The Department of Physics is glad to announce that Dr Ranjit Thapa and his PhD scholar Mr Samadhan Kapse have published their research paper “Descriptors and graphical construction for in silico design of efficient and selective single-atom catalysts for eNRR” in the journal Chemical Science, having an Impact Factor of 9.969. The paper was published in collaboration with Prof Shobhana Narasimhan, Theoretical Sciences Unit and School of Advanced Materials, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore. Chemical Science is a highly prestigious nature Index journal, which accepts only breakthrough research contributions for publication.
The Haber-Bosch process for ammonia synthesis has been described as possibly the most important scientific discovery of the twentieth century. However, it requires high temperatures and pressures and results in large energy consumption and emission of greenhouse gases. That is where electrochemical nitrogen reduction reaction (eNRR) comes into the picture. It synthesizes ammonia from nitrogen and water under mild conditions (N2 + 6H+ + 6e- → 2NH3). However, currently available eNRR catalysts need improvement in three respects: (i) the efficiency of nitrogen fixation needs to be increased, (ii) the competing hydrogen evolution reaction (HER) needs to be suppressed, and (iii) hydrogen poisoning of active sites must be avoided. Transition metals are popular eNRR catalysts; however, they tend to favour hydrogen adsorption due to the formation of strong metal d – hydrogen σ bonds, and tend to have a low affinity for N2 adsorption. Their research mitigates these problems by appropriately tuning the electronic structure by altering the environment surrounding metal atoms at the active site of single-atom catalysts (SACs). Moreover, in previous works, typically, only one criterion (usually competing HER) was used to optimize catalyst function, whereas they simultaneously optimised the catalyst function with respect to multiple criteria.
They have screened 66 different transition metal-based SACs for possible use in eNRR. To determine the best possible catalyst, they considered three factors: N2 adsorption, hydrogen poisoning and the overpotential of eNRR. Here, the valence electron occupancy (Oval) is identified as a new electronic descriptor that can predict the overpotential value. They emphasised that having a low η_NRR alone does not suffice to indicate a suitable eNRR catalyst, since if the adsorption free energy is higher for H than N2, active sites will be poisoned, hindering eNRR. Thus, they present a simple graphical procedure for identifying the most promising catalysts. To carry out this procedure, one must compute only 〖ΔG〗_(H^* ) and 〖ΔG〗_(NNH^* ), the changes in the free energies of H and NNH adsorption, respectively (note that η_NRR can be deduced if 〖ΔG〗_(NNH^* ) is known). The most promising candidate is identified as Sc-Pc, which they predict will have no H poisoning and will be highly selective for eNRR over HER. Moreover, they predict that Mn-Pc, Cr-N4, Fe-N2C2 should also be highly efficient, with low overpotential (η_NRR < 1 V) toward eNRR, and no H poisoning. In future they aim to find the selective materials for catalytic reactions by studying the origin of activity, reaction mechanism, etc.
Abstract of the Research
The electrochemical nitrogen reduction reaction (eNRR) offers the possibility of ammonia synthesis under mild conditions; however, it suffers from low yields, a competing hydrogen evolution reaction pathway, and hydrogen poisoning. We present a systematic approach toward screening single atom catalysts (SACs) for eNRR, by focusing on key parameters computed from density functional theory, and relationships between them. We illustrate this by application to 66 model catalysts of the types, TM-Pc, TM-NXCY, and TM-N3, where TM is a 3d transition metal or molybdenum. We identified the best SACs as Sc-Pc, Cr-N4, Mn-Pc, and Fe-N2C2; these show eNRR selectivity over HER and no hydrogen poisoning. The catalysts are identified through multi-parameter optimization which includes the condition of hydrogen poisoning. We propose a new electronic descriptor Oval, the valence electron occupancy of the metal center, that exhibits a volcano-type relationship with eNRR overpotential. Our multi-parameter optimization approach can be mapped onto a simple graphical construction to find the best catalyst for eNRR over HER and hydrogen poisoning.