Activation of Phosphorene-like Two-dimensional GeSe for Efficient Electrocatalytic Nitrogen Reduction via States Filtering of Ru

TL;DR

This study uses first-principles calculations to demonstrate that Ru-dimer decorated GeSe monolayers exhibit enhanced catalytic activity for nitrogen reduction, with potential for broadband solar absorption and photocatalysis.

Contribution

It introduces a novel Ru-dimer decorated GeSe monolayer as an efficient catalyst for NRR, highlighting the role of states filtering and hybridization in activity enhancement.

Findings

Ru2@GeSe shows superior NRR catalytic activity.

Distal and enzymatic pathways are thermodynamically favorable.

GeSe-Ru-N2 complex enables broadband solar absorption.

Abstract

Nitrogen reduction reaction (NRR) which converts nitrogen (N2) to ammonia (NH3) normally requires harsh conditions to break the bound nitrogen bond. Herein, via first-principles calculation we reveal that a superior NRR catalytic activity could be obtained through anchoring atomic catalyst above a phosphorene-like puckering surface of germanium selenide (GeSe). Through examining the single- and double- atoms (B, Fe, W, Mo and Ru) decorated on GeSe, we find that its rippled structure allows an intimate contact between the deposited species and the GeSe which significantly promotes the states hybridization. Amongst the various atomic catalyst, we predict that the Ru dimer decorated GeSe monolayer (Ru2@GeSe) has superior catalytic activity for the N2 fixation and reduction. Through examining the three NRR pathways (distal, alternating and enzymatic), the distal and enzymatic pathway is both the thermodynamically favorable with the maximum Gibbs free energy change ({\Delta}GMAX) of 0.25 and 0.26 eV, respectively. Such a superior activity could be attributed to the filtered states of GeSe by Ru dimer which leads to the effective activation of the adsorbed N2 bond. As an efficient near-infrared absorber of GeSe, the Ru mediated hybridization of GeSe-Ru-N2 complex enables an in-gap state which further broadens the absorbing window, rendering for a broadband solar absorption and possible photocatalysis.