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Pressurized formic acid dehydrogenation: an entropic spring replaces hydrogen compression cost

Journal Article · · Catalysis Science and Technology
DOI:https://doi.org/10.1039/d2cy00676f· OSTI ID:2337964
 [1];  [2];  [2];  [2];  [2];  [2];  [3];  [3];  [3];  [2]
  1. University of Southern California, Los Angeles, CA (United States); University of Southern California
  2. University of Southern California, Los Angeles, CA (United States)
  3. Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
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Formic acid is unique among liquid organic hydrogen carriers (LOHCs), because its dehydrogenation is highly entropically driven. This enables the evolution of high-pressure hydrogen at mild temperatures that is difficult to achieve with other LOHCs, conceptually by releasing the “spring” of energy stored entropically in the liquid carrier. Applications calling for hydrogen-on-demand, such as vehicle filling, require pressurized H2. Hydrogen compression dominates the cost for such applications, yet there are very few reports of selective, catalytic dehydrogenation of formic acid at elevated pressure. Herein, we show that homogenous catalysts with various ligand frameworks, including Noyori-type tridentate (PNP, SNS, SNP, SNPO), bidentate chelates (pyridyl)NHC, (pyridyl)phosphine, (pyridyl)sulfonamide, and their metallic precursors, are suitable catalysts for the dehydrogenation of neat formic acid under self-pressurizing conditions. Quite surprisingly, we discovered that their structural differences can be related to performance differences in their respective structural families, with some tolerant or intolerant of pressure and others that are significantly advantaged by pressurized conditions. Here, we further find important roles for H2 and CO in catalyst activation and speciation. In fact, for certain systems, CO behaves as a healing reagent when trapped in a pressurizing reactor system, enabling extended life from systems that would be otherwise deactivated.

Research Organization:
University of Southern California, Los Angeles, CA (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Grant/Contract Number:
EE0008825
OSTI ID:
2337964
Alternate ID(s):
OSTI ID: 1896312
Journal Information:
Catalysis Science and Technology, Journal Name: Catalysis Science and Technology Journal Issue: 23 Vol. 12; ISSN 2044-4753
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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