Hybrid Metal–Boron Diatomic Site Embedded in C2N Monolayer Promotes C–C Coupling in CO2 Electroreduction. Issue 42 (23rd September 2021)

• Record Type: Journal Article
• Authors: He, Miaomiao; An, Wei; Wang, Yuanqiang; Men, Yong; Liu, Shuang
• Is Part Of: Small. Volume 17:Issue 42(2021)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-09-23
• Subjects: CO 2 electroreduction -- C–C coupling -- C 2N -- double‐atom catalyst -- density functional theory; Nanotechnology -- Periodicals; Nanoparticles -- Periodicals; Microtechnology -- Periodicals; 620.5
• DOI: 10.1002/smll.202104445
• Languages: English
• ISSNs: 1613-6810

Abstract

Abstract: Double‐atom catalyst (DAC) has gained much interest for its versatile tuning and synergistic effect of dual‐atom active sites. Metal (M)–metal (M) diatomic sites, either homo‐ or heteronuclear, are typically researched. Hybrid metal‐non‐metal combined sites have rarely been studied and even the viability of such active sites are unknown. Herein, CO2 electroreduction (CO2 RR) is explored on M@X‐C2 N (M = Fe, Co, Ni, and Cu; X = S, P, and B) which renders naturally generated M–X diatomic site. Using spin‐polarized density functional theory coupled with computational hydrogen electrode model, it is demonstrated that the functionality of hybrid M–B dual‐atom center is superior over that of a single‐ or double‐M center in driving CO2 RR especially C–C coupling. Among metal–boron DACs studies, Fe@B‐C2 N (μ = 2μB ) exhibits the lowest free energy barrier of 0.17 eV in C–C coupling whereas Ni@B‐C2 N (μ = 0μB ) mainly produces CH4 with the lowest barrier of 0.42 eV. Hence, the electronic spin state of M can be particularly important in modulating selectivity and C–C coupling barrier in CO2 RR. Fe@B‐C2 N is predicted as the promising catalyst for CO2 RR towards C2+ products owing partially to its enhanced spin state. The findings can enrich the design strategy of electrocatalysts normally running at ambient conditions. Abstract : Hybrid M–B dual‐atom center has been theoretically confirmed as the active site for CO2 electroreduction. Fe@B‐C2 N (μ = 2μB ) is predicted to be most active for promoting C–C coupling towards C2+ products owing partially to its enhanced spin state, whereas Ni@B‐C2 N (μ = 0μB ) mainly produces CH4 . The study provides the fundamental understanding of a well‐defined active site that enables facile CO2 electroreduction.