Tuning Internal Strain in Metal–Organic Frameworks via Vapor Phase Infiltration for CO2 Reduction. Issue 11 (29th January 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 international edition. Volume 59:Issue 11(2020)
• Page Start: 4572
• Page End: 4580
• Publication Date: 2020-01-29
• Subjects: CO2 reduction -- internal strain -- metal–organic frameworks -- vapor-phase infiltration; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202000022
• Languages: English
• ISSNs: 1433-7851

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 : Internal strain was precisely controlled to advance the innate catalytic activity of a metalloporphyrin on MOFs. Vapor‐phase infiltration (VPI) was utilized to produce metal oxide clusters inside the MOF structure. The strained catalyst demonstrated pronounced catalytic activity improvement, showing the potential of the VPI strategy to improve intrinsic catalytic performance of a variety of catalysts.