Work Function-Tailored Nitrogenase-like Fe Double-Atom Catalysts on Transition Metal Dichalcogenides for Nitrogen Fixation

Abstract

The work function−activity relationship provides a new strategy to design catalysts by tailoring the work function. A lower work function (φ) is widely believed to be in favor of better catalytic activity due to the easier electron transfer from the catalyst surface to reactants and/or intermediates. In this work, the φ values of nitrogenase-like Fe double-atom catalysts (Fe 2 /MX 2 , MX 2 : transition metal dichalcogenides) were tailored by altering the MX 2 supports for nitrogen (N 2 ) fixation. By density functional theory calculations, it is found that a lower φ caused by the increasing period number of the transition metal or chalcogen of MX 2 impairs the catalytic activity. This abnormal φ-activity relationship is mainly due to the overstrong N 2 adsorption on Fe 2 /MX 2 . Based on our strategy, Fe 2 /VS 2 , Fe 2 /CrS 2 , Fe 2 /MoS 2 , and Fe 2 /WS 2 having relatively large φ values (4.44−5.81 eV) show excellent activity toward N 2 fixation with the overpotential values of 0.21−0.25 V.

Experimentally revealed and theoretically certified synergistic electronic interaction of V-doped CoS for facilitating the oxygen evolution reaction

“…57 The work function ( W F ) of metal materials is an initial energy electron from the metal within the minimum energy required to escape to a vacuum. 58 The W F is usually about half the ionization energy of a metal free atom. The W F can be calculated using the formula in Supplementary Note S1 (ESI†).…”

Theoretical Revelation and Experimental Verification Synergistic Electronic Interaction of V-Doped RuNi as an Efficient Bifunctional Electrocatalyst for Overall Water Splitting

“…According to the UPS results depicted in Figure e, it can be inferred that there is a significant correlation between the doping of V and Mo metals . The metal work function (W F ) represents the minimum energy required for an electron to escape from the metal and enter a vacuum . An alternative expression for calculating the W F can be found in eq S8 .…”

Optimizing the NRR activity of single and double boron atom catalysts using a suitable support: a first principles investigation

“…17,18 Until now single and double atom catalysts (SACs and DACs) of different transition metals with variable supports have been screened efficiently both experimentally and theoretically, leading to various design principles and important generalizations for catalyst design with respect to the NRR. 19–42 Along similar directions, there has been a greater demand to design transition metal free catalysts (TMFCs) for the NRR due to their promising catalytic activity and durability. In addition, the cheap and abundant nature of TMFCs makes their development for N 2 reduction highly imperative from an economic point of view.…”