DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Kinetic Control via Binding Sites within the Confined Space of Metal Metalloporphyrin-Frameworks for Enhanced Shape-Selectivity Catalysis

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [1];  [2];  [3];  [4];  [5];  [6];  [6]; ORCiD logo [1]
  1. University of North Texas, Denton, TX (United States)
  2. University of South Florida, Tampa, FL (United States)
  3. University of Chicago, Argonne, IL (United States)
  4. Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
  5. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
  6. King Saud University, Riyadh (Saudi Arabia)

Abstract One striking feature of enzyme is its controllable ability to trap substrates via synergistic or cooperative binding in the enzymatic pocket, which renders the shape‐selectivity of product by the confined spatial environment. The success of shape‐selective catalysis relies on the ability of enzyme to tune the thermodynamics and kinetics for chemical reactions. In emulation of enzyme's ability, we showcase herein a targeting strategy with the substrate being anchored on the internal pore wall of metal‐organic frameworks (MOFs), taking full advantage of the sterically kinetic control to achieve shape‐selectivity for the reactions. For this purpose, a series of binding site‐accessible metal metalloporphyrin‐frameworks (MMPFs) have been investigated to shed light on the nature of enzyme‐mimic catalysis. They exhibit a different density of binding sites that are well arranged into the nanospace with corresponding distances of opposite binding sites. Such a structural specificity results in a facile switch in selectivity from an exclusive formation of the thermodynamically stable product to the kinetic product. Thus, the proposed targeting strategy, based on the combination of porous materials and binding events, paves a new way to develop highly efficient heterogeneous catalysts for shifting selectivity.

Research Organization:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF); Robert A. Welch Foundation
Grant/Contract Number:
AC52-07NA27344; AC02-05CH11231; NSF/CHE-1834750; CHE-1531468; B-0027
OSTI ID:
2008190
Alternate ID(s):
OSTI ID: 1974077
Report Number(s):
LLNL-JRNL-844877; 1067127
Journal Information:
Angewandte Chemie (International Edition), Vol. 62, Issue 26; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

References (46)

Demystifying the roles of single metal site and cluster in CO 2 reduction via light and electric dual-responsive polyoxometalate-based metal-organic frameworks journal December 2022
In(III) Metal–Organic Framework Incorporated with Enzyme-Mimicking Nickel Bis(dithiolene) Ligand for Highly Selective CO2 Electroreduction journal August 2021
Porous Metalloporphyrinic Frameworks Constructed from Metal 5,10,15,20-Tetrakis(3,5-biscarboxylphenyl)porphyrin for Highly Efficient and Selective Catalytic Oxidation of Alkylbenzenes journal June 2012
Gas reactions under intrapore condensation regime within tailored metal–organic framework catalysts journal May 2019
The mechanism of the hantzsch pyridine synthesis: A study by 15N and 13C NMR spectroscopy journal January 1986
Creating enzyme-mimicking nanopockets in metal-organic frameworks for catalysis journal October 2022
Crystal Engineering of a Microporous, Catalytically Active fcu Topology MOF Using a Custom-Designed Metalloporphyrin Linker journal September 2012
Light-Harvesting Metal–Organic Frameworks (MOFs) Efficient Strut-to-Strut Energy Transfer in Bodipy and Porphyrin-Based MOFs journal October 2011
Functional Porphyrinic Metal–Organic Framework as a New Class of Heterogeneous Halogen‐Bond‐Donor Catalyst journal October 2021
Cooperative copper centres in a metal–organic framework for selective conversion of CO2 to ethanol journal July 2019
Selective Catalytic Chemistry at Rhodium(II) Nodes in Bimetallic Metal–Organic Frameworks journal November 2019
Formation of a Metalloporphyrin-Based Nanoreactor by Postsynthetic Metal-Ion Exchange of a Polyhedral-Cage Containing a Metal-Metalloporphyrin Framework journal February 2013
Boosting Interfacial Charge-Transfer Kinetics for Efficient Overall CO 2 Photoreduction via Rational Design of Coordination Spheres on Metal–Organic Frameworks journal June 2020
Acid Catalysis in Confined Channels of Metal–Organic Frameworks: Boosting Orthoformate Hydrolysis in Basic Solutions journal August 2020
Metal–Organic Frameworks in Heterogeneous Catalysis: Recent Progress, New Trends, and Future Perspectives journal March 2020
Metal–organic framework materials as catalysts journal January 2009
Heterogeneous catalysts with programmable topologies generated by reticulation of organocatalysts into metal-organic frameworks: The case of squaramide journal April 2020
Tuning Lewis Acidity of Metal–Organic Frameworks via Perfluorination of Bridging Ligands: Spectroscopic, Theoretical, and Catalytic Studies journal July 2018
Framework-Topology-Dependent Catalytic Activity of Zirconium-Based (Porphinato)zinc(II) MOFs journal October 2016
Shape-selective catalysis in zeolites journal July 1984
Stepwise Synthesis of Metal–Organic Frameworks Replacement of Structural Organic Linkers journal July 2011
1,4-Dihydropyridines—a basis for developing new drugs journal July 1989
Confinement-guided photophysics in MOFs, COFs, and cages journal January 2021
The Multicomponent Hantzsch Reaction: Comprehensive Mass Spectrometry Monitoring Using Charge-Tagged Reagents journal September 2014
Modulating Adsorption and Stability Properties in Pillared Metal–Organic Frameworks: A Model System for Understanding Ligand Effects journal October 2015
Application of soft X-ray absorption spectroscopy in chemical characterization of antiwear films generated by ZDDP Part II: the effect of detergents and dispersants journal January 1997
An electron rich porous extended framework as a heterogeneous catalyst for Diels–Alder reactions journal January 2013
Highly Efficient Cooperative Catalysis by Co III (Porphyrin) Pairs in Interpenetrating Metal-Organic Frameworks journal October 2016
Al- Al 2 O 3 interface study using surface soft-x-ray absorption and photoemission spectroscopy journal March 1979
Pore Space Partition by Symmetry-Matching Regulated Ligand Insertion and Dramatic Tuning on Carbon Dioxide Uptake journal January 2015
Protecting-Group-Free Site-Selective Reactions in a Metal–Organic Framework Reaction Vessel journal April 2018
A revisit to the Hantzsch reaction: Unexpected products beyond 1,4-dihydropyridines journal January 2009
K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites journal August 2017
Regulating Photocatalysis by Spin-State Manipulation of Cobalt in Covalent Organic Frameworks journal September 2020
Quest for highly porous metal–metalloporphyrin framework based upon a custom-designed octatopic porphyrin ligand journal January 2012
Adsorption of Gases in Multimolecular Layers journal February 1938
MOF-enabled confinement and related effects for chemical catalyst presentation and utilization journal January 2022
Integration of Enzymes and Photosensitizers in a Hierarchical Mesoporous Metal–Organic Framework for Light-Driven CO 2 Reduction journal December 2019
Recent progress in host–guest metal–organic frameworks: Construction and emergent properties journal February 2023
Self-adaptive dual-metal-site pairs in metal-organic frameworks for selective CO2 photoreduction to CH4 journal August 2021
A Catalytically Active, Permanently Microporous MOF with Metalloporphyrin Struts journal April 2009
Turning On Catalysis: Incorporation of a Hydrogen-Bond-Donating Squaramide Moiety into a Zr Metal–Organic Framework journal January 2015
Metal–Organic Framework-Based Catalysts with Single Metal Sites journal May 2020
Design and synthesis of squaramide-based MOFs as efficient MOF-supported hydrogen-bonding organocatalysts journal January 2016
Towards a molecular understanding of shape selectivity journal February 2008
Selective, Tunable O 2 Binding in Cobalt(II)–Triazolate/Pyrazolate Metal–Organic Frameworks journal May 2016