Targeted Regulation of the Electronic States of Nickel Toward the Efficient Electrosynthesis of Benzonitrile and Hydrogen Production

Abstract

Highly efficient electro-oxidation of benzylamine to generate value-added chemicals coupled with the hydrogen evolution reaction (HER) is crucial but challenging. Herein, targeted regulation of the electronic states of Ni sites was realized via simple yet precise nitridation engineering. Benefiting from the insertion of N atoms into the Ni lattice, the Ni3N electrode exhibits superior activity, selectivity, and stability for the benzylamine oxidation reaction (BOR). Especially, under the industrially relevant current (∼250 mA), the Ni3N catalyst remains ∼95% selective for benzonitrile production, reaching 1.43 mmol h–1 cm–2. Experimental and theoretical findings reveal that the formation of Ni–N bonds upshifts the Ni d-band center and optimizes the electrophilic properties of Ni sites, which contributes to the adsorption and dehydrogenations process of benzylamine. Furthermore, due to the work function difference between Ni and Ni3N, a strong mutual interaction occurs at the heterogeneous interface for Ni-Ni3N, which endows it with the appropriate H* adsorption energy and thus excellent HER performance. Impressively, the integrated solar-energy-driven BOR coupled with the HER electrolyzer affords 10 mA cm–2 at an ultralow voltage of 1.4 V and exhibits a promising practical application (ηsolar‑to‑hydrogen = 13.8%). This work offers a new perspective for the bifunctional design of nitrides in the field of electrosynthesis.

Optimizing the Reaction Pathway by Active Site Regulation in the CdS/Fe2O3 Z-Scheme Heterojunction System for Highly Selective Photocatalytic Benzylamine Oxidation Integrated with H2 Production

“…To simplify the DFT calculation, two models, CdS (002) and Pt 10 /CdS (002) in Figure S24 , were constructed to explore the Gibbs free energy of hydrogen adsorption (Δ G H* ). Generally, Δ G H* is a useful descriptor to determine the H 2 production performance . The optimized models for H* adsorption on CdS (002) and Pt 10 /CdS (002) are shown in Figure S25.…”

“…Generally, ΔG H* is a useful descriptor to determine the H 2 production performance. 47 The optimized models for H* adsorption on CdS (002) and Pt 10 /CdS (002) are shown in Figure S25. In Figure 4h, the ΔG H* of CdS is 1.6 eV.…”

Plasmon-Enhanced Water Activation for Hydrogen Evolution from Ammonia-Borane Studied at a Single-Particle Level

“…48,49 As Figure S20 suggests, the contact angle of Pt− Au NRs with H 2 O is 12.16°, which is smaller than that of Au NRs (26.25°), indicating the stronger adsorption behavior of Pt−Au NRs than Au NRs. 50 We hypothesized that the difference in interfacial charge transfer could be explained by the Pt−H 2 O complexes formed when water molecules were adsorbed on the surface of Pt−Au NRs. 41,51 In addition, we applied atomic layer deposition (ALD) to deposit the Al 2 O 3 shell on the surface of Pt−Au NRs, which can insulate interaction between Pt atoms and water molecules.…”

BiVO4 quadrangular nanoprisms with highly exposed {101} facets for selective photocatalytic oxidation of benzylamine

“…Obviously, the N atom exhibits a negative potential relative to other groups in BnNH 2 , which may lie in the lone pair electrons of unequal sp 3 hybrid orbitals. 31,32 As a consequence, BnNH 2 molecules with a negatively charged N site may more easily adsorb on the surface Bi sites of m-BiVO 4 through the strong electrostatic interaction. The BnNH 2 adsorption energy on the (101) facet (À0.65 eV) is much lower than that on the (110) facet (À0.54 eV), indicating that {101} facets possess stronger BnNH 2 adsorption ability than {110} facets, which is favorable for the subsequent BnNH 2 oxidation process.…”