循環農業：農業廢棄物高價值化【環境工程學系/林坤儀特聘教授】
| 論文篇名 | 英文：Selective Aerobic Upgrading of Lignin-Derived Compound Using a Recyclable Dual-Functional TPO-Loaded Cu-BTC Catalyst 中文：使用可回收的雙功能TPO負載Cu-BTC催化劑對木質素衍生化合物進行選擇性好氧降解 |
| 期刊名稱 | WASTE AND BIOMASS VALORIZATION |
| 發表年份,卷數,起迄頁數 | 2020, in press |
| 作者 | Lin, Jia-Yin; Ghanbari, Farshid; Ok, Yong Sik; Lisak, Grzegorz; Lin, Kun-Yi Andrew(林坤儀)*; Chang, Fang-Chih* |
| DOI | 10.1007/s12649-020-01009-1 |
| 中文摘要 | 作為木質素衍生化合物的氧化轉化，香草醇（VA）轉化為香草醛（VL）代表了木質纖維素生物質增值的有用方法。雖然有人建議使用O和O 2作為氧化劑，通過Cu和2,2,6,6-四甲基哌啶1-氧基（TPO）催化有氧氧化進行VA轉化，但這種常規的Cu / TPO採用均相Cu離子和TPO，從反應介質中回收均相銅離子和TPO極具挑戰性。在此，Cu和TPO通過共沉澱法被整合到單一的非均相催化劑中，從而將TPO嵌入到1,3,5-三羧酸銅苯（CuBTC）金屬有機骨架（MOFs）中，形成雙功能的非均相催化劑。嵌入TPO的CuBTC（TEC）保留了CuBTC的典型八面體形態和晶體結構，同時將TPO封裝在CuBTC內。與原始CuBTC和TPO的簡單組合相比，TEC顯示出更高的VA轉換效率。在TEC中較高的TPO嵌入度，較高的溫度和更長的反應時間可顯著增強VA氧化，因此在120°C和2小時的反應時間下，TPO嵌入度為12.5 wt％的TEC可以達到CVA> 98％，SVL = 100％和YVL> 98％。事實證明，TEC可重複用於VA連續氧化。這些特徵表明，TEC是一種有前途的非均相催化劑，它將Cu位和TPO部分的雙重催化功能結合到催化體系中，可以連續，有效和選擇性地將VA氧化為VL。 |
| 英文摘要 | As oxidative conversion of lignin-derived compound, vanillic alcohol (VA), to vanillin aldehyde (VL) represents as a useful process for lignocellulosic biomass valorization. While catalytic aerobic oxidation by Cu and 2,2,6,6-tetramethylpiperidine 1-oxyl (TPO) with O2 as an oxidant is proposed as a promising oxidative process for VA conversion, this conventional Cu/TPO employs homogeneous Cu ions and TPO, making recovery of homogeneous Cu ion and TPO from reaction media extremely challenging. Herein, Cu species and TPO are integrated into a single heterogeneous catalyst through a co-precipitation method to embed TPO into copper benzene-1,3,5-tricarboxylate (CuBTC) metal organic frameworks (MOFs), forming a bifunctional heterogeneous catalyst. The resulting TPO-embedded CuBTC (TEC) retained the typical octahedral morphology and crystalline structure of CuBTC, while encapsulating TPO within CuBTC. The TEC exhibited higher conversion efficiencies of VA than the simple combination of pristine CuBTC and TPO. A higher TPO embedment in TEC, higher temperature and longer reaction time substantially enhanced VA oxidation, and thus TEC with 12.5 wt% of TPO embedment at 120 °C and 2-h reaction time could achieve CVA > 98%, SVL = 100% and YVL > 98%. The TEC is also proven to be reusable for continuous VA oxidation. These features indicate that TEC is a promising heterogeneous catalyst which incorporates the dual catalytic functions of Cu sites and TPO moieties into a catalytic system to continuously, effectively and selectively oxidize VA to VL. |
