Recycling Agriculture: Rising value of Agricultural Waste【Department of Environmental Engineering / Lin, Kun-Yirew / Distinguished Professor】
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：Nanopetal-like copper hydroxide nitrate as a highly selective heterogeneous catalyst for valorization of vanillic alcohol via oxidation
中文：納米花瓣狀氫氧化硝酸銅作為高選擇性多相催化劑用於通過氧化使香草醇增值
期刊名稱 Journal of Environmental Chemical Engineering
發表年份,卷數,起迄頁數 2021, 9(5),106092
作者 Li, Bing-Cheng; NhatHuy, Nguyen; Lin, Jia-Yin; Phattarapattamawong, Songkeart; Lisak, Grzegorz; Wang, Haitao*; Lin, Kun-Yi Andrew(林坤儀)*
DOI 10.1016/j.jece.2021.106092
中文摘要 木質素衍生物香草醇 (VL) 轉化為香草醛 (VE) 是實現木質纖維素生物質可持續利用的關鍵一步。由於 VL 轉化為 VE 需要將 VL 的醇部分特定氧化成醛部分，因此開發有效的方法來選擇性氧化 VL 的醇基是至關重要的。最近，2,2,6,6-四甲基哌啶-氧基（TPO）與 Cu 一起被證實是一種有前途的氧化醇的氧化催化工藝。由於 Cu-O 簇在基於 TPO 的醇氧化中起重要作用，並且 NO 部分將促進 TPO 再生的催化循環，因此首次提出了一種有趣的固相材料，氫氧化銅（CHN），用於共催化 TPO 將 VL 氧化成 VE。特別是，開發了一種方便的方法來製造具有 2D 橢圓形納米花瓣特殊形態的 CHN，形成納米花瓣 CHN（NPCHN）。由於 TPO 或 NPCHN 不能單獨將 VL 轉化為 VE，NPCHN/TPO 的組合以 100% 的選擇性快速將 VL 氧化為 VE。隨著 NPCHN 和 TPO 濃度的增加，VL 向 VE 的轉化效率可以顯著提高，達到 CVL 和 YVE 的~99%，SVE = 100%。延長的反應持續時間和升高的反應溫度也將導致顯著高的 VL 轉化效率，這也優於許多報導的轉化效率。 NPCHN 也可以回收利用，與 TPO 共催化將 VL 轉化為 VE。這些發現證實 NPCHN 無疑是一種有利的多相催化劑，可通過選擇性氧化使 VL 升值。
英文摘要 Valorization of lignin derivative, vanillic alcohol (VL), to vanillic aldehyde (VE) represents a critical move towards sustainable utilization of lignocellulosic biomass. As conversion of VL into VE requires the specific oxidation of alcohol moiety of VL into an aldehyde moiety, it is crucial to develop effective processes to selectively oxidize the alcohol group of VL. Lately, 2,2,6,6-tetramethylpiperidin-oxyl (TPO) accompanied with Cu has been validated as a promising oxidative catalytic process for oxidizing alcohols. Since Cu-O cluster plays an important role in TPO-based oxidation of alcohols, and N-O moiety would facilitate the catalytic cycle of TPO regeneration, an interesting solid-phase material, copper hydroxide nitrate (CHN) is proposed here for the first time for co-catalyzing TPO to oxidize VL into VE. In particular, a convenient method is developed to fabricate CHN with a special morphology of 2D elliptical nanopetal, forming nanopetal CHN (NPCHN). As TPO or NPCHN could not convert VL into VE separately, the combination of NPCHN/TPO quickly oxidizes VL to VE with a selectivity of 100%. With higher concentrations of NPCHN and TPO, the conversion efficiency of VL into VE could be considerably enhanced and reached ~99% of CVL and YVE with SVE = 100%. The extended reaction duration and elevated reaction temperature would also lead to the significantly high VL conversion efficiency, which also outperforms many reported conversion efficiencies. NPCHN could be also recyclable for co-catalyzing with TPO for converting VL to VE. These findings confirm that NPCHN is certainly an advantageous heterogeneous catalyst for valorizing VL via selective oxidation.
發表成果與本中心研究主題相關性 透過本研究可進一步建立可用於循環農業中將農業廢棄物及衍生物轉換成價值附加產物之技術。