Selective electrochemical hydrogenation of furfural to 2-methylfuran over a single atom Cu catalyst under mild pH conditions

Furfural is regarded as one of the most promising bio-based feedstocks in the bio-refinery industry. Selective hydrogenation of the carbonyl bond in furfural plays a vital role in its conversion to downstream products. Electrochemical hydrogenation (ECH) method provides a green and sustainable way for this reaction. Yet, it still suffers from harsh pH conditions and low selectivity for highly reduced products, such as 2-methylfuran. In this study, high faradaic efficiencies of over 90% for furfuryl alcohol and 60% for 2-methylfuran were obtained in a near-neutral environment (pH = 5) at −0.75 V and −0.90 Vvs. the reversible hydrogen electrode, respectively. The key to this success is the integration of single atom copper active sites and the oxophilic phosphorus dopants in a single catalyst. Single atom Cu sites are found to be the active centers for this reaction and decreasing the size of Cu sites to a single atom enhances the efficiencies of the ECH reactions by suppressing the competing hydrogen evolution reaction. Phosphorus doping facilitates furfural hydrogenation to 2-methylfuranviaa sequential two-step reduction process. This study opens up possibilities for the selective electrochemical hydrogenation of furfural to 2-methylfuran under mild conditions.