Premium
Tuning Internal Strain in Metal–Organic Frameworks via Vapor Phase Infiltration for CO 2 Reduction
Author(s) -
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
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202000022
Subject(s) - porosity , absorption spectroscopy , catalysis , metal organic framework , metal , materials science , phase (matter) , infrared spectroscopy , extended x ray absorption fine structure , chemistry , analytical chemistry (journal) , chemical engineering , composite material , organic chemistry , metallurgy , optics , adsorption , physics , engineering
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 CO 2 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‐OH 2 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.