Facet-dependent solar ammonia synthesis of BiOCl nanosheets via a proton-assisted electron transfer pathway. Issue 4 (24th December 2015)

• Record Type: Journal Article
• Authors: Li, Hao; Shang, Jian; Shi, Jingu; Zhao, Kun; Zhang, Lizhi
• Is Part Of: Nanoscale. Volume 8:Issue 4(2016)
• Page Start: 1986
• Page End: 1993
• Publication Date: 2015-12-24
• Subjects: Nanoscience -- Periodicals; Nanotechnology -- Periodicals; 620.505
• DOI: 10.1039/c5nr07380d
• Languages: English
• ISSNs: 2040-3364

Abstract

Abstract : The distinct structures of oxygen vacancies on different BiOCl facets strongly affect their solar N2 fixation via a proton-assisted electron transfer pathway. Abstract : Under the pressure of a fossil fuels shortage and global climate change, solar ammonia synthesis and the need to develop N2 fixation under mild conditions is becoming more urgent need; however, their intrinsic mechanisms still remain unclear. Herein, we demonstrate that the kinetic inertia of N2 can be overcome using oxygen vacancies (OVs) of BiOCl as the catalytic centers to create lower energy molecular steps, which are amendable for the solar light driven N–N triple bond cleavage via a proton-assisted electron transfer pathway. Moreover, the distinct structures of OVs on different BiOCl facets strongly determine the N2 fixation pathways by influencing both the adsorption structure and the activation level of N2 . The fixation of terminal end-on bound N2 on the OVs of BiOCl {001} facets follows an asymmetric distal mode by selectively generating NH3, while the reduction of side-on bridging N2 on the OVs of BiOCl {010} facets is more energetically favorable in a symmetric alternating mode to produce N2 H4 as the main intermediate.