The global excess of crude glycerol has led to a glycerol market price decline and left negative impacts on the biodiesel economy. The high cost associated with purifying the crude glycerol raw material restricts its applicability and necessitates the development of innovative ways for its valorization. In contrast to typical thermocatalytic approaches, electrocatalytic techniques facilitate selective conversion under ambient conditions and promote efficient co-production of hydrogen through paired cathodic reactions. An emerging focus has been dedicated to developing low‐cost, selective, and durable non-noble metal catalysts. Almost all studies carried out under strong basic media (pH ≥13) and high applied potential report formic acid as the main product and low selectivity toward 3-carbon products (i.e., 1,3 dihydroxyacetone, glyceraldehyde, glyceric acid, tartronic acid,...).
In this study, a cheap and robust electrocatalyst, α-MnO2, was developed to convert glycerol to various 3-carbon compounds. α-MnO2 showed high selectivity toward 1,3-dihydroxyacetone (about 45%) under a high current density of 6.0 mA cm-2 and applied potential of 2.05 V vs. RHE. By combining HPLC analysis and operando Raman spectroscopy, a hypothesized reaction route for the electrooxidation of glycerol on the MnO2 catalyst in pH 9 media was tentatively suggested. The observed high formic acid selectivity at low applied potential may be attributed to the predominant of α-MnO2 on the catalyst surface. Conversely, at higher applied potential, the formation of the δ-MnO2 phase becomes more prominent, leading to a decrease in C-C bond breaking, resulting in high selectivity towards 1,3-dihydroxyacetone.
The next part evaluated the catalytic activity towards GEOR of three primary MnO2 crystal structures, namely α-, β-, and γ-MnO2. Although three crystal structure catalysts yielded similar product distribution toward the 3-carbon product (~50% for 1,3 dihydroxyacetone and 40% for glyceraldehyde), the γ-MnO2 exhibited superior glycerol electrooxidation performance due to high geometric current density (~1.9 mA cm-2) and satisfactory stability. The HPLC and operando Raman findings indicated that high applied potential facilitated the formation of low crystalline δ-MnO2, which might hinder C-C bond breakage, resulting in high selectivity of 1,3-dihydroxyacetone and glyceraldehyde. The initial crystal structure played a pivotal role in the surface evolution process, resulting in a unique surface composition and yielding diverse catalytic activity.

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