Tailoring the Size of Ru Nanoparticles via Template Evaporation for One-Step Conversion of Cellulose to Sorbitol
Tailoring the Size of Ru Nanoparticles via Template Evaporation for One-Step Conversion of Cellulose to Sorbitol
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DOI：
10.1021/acssuschemeng.3c04572
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发表时间：
2023-10
期刊：
影响因子：
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通讯作者：
Jingnan Yang;Longxin Liu;Huili Zhang;Mo Qiu;Qingxin Guan;Wei Li
中科院分区：
文献类型：
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作者：
Jingnan Yang;Longxin Liu;Huili Zhang;Mo Qiu;Qingxin Guan;Wei Li
纤维素直接转化为山梨醇对食品级山梨醇的生产具有重要意义。然而，纤维素的水解需要苛刻的反应条件，限制了其水解产物的进一步升级。本文以三聚氰胺为模板和氮前驱体，采用简便的方法制备了负载在活性炭上的n修饰钌纳米颗粒。以三聚氰胺和活性炭为原料，采用球磨法制备了尺寸合适、金属钌含量高的钌NPs，并进行了rucl3浸渍和共解。同时，详细研究了不同制备工艺的影响，论证了三聚氰胺与金属前驱体混合的必要性。Ru-N /C-1.3催化剂成功地将纤维素转化为山梨醇，产率达到82%。具有合理直径的Ru NPs描述了有限的氢化活性，保护山梨醇在纤维素水解的高温下免于进一步氢化。密度泛函数理论表明，吡啶N平衡了葡萄糖和山梨醇分子的吸附，有利于葡萄糖的氢化。放大后的Ru NPs具有较低的加氢活性，并能抑制山梨醇的副反应。本研究为制备具有可控尺寸和活性的金属纳米颗粒催化剂提供了一种有效的方法。
Directly converting cellulose to sorbitol is of great significance for the production of food-grade sorbitol. However, the hydrolysis of cellulose requires harsh reaction conditions, limiting further upgrading of its hydrolysate. Herein, N-modified Ru nanoparticles (NPs) supported on active carbon were fabricated by a facile approach using melamine as both template and nitrogen precursor. Ru NPs with appropriate sizes and high metallic Ru0content were synthesized via the ball-milling process of melamine and active carbon, followed by impregnation of RuCl3and subsequent copyrolysis. Meanwhile, the impacts of different fabrication procedures were studied in detail, demonstrating the necessity of mixing melamine and metal precursors together. The catalyst Ru–N/C-1.3 converted cellulose into sorbitol successfully, with a satisfactory yield of 82%. Ru NPs with reasonable diameters depicted limited hydrogenation activity, protecting sorbitol from further hydrogenation at the high temperature of cellulose hydrolysis. Density functional theory revealed that pyridinic N species balanced the adsorption of glucose and sorbitol molecules, favoring the hydrogenation of glucose. It also demonstrated that enlarged Ru NPs have lower hydrogenation activity and prevent sorbitol from side reactions. Our work provides an effective strategy to fabricate metal nanoparticle catalysts with controllable sizes and activities for biomass macromolecule refining.