Activation of phosphorene-like two-dimensional GeSe for efficient electrocatalytic nitrogen reduction via states filtering of Ru. Issue 29 (29th June 2021)

• Record Type: Journal Article
• Authors: Shu, Zheng; Cai, Yongqing
• Is Part Of: Journal of materials chemistry. Volume 9:Issue 29(2021)
• Page Start: 16056
• Page End: 16064
• Publication Date: 2021-06-29
• Subjects: Materials -- Research -- Periodicals; Chemistry, Analytic -- Periodicals; Environmental sciences -- Research -- Periodicals; 543.0284
• DOI: 10.1039/d1ta03420k
• Languages: English
• ISSNs: 2050-7488

Abstract

Abstract : The filtered states of GeSe by a Ru dimer could lead to a superior NRR catalytic activity for the promoted activation of inert nitrogen bonds and subsequent reduction of nitrogen by hydrogenation. Abstract : A 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 it is revealed that a superior NRR catalytic activity could be obtained by anchoring an atomic catalyst above the phosphorene-like puckered surface of germanium selenide (GeSe). By examining the single- and double-atoms (B, Fe, Mo Ru and W) decorated on GeSe, it is found that its rippled structure allows an intimate contact between the deposited species and the GeSe which significantly promotes the states hybridization. Out of all the various atomic catalysts, it is found that the Ru dimer decorated GeSe monolayer (Ru2 @GeSe) has superior catalytic activity for the N2 fixation and reduction. By examining the three NRR pathways (distal, alternating and enzymatic), it was found that the distal and enzymatic pathways are both thermodynamically favorable with the maximum Gibbs free energy change (Δ G MAX ) of 0.25 and 0.26 eV, respectively. Such a superior activity could be attributed to the Ru dimer filtering the states of GeSe which leads to the effective activation of the adsorbed N2 bond. As an efficient near-infrared absorber of GeSe, the Ru mediated hybridization of the GeSe–Ru–N2 complex enables an in-gap state which further broadens the absorption window, rendering for a broadband solar absorption and possible photocatalysis.