Universal Mass Production of Biomass-Derived Nanosized Porous Carbon Spheres as a Superior Nonmetal Catalyst for Aerobic Oxidation of Hydrocarbons
Universal Mass Production of Biomass-Derived Nanosized Porous Carbon Spheres as a Superior Nonmetal Catalyst for Aerobic Oxidation of Hydrocarbons
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DOI：
10.1021/acssuschemeng.2c03702
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发表时间：
2022-10
期刊：
影响因子：
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通讯作者：
Xinran Yu;Pingyu Ye;Ziyu Shao;Yan Zhu;Qiming Zhao
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文献类型：
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作者：
Xinran Yu;Pingyu Ye;Ziyu Shao;Yan Zhu;Qiming Zhao
微观量子效应、球形形态和快速传质特性使得纳米多孔碳球（NPCSs，<100 nm）在包括催化在内的许多应用中具有巨大的实用价值。然而，单分散NPCSs的制备通常是低产量和高成本的，这是由于它们的大表面能沿着纳米尺寸的颗粒。在这项研究中，我们设计了一个高产率的水热碳化过程中的可溶性淀粉与援助的聚（二烯丙基二甲基氯化铵），以制备单分散的碳球与可调的纳米尺寸为43-97 nm。该合成在淀粉浓度高达520 g/L时仍能很好地发挥作用，并且在10倍扩展实验中产量为49.1 g。所提出的方法在各种基于生物质的碳源之间表现出良好的通用性，包括葡萄糖、麦芽糖、葡聚糖、马铃薯淀粉、大麦淀粉和玉米淀粉。首先通过聚酰胺胺树状大分子的季铵化反应和4-羧基-NHPI的酰胺化修饰，制备了共价锚定在NPCS上的N-羟基邻苯二甲酰亚胺（NHPI）多相催化剂。这些树枝状NPCS有助于高NHPI负载（6.09 mmol/g）。负载NHPI和季铵化树枝状大分子之间的协同效应在95 °C和1 atm O2下催化氧化16 h使NH3转化为苯乙酮的转化率为45%，选择性为72%，上级未负载NHPI的性能。这种锚定的NHPI表现出良好的催化氧化性能的各种烃类和良好的可重复使用性，在九个运行的测试。其表面带正电荷，可以防止纳米催化剂在催化过程中的团聚。非金属体系、可持续的高收率纳米载体材料、高负载量的活性催化剂和良好的重复使用性是所设计催化剂的优点。
The microscopic quantum effect, spherical morphology, and fast mass transfer properties render nanosized porous carbon spheres (NPCSs, <100 nm) of great utilitarian value in numerous applications, including catalysis. However, the preparation of monodisperse NPCSs was typically low output and high cost due to their large surface energy along with nanosized particles. In this study, we designed a high-yield hydrothermal carbonization process of soluble starch with the aid of poly(diallyldimethylammonium chloride) to fabricate monodisperse carbonaceous spheres with a tunable nanosize of 43–97 nm. This synthesis still functioned well at starch concentrations as high as 520 g/L and in a 10-fold extended experiment with a yield of 49.1 g. The proposed methodology showed good versatility among various biomass-based carbon sources, including glucose, maltose, glucan, potato starch, barley starch, and corn starch. The subsequent static-air calcinations could facilely introduce rich mesoporosity onto nanosized carbonaceous spheres.N-Hydroxyphthalimide (NHPI) covalently anchored on NPCSs were first prepared as heterogeneous catalysts by polyamidamine dendrimer-based quaternization and amidate modification with 4-carboxyl-NHPI. These dendrimeric NPCSs contributed to the high NHPI loading (6.09 mmol/g). The synergistic effects between the loaded NHPI and the quaternized dendrimer afforded 45% conversion and 72% selectivity in the catalytic oxidation of ethylbenzene into acetophenone at 95 °C under 1 atm O2for 16 h, which was superior to the performance of unsupported NHPI. This anchored NHPI demonstrated good catalytic oxidation performance for various hydrocarbons and favorable reusability in a nine-run test. Their positively charged surface could prevent nanocatalyst agglomeration during the catalytic process. The nonmetal system, sustainable high-yield nanocarrier material, and high-loading active catalyst with good reusability are the advantages of the designed catalysis.