Catalytic Reaction Engineering Lab, Department of Chemical Engineering, Indian Institute of Technology Delhi, Delhi 110016, India.
School of Materials Sciences, Indian Association for the Cultivation of Science, 2A & 2B Raja S. C. Mullick Road, Jadavpur, Kolkata 700032, India.
Molecules. 2021 Apr 26;26(9):2519. doi: 10.3390/molecules26092519.
Solid acid catalysts occupy a special class in heterogeneous catalysis for their efficiency in eco-friendly conversion of biomass into demanding chemicals. We synthesized porphyrin containing porous organic polymers (PorPOPs) using colloidal silica as a support. Post-modification with chlorosulfonic acid enabled sulfonic acid functionalization, and the resulting material (PorPOPS) showed excellent activity and durability for the conversion of fructose to 5-hydroxymethyl furfural (HMF) in green solvent water. PorPOPS composite was characterized by N sorption, FTIR, TGA, CHNS, FESEM, TEM and XPS techniques, justifying the successful synthesis of organic networks and the grafting of sulfonic acid sites (5 wt%). Furthermore, a high surface area (260 m/g) and the presence of distinct mesopores of ~15 nm were distinctly different from the porphyrin containing sulfonated porous organic polymer (FePOP-1S). Surprisingly the hybrid PorPOPS showed an excellent yield of HMF (85%) and high selectivity (>90%) in water as compared to microporous pristine-FePOP-1S (yield of HMF = 35%). This research demonstrates the requirement of organic modification on silica surfaces to tailor the activity and selectivity of the catalysts. We foresee that this research may inspire further applications of biomass conversion in water in future environmental research.
固体酸催化剂在多相催化中占据着特殊的地位，因为它们在将生物质高效、环保地转化为高附加值化学品方面具有独特的优势。我们使用胶体二氧化硅作为载体，合成了含有卟啉的多孔有机聚合物（PorPOPs）。用氯磺酸进行后修饰，实现了磺酸基功能化，得到的材料（PorPOPS）在绿色溶剂水中将果糖转化为 5-羟甲基糠醛（HMF）的反应中表现出优异的活性和稳定性。PorPOPS 复合材料通过氮气吸附、FTIR、TGA、CHNS、FESEM、TEM 和 XPS 技术进行了表征，证明了有机网络的成功合成和磺酸基（5wt%）的接枝。此外，PorPOPS 还具有 260 m/g 的高比表面积和明显的介孔（~15nm），这与含有磺化卟啉的多孔有机聚合物（FePOP-1S）明显不同。令人惊讶的是，与微孔原始 FePOP-1S 相比（HMF 的产率为 35%），杂化 PorPOPS 在水中表现出优异的 HMF 收率（85%）和高选择性（>90%）。这项研究表明，需要对二氧化硅表面进行有机修饰，以调整催化剂的活性和选择性。我们预计，这项研究可能会激发未来环境研究中在水中进行生物质转化的进一步应用。
