As a result of this, in this thesis, the catalysts for the synthesis of hydrogen from water-splitting (hydrogen evolution reaction- HER), conversion of CO2 to CO via carbon dioxide reduction reaction (CO2RR), and reduction of N2 from air to NH3 (Nitrogen reduction reaction-N2RR) are studied. The conventional catalysts used for these reactions are Pt for HER, Cu for CO2RR Cu, and Ru for N2RR. Although these catalysts are active and exhibit a high yield of products, they have some disadvantages, such as the long-term availability and cost of Pt and Ru. On the other hand, Cu suffers from the low selectivity for the conversion from CO2 to CO. To overcome these disadvantages; scientists have developed a new kind of catalyst with a higher specific activity, known as the Single-Atom Catalysts (SAC). The SACs use fewer precious elements than the conventional bulk catalysts without compromising the activity. The use of binding energy (EB) as a descriptor for the reactions mentioned has been proven in the literature. Therefore, EB is used in this thesis to predict novel SACs through high-throughput DFT calculations using 3-N doped graphene as the substrate. The descriptor for HER is the EB of H atom, for CO2RR is EB of CO, and that of N2RR is EB of N on the respective catalyst surfaces. These calculated binding energies are compared against the descriptor EB on the conventional catalysts to obtain the novel SACs. With EB as the descriptor, the candidate catalysts for HER are B, Cr, Mn, Fe, Co, Ni, Ge, Ru, In, Sb, La, and Pb. The candidate catalysts for N2RR are Ru, Mo, and Cr. The candidate catalysts for CO2RR are Mg, Al, Ca, Zn and Se,. In addition to this, the charge dissipation of the adsorbent species on the SAC and the effect of atomic size on the EB is studied. It was seen that the computational predictions go hand in hand with the predictions of existing experiments for HER and CO2RR.