Physics

Plug flow reactor model

Organic chemistry

Continuous production

Hydrogen

Mechanics

Dehydrogenation

Decomposition

Engineering

Catalysis

Stoichiometry

Physical chemistry

Continuous reactor

Hydrogen production

Inorganic chemistry

Chemistry

Plug flow

Formic acid

Formate

Batch reactor

Continuous flow

Chemical engineering

Continuous stirred-tank reactor

Steady state (chemistry)

Thermodynamics

ACS Catalysis

We investigate the continuous generation of hydrogen via the low temperature (<110 °C), additive-free dehydrogenation of formic acid over heterogeneous Pd/C. Through a combination of kinetic (batch and continuous), spectroscopic, and mechanistic studies, we develop structure–activity–lifetime relationships for this process and in doing so reveal that a combination of pore fouling and poisoning by formate ions results in deactivation of the catalyst during continuous operation. Although these factors result in extensive deactivation in Plug Flow mode, promising results can be obtained by minimizing the steady state concentration of formic acid by operating in a continuous stirred tank reactor. In doing so, continuous operation of the system without a loss of activity for over 2500 turnovers is achieved, under mild conditions and in the absence of stoichiometric additives.

Continuous Production of Hydrogen from Formic Acid Decomposition Over Heterogeneous Nanoparticle Catalysts: From Batch to Continuous Flow