RESUMO
The development of an efficient, selective, and durable catalysis system for the electrocatalytic N2 reduction reaction (ENRR) is a promising strategy for the sustainable production of ammonia. The high-performance ENRR is limited by two major challenges: poor adsorption of N2 over the catalyst surface and abysmal N2 solubility in aqueous electrolytes. Herein, with the help of our combined density functional theory (DFT) calculations and experimental electrocatalysis study, we demonstrate that concurrently induced electron-deficient Lewis acid sites in an electrocatalyst and in an electrolyte medium can significantly boost the ENRR performance. The DFT calculations, ex situ X-ray photoelectron and FTIR spectroscopy, electrochemical measurements, and N2-TPD (temperature-programmed desorption) over boron-doped strontium titanate (BSTO) samples reveal that the Lewis acid-base interactions of N2 synergistically enhance the adsorption and activation of N2. Besides, the B-dopant induces the defect sites (oxygen vacancies and Ti3+) that assist in enhanced N2 adsorption and results in suppressed hydrogen evolution due to B-induced electron-deficient sites for H+ adsorption. The insights from the DFT study evince that B prefers the Srtop position (on top of Sr) where N2 adsorbs in an end-on configuration, which favors the associative alternating pathway and suppresses the competitive hydrogen evolution. Thus, our combined experimental and DFT study demonstrates an insight toward enhancing the ENRR performance along with the suppressed hydrogen evolution via concurrently engineered electron-deficient sites at electrode and electrolyte interfaces.
RESUMO
The development of sustainable catalysts to get methanol from CO2 under milder conditions and without any additives is still considered an arduous task. In many instances, transition-metal-catalyzed carbon dioxide to formic acid formation is more facile than methanol formation. This article provides comprehensive density functional theoretic investigations of six new Mn(I)PNN complexes, which are designed to perform CO2 to methanol conversion under milder reaction conditions. All these six catalysts have similar structural features except at terminal nitrogen, -N (1), where adenine-inspired nitrogen heterocycles containing pyridine and pyrimidine moieties are attached to instill an electron withdrawing effect on the central metal and thus to facilitate dihydrogen polarization during the catalyst regeneration. All these computationally modeled Mn(I)PNN complexes demonstrate the promising catalytic activity to get methanol through cascade catalytic cycles at 298.15 K. The metal-ligand cooperative (MLC) as well as noncooperative (NC) pathways are investigated for each catalytic cycle. The NC pathway is the preferred pathway for formic acid and formaldehyde formation, whereas methanol formation proceeds through only the MLC pathway. Different nitrogen heterocycles attached to the -N (1) terminal manifested a considerable amount of impact on the Gibbs free energies, overall activation energies, and computed turnover frequencies (TOFs). Among all the catalysts, SPCAT02 provides excellent TOFs for HCO2H (500 151 h-1), HCHO (11 912 h-1), and CH3OH (2 372 400 h-1) formation at 50 °C. SPCAT04 is found to be a better catalyst for the selective formation of formic acid formation at room temperature than the rest of the catalysts. The computed TOF results are found reliable upon comparison with experimentally established catalysts. To establish the structure-activity relationship, the activation strain model and Fukui function calculations are performed on all the catalysts. Both these studies provide complementary results. The present study revealed a very important finding that a more electrophilic metal center could facilitate the CO2 hydrogenation reaction robustly. All computationally designed catalysts could be cheaper and better alternatives to convert CO2 to methanol under mild reaction conditions in an aqueous medium.