Biomass-derived value-added materials such as levulinic acid (LA) are favorable natural resources for producing ester-based biolubricants owing to their biodegradability, nontoxicity, and excellent metal-adhering properties. However, highly active catalysts must be developed to carry out efficient esterification of LA with aliphatic alcohols, especially long-chain aliphatic alcohols. In this study, we developed a novel porous covalent organic polymer catalyst (BPOP-SO₃H) with dual acid sites, phosphate and sulfonic acid sites, for the esterification of LA. The prepared BPOP-SO₃H catalyst was verified using various surface analysis techniques. BPOP-SO₃H exhibited 98% LA conversion with n-butanol and 99% selectivity for butyl levulinate ester within 30 min, which is superior to that of most reported catalysts. BPOP-SO₃H also showed high LA conversion and ester selectivity when other aliphatic alcohols were used. Moreover, BPOP-SO₃H showed good recyclability for five consecutive cycles. We believe that incorporating a high density of acid sites into a porous polymer with a large surface area and hierarchical pores is a promising approach for developing heterogeneous acid catalysts for the production of alkyl levulinate esters from LA.

https://doi.org/10.1021/acsami.3c08640