Transition-metal-catalyzed transfer
hydrogenation with an in situ hydrogen donor has
received a great deal of attention
from both academia and industry as an alternative to the traditional
high-pressure-hydrogen process, owing to its better efficiency, atom
economy, and sustainability features. Hydrogen stored in the chemical
bonds of formic acid (FA), a promising hydrogen storage compound that
could be derived from biomass or reduction of CO2, can
be extracted selectively and used for diverse catalytic transformations.
This Review summarizes and compares recent progress in catalytic transfer
hydrogenation (CTH) via heterogeneous hydrogen transfer from FA. Transformations
of biomass-derived platform chemicals (e.g., aromatic units, C5 and
C6 sugars, furans, glycerol, fatty acids, levulinic acid (LA)), nitrogen-containing
compounds (e.g., nitroarenes, quinolines), and organochlorinated compounds
via transfer hydrogenation, hydrogenolysis, and hydrodechlorination
(HDC) are outlined. Synthesis strategies of the heterogeneous metal
catalysts (e.g., metal and support type, metal–support interaction,
single-atom, alloy effect, and confinement effect) and optimization
of the reaction conditions (e.g., temperature, solvents, additives,
and FA dosages) for enhancing the catalytic activity and regulating
the product distribution are presented. Structure–activity
relationships based on both dehydrogenation and hydrogenation of metal
catalysts as well as the mechanistic interpretation of CTH with FA
are also highlighted. Finally, current challenges and outlook for
the future development of the field are discussed.