Data and code from: Selective oxidation of 3-hydroxypropionic acid to malonic acid over Pd/C: Mechanistic and kinetic study

Malonic acid (MA) is a high-value dicarboxylic acid with strong industrial
demand, yet its current production heavily relies on petrochemical
feedstocks. Here, we report the first systematic study for the sustainable
production of MA via oxidation of 3-hydroxypropionic acid (3-HP) with a
Pd/Carbon catalyst. The effects of oxidant type (O2 and H2O2), pH, and
temperature on the reaction chemistry were comprehensively evaluated.
Guided by experimental observation and DFT-calculated thermochemical
energetics, reaction networks for 3-HP oxidation with both oxidants are
proposed and validated through kinetic modeling. MA was identified as the
primary oxidation product, while further oxidation yields acetic acid and
oxalic acid. The kinetic model validated the network, displaying excellent
agreement (R2 > 0.95). Kinetic observations also enabled a direct
comparison between O2 and H2O2 and revealed their distinct behaviors. The
model was further developed into a temperature-time map, providing insight
into conditions that maximize MA production. Malonic acid selectivity of
56.9 % and yield of 50.5 % were achieved at 3 bar oxygen, equimolar
NaOH:3-HP ratio, and 50 °C.