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Title: Reaction: Earth-Abundant Metal Catalysts for Energy Conversions

Authors:
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388882
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chem; Journal Volume: 2; Journal Issue: 4; Related Information: CME partners with Pacific Northwest National Laboratory (lead); University of Illinois, Urbana-Champaign; Pennsylvania State University; University of Washington; University of Wyoming
Country of Publication:
United States
Language:
English
Subject:
catalysis (homogeneous), catalysis (heterogeneous), solar (fuels), bio-inspired, energy storage (including batteries and capacitors), hydrogen and fuel cells, charge transport, materials and chemistry by design, synthesis (novel materials)

Citation Formats

Bullock, R. Morris. Reaction: Earth-Abundant Metal Catalysts for Energy Conversions. United States: N. p., 2017. Web. doi:10.1016/j.chempr.2017.03.019.
Bullock, R. Morris. Reaction: Earth-Abundant Metal Catalysts for Energy Conversions. United States. doi:10.1016/j.chempr.2017.03.019.
Bullock, R. Morris. Sat . "Reaction: Earth-Abundant Metal Catalysts for Energy Conversions". United States. doi:10.1016/j.chempr.2017.03.019.
@article{osti_1388882,
title = {Reaction: Earth-Abundant Metal Catalysts for Energy Conversions},
author = {Bullock, R. Morris},
abstractNote = {},
doi = {10.1016/j.chempr.2017.03.019},
journal = {Chem},
number = 4,
volume = 2,
place = {United States},
year = {Sat Apr 01 00:00:00 EDT 2017},
month = {Sat Apr 01 00:00:00 EDT 2017}
}
  • Earth-abundant metal catalysts offer many advantages over traditionally used precious metal catalysts for energy conversions.
  • Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturatedmore » metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.« less
  • We describe the development of solar water-splitting cells comprising earth-abundant elements that operate in near-neutral pH conditions, both with and without connecting wires. The cells consist of a triple junction, amorphous silicon photovoltaic interfaced to hydrogen- and oxygen-evolving catalysts made from an alloy of earth-abundant metals and a cobalt|borate catalyst, respectively. The devices described here carry out the solar-driven water-splitting reaction at efficiencies of 4.7% for a wired configuration and 2.5% for a wireless configuration when illuminated with 1 sun (100 milliwatts per square centimeter) of air mass 1.5 simulated sunlight. Fuel-forming catalysts interfaced with light-harvesting semiconductors afford a pathwaymore » to direct solar-to-fuels conversion that captures many of the basic functional elements of a leaf.« less
  • We have designed a strategy for postsynthesis installation of the β-diketiminate (NacNac) functionality in a metal–organic framework (MOF) of UiO-topology. Metalation of the NacNac-MOF (I) with earth-abundant metal salts afforded the desired MOF-supported NacNac-M complexes (M = Fe, Cu, and Co) with coordination environments established by detailed EXAFS studies. The NacNac-Fe-MOF catalyst, I•Fe(Me), efficiently catalyzed the challenging intramolecular sp 3 C–H amination of a series of alkyl azides to afford α-substituted pyrrolidines. The NacNac-Cu-MOF catalyst, I•Cu(THF), was effective in promoting the intermolecular sp 3 C–H amination of cyclohexene using unprotected anilines to provide access to secondary amines in excellent selectivity.more » Finally, the NacNac-Co-MOF catalyst, I•Co(H), was used to catalyze alkene hydrogenation with turnover numbers (TONs) as high as 700 000. All of the NacNac-M-MOF catalysts were more effective than their analogous homogeneous catalysts and could be recycled and reused without a noticeable decrease in yield. The NacNac-MOFs thus provide a novel platform for engineering recyclable earth-abundant-element-based single-site solid catalysts for many important organic transformations.« less