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Title: Photoactive Zeolitic Imidazolate Framework as Intrinsic Heterogeneous Catalysts for Light-Driven Hydrogen Generation

Authors:
; ORCiD logo; ; ORCiD logo
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
UNIVERSITY
OSTI Identifier:
1351376
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Energy Letters; Journal Volume: 2; Journal Issue: 1
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Yang, Sizhuo, Pattengale, Brian, Kovrigin, Evgenii L., and Huang, Jier. Photoactive Zeolitic Imidazolate Framework as Intrinsic Heterogeneous Catalysts for Light-Driven Hydrogen Generation. United States: N. p., 2017. Web. doi:10.1021/acsenergylett.6b00540.
Yang, Sizhuo, Pattengale, Brian, Kovrigin, Evgenii L., & Huang, Jier. Photoactive Zeolitic Imidazolate Framework as Intrinsic Heterogeneous Catalysts for Light-Driven Hydrogen Generation. United States. doi:10.1021/acsenergylett.6b00540.
Yang, Sizhuo, Pattengale, Brian, Kovrigin, Evgenii L., and Huang, Jier. Fri . "Photoactive Zeolitic Imidazolate Framework as Intrinsic Heterogeneous Catalysts for Light-Driven Hydrogen Generation". United States. doi:10.1021/acsenergylett.6b00540.
@article{osti_1351376,
title = {Photoactive Zeolitic Imidazolate Framework as Intrinsic Heterogeneous Catalysts for Light-Driven Hydrogen Generation},
author = {Yang, Sizhuo and Pattengale, Brian and Kovrigin, Evgenii L. and Huang, Jier},
abstractNote = {},
doi = {10.1021/acsenergylett.6b00540},
journal = {ACS Energy Letters},
number = 1,
volume = 2,
place = {United States},
year = {Fri Jan 13 00:00:00 EST 2017},
month = {Fri Jan 13 00:00:00 EST 2017}
}
  • Cobalt-based bimetallic phosphide encapsulated in carbonized zeolitic imadazolate frameworks has been successfully synthesized and showed excellent activities toward both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Density functional theory calculation and electrochemical measurements reveal that the electrical conductivity and electrochemical activity are closely associated with the Co2P/CoP mixed phase behaviors upon Cu metal doping. This relationship is found to be the decisive factor for enhanced electrocatalytic performance. Moreover, the precise control of Cu content in Co-host lattice effectively alters the Gibbs free energy for H* adsorption, which is favorable for facilitating reaction kinetics. Impressively, an optimized performance hasmore » been achieved with mild Cu doping in Cu0.3Co2.7P/nitrogen-doped carbon (NC) which exhibits an ultralow overpotential of 0.19 V at 10 mA cm–2 and satisfying stability for OER. Cu0.3Co2.7P/NC also shows excellent HER activity, affording a current density of 10 mA cm–2 at a low overpotential of 0.22 V. In addition, a homemade electrolyzer with Cu0.3Co2.7P/NC paired electrodes shows 60% larger current density than Pt/ RuO2 couple at 1.74 V, along with negligible catalytic deactivation after 50 h operation. The manipulation of electronic structure by controlled incorporation of second metal sheds light on understanding and synthesizing bimetallic transition metal phosphides for electrolysis-based energy conversion.« less
  • Herein, we demonstrate that a prototypical type of metal organic framework, zeolitic imidazolate framework-8 (ZIF-8), in membrane form, can effectively separate Kr/Xe gas mixtures at industrially relevant compositions. The best membranes separated Kr/Xe mixtures with average Kr permeances as high as 1.5 × 10 -8 ± 0.2 mol/m 2 s Pa and average separation selectivities of 14.2 ± 1.9 for molar feed compositions corresponding to Kr/Xe ratio encountered typically in air. Molecular sieving, competitive adsorption, and differences in diffusivities were identified as the prevailing separation mechanisms. These membranes potentially represent a less-energy-intensive alternative to cryogenic distillation, which is the benchmarkmore » technology used to separate this challenging gas mixture. To our best knowledge, this is the first example of any metal organic membrane composition displaying separation ability for Kr/Xe gas mixtures.« less
  • Here we show that sub-micron coatings of zeolitic imidazolate frameworks (ZIFs) and even ZIF–ZIF bilayers can be grown directly on polymers of intrinsic microporosity from zinc oxide (ZnO) nanocrystal precursor films, yielding a new class of all-microporous layered hybrids. The ZnO-to-ZIF chemical transformation proceeded in less than 30 min under microwave conditions using a solution of the imidazole ligand in N,N-dimethylformamide (DMF), water, or mixtures thereof. By varying the ratio of DMF to water, it was possible to control the morphology of the ZIF-on-polymer from isolated crystallites to continuous films. Grazing incidence X-ray diffraction was used to confirm the presencemore » of crystalline ZIF in the thin films, and X-ray absorption spectroscopy was used to quantify film purity, revealing films with little to no residual ZnO. The role solvent plays in the transformation mechanism is discussed in light of these findings, which suggest the ZnO nanocrystals may be necessary to localize heterogeneous nucleation of the ZIF to the polymer surface.« less