Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Electronic and catalytic engineering in two-dimensional vdW metal–organic frameworks through alloying

Journal Article · · Applied Physics Reviews
DOI: https://doi.org/10.1063/5.0051219 · OSTI ID:1853664
ORCiD logo [1];  [2];  [2];  [2];  [2];  [2]; ORCiD logo [2];  [2];  [2];  [2]; ORCiD logo [2]
  1. Arizona State University, Tempe, AZ (United States). School for Engineering of Matter Transport and Energy; Arizona State Univ., Tempe, AZ (United States)
  2. Arizona State University, Tempe, AZ (United States). School for Engineering of Matter Transport and Energy
+ Show Author Affiliations

Bimetallic metal-organic framework (MOFs) alloys, in which heterogeneous metal clusters are incorporated into their backbone, are capable of highly selective separations and catalysis. Due to limitations in our fundamental understanding of their alloying, however, established methods result in phase-separated or amorphous two-dimensional (2D) MOFs or lack precise control over alloy ratios. Here, our results demonstrate 2D MOF alloys where metal cation ratios (M1 and M2) in M1xM21-xBDC (M1 or M2= Zn, Cu, Ni, Co, Fe, Mn) can be engineered on demand by controlling the metal salt dissociation constants. Resulting MOF alloys exhibit a highly 2D nature with excellent crystallinity and minute control over metal cation ratios. Overall, our experimental and theoretical results show that their electronic bandgaps and photoexcited carrier lifetimes can be engineered by metal cation alloying. Interestingly, 2D alloyed MOFs enable high-efficiency photo-catalytic water reduction performance in Co/Ni MOF alloys owing to the spatially separated metal clusters in 2D MOF alloys.

Research Organization:
Arizona State Univ., Tempe, AZ (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC)
Grant/Contract Number:
SC0020653
OSTI ID:
1853664
Journal Information:
Applied Physics Reviews, Journal Name: Applied Physics Reviews Journal Issue: 3 Vol. 8; ISSN 1931-9401
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (26)

Ultimate Control over Hydrogen Bond Formation and Reaction Rates for Scalable Synthesis of Highly Crystalline vdW MOF Nanosheets with Large Aspect Ratio journal November 2018
Phase Transition across Anisotropic NbS 3 and Direct Gap Semiconductor TiS 3 at Nominal Titanium Alloying Limit journal March 2020
Recent Progress in Metal-Organic Frameworks for Applications in Electrocatalytic and Photocatalytic Water Splitting journal January 2017
Chemical Engineering of Photoactivity in Heterometallic Titanium-Organic Frameworks by Metal Doping journal June 2018
A Redox‐Active 2D Metal–Organic Framework for Efficient Lithium Storage with Extraordinary High Capacity journal March 2020
Two-Dimensional Metal-Organic Framework Nanosheets journal December 2016
Recent Progress on Engineering Highly Efficient Porous Semiconductor Photocatalysts Derived from Metal–Organic Frameworks journal January 2019
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Characterization of TiO2-based semiconductors for photocatalysis by electrochemical impedance spectroscopy journal November 2016
Enhanced photocatalytic activity and photocurrent properties of plasma-synthesized indium-doped zinc oxide nanopowder journal March 2019
Ultrathin Manganese-Based Metal–Organic Framework Nanosheets: Low-Cost and Energy-Dense Lithium Storage Anodes with the Coexistence of Metal and Ligand Redox Activities journal August 2017
Bimetallic Metal–Organic Frameworks as Efficient Cathode Catalysts for Li–O 2 Batteries journal December 2017
Synthesis and Characterization of Metal–Organic Framework-74 Containing 2, 4, 6, 8, and 10 Different Metals journal May 2014
Highly Efficient Visible-Light-Driven Photocatalytic Hydrogen Production of CdS-Cluster-Decorated Graphene Nanosheets journal July 2011
Metal Substitution as the Method of Modifying Electronic Structure of Metal–Organic Frameworks journal March 2019
Methane storage in flexible metal–organic frameworks with intrinsic thermal management journal October 2015
Ultrathin metal–organic framework nanosheets for electrocatalytic oxygen evolution journal November 2016
A partially interpenetrated metal–organic framework for selective hysteretic sorption of carbon dioxide journal June 2012
Synthesis and characterization of bimetallic metal–organic framework Cu–Ru-BTC with HKUST-1 structure journal January 2015
Boosting the photocatalytic CO 2 reduction of metal–organic frameworks by encapsulating carbon dots journal January 2020
Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)] journal June 2006
Monolayer semiconducting transition metal dichalcogenide alloys: Stability and band bowing journal April 2013
Spatially separating redox centers on 2D carbon nitride with cobalt single atom for photocatalytic H 2 O 2 production journal March 2020
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Alloy Engineering of Defect Properties in Semiconductors: Suppression of Deep Levels in Transition-Metal Dichalcogenides journal September 2015
The Chemistry and Applications of Metal-Organic Frameworks journal August 2013

Similar Records

Related Subjects

2D materials
42 ENGINEERING
Physics
absorption spectroscopy
catalysts and catalysis
chemical thermodynamics
crystal structure
crystalline solids
density functional theory
electronic band structure
photocatalysis
photoexcitations