Tuning Internal Strain in Metal–Organic Frameworks via Vapor Phase Infiltration for CO2 Reduction. (14th February 2020)

• Record Type: Journal Article
• Authors: Yang, Fan; Hu, Wenhui; Yang, Chongqing; Patrick, Margaret; Cooksy, Andrew L.; Zhang, Jian; Aguiar, Jeffery A.; Fang, Chengcheng; Zhou, Yinghua; Meng, Ying Shirley; Huang, Jier; Gu, Jing
• Is Part Of: Angewandte Chemie. Volume 132:Number 11(2020)
• Page Start: 4602
• Page End: 4610
• Publication Date: 2020-02-14
• Subjects: CO2-Reduktion -- Interne Spannung -- Metallorganische Gerüste -- Dampfphaseninfiltration; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202000022
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: A gas‐phase approach to form Zn coordination sites on metal–organic frameworks (MOFs) by vapor‐phase infiltration (VPI) was developed. Compared to Zn sites synthesized by the solution‐phase method, VPI samples revealed approximately 2.8 % internal strain. Faradaic efficiency towards conversion of CO2 to CO was enhanced by up to a factor of four, and the initial potential was positively shifted by 200–300 mV. Using element‐specific X‐ray absorption spectroscopy, the local coordination environment of the Zn center was determined to have square‐pyramidal geometry with four Zn−N bonds in the equatorial plane and one Zn‐OH2 bond in the axial plane. The fine‐tuned internal strain was further supported by monitoring changes in XRD and UV/Visible absorption spectra across a range of infiltration cycles. The ability to use internal strain to increase catalytic activity of MOFs suggests that applying this strategy will enhance intrinsic catalytic capabilities of a variety of porous materials. Abstract : Die interne Spannung wurde genau kontrolliert, um die katalytische Aktivität eines Metalloporphyrins auf MOFs zu fördern. Dampfphaseninfiltration (VPI) wurde genutzt, um Metalloxid‐Cluster innerhalb der MOF‐Struktur zu erzeugen. Der gespannte Katalysator zeigte eine ausgeprägte Verbesserung der katalytischen Aktivität, was das Potenzial der VPI‐Strategie zur Verbesserung der intrinsischen katalytischen Leistung einer Vielzahl von Katalysatoren zeigt.