Recycling Agriculture: Valorization of Agricultural Residual Materials【Department of Environmental Engineering / Lin, Kun-Yirew / Distinguished Professor】
循環農業：農業剩餘資材及生質衍生物高值化轉換再利用【環境工程學系/林坤儀特聘教授】
論文篇名 英文： Enhanced Lewis basicity of ZIF-8 from metal incorporation (Mg, Cu, or Ce) for glycerol carboxylation using CO2 as a feedstock  
中文：透過金屬摻入（Mg、Cu 或 Ce）增強 ZIF-8 的路易斯鹼性，以 CO2 作為原料進行甘油羧化
期刊名稱 Materials Today Sustainability
發表年份,卷數,起迄頁數 2023, 24, 100511
作者 Hu, C.*; Chang, A. -L.; Catherine, H. N.; Lee, Y. -L.; Lin, K. -Y. Andrew(林坤儀)*; Chou, Y. -J.; Yu, W. -Y.
DOI 10.1016/j.mtsust.2023.100511
中文摘要 在此，將 Mg、Ce 和 Cu 引入到 ZIF-8 中以提高其甘油羧化的路易斯鹼性。金屬摻入後，摻入Ce 和Cu 的ZIF-8 保持結構完整，路易斯鹼度略有增加，而摻入Mg 的ZIF-8 表現出更擾動的結構，包含額外的暴露N 原子和金屬位點（Zn 和Mg）。在 CH3CN 作為均相脫水劑存在的情況下，改進的路易斯鹼度有助於提高摻鎂 ZIF-8 的甘油轉化率及其碳酸甘油酯的產率。使用NaHCO3 作為多相脫水劑，與CH3CN 相比，摻鎂ZIF-8 獲得了更高的選擇性(90%)（高出約60%），這歸因於NaHCO3 的高吸水能力，可抑制副反應。NaHCO3 的異質性能夠實現重複催化甘油羧化的有效回收（>3 個循環）。結果表明，金屬摻入是提高ZIF-8路易斯鹼度的有效且簡單的方法，結合異質NaHCO3作為脫水劑，有利於以CO2為原料的甘油羧化。
英文摘要 Herein, Mg, Ce, and Cu were incorporated into ZIF-8 to improve its Lewis basicity for glycerol carboxylation. Upon metal incorporation, the Ce- and Cu-incorporated ZIF-8 remained structurally intact with slightly increased Lewis basicity, whereas the Mg-incorporated ZIF-8 exhibited a more perturbed structure containing additional exposed N atoms and metal sites (Zn and Mg). The improved Lewis basicity facilitated the increased glycerol conversion of the Mg-incorporated ZIF-8 and its yield of glycerol carbonate in the presence of CH3CN as a homogeneous dehydrating agent. Using NaHCO3 as the heterogeneous dehydrating agent, a much higher selectivity (90%) was obtained over Mg-incorporated ZIF-8 compared to that of CH3CN (∼60% higher), attributed to a high water sorption capability of NaHCO3 that inhibits side reactions. The heterogeneity of NaHCO3 enables efficient recycling (>3 cycles) for repeated catalytic glycerol carboxylation. The results suggested that metal incorporation is an effective and facile approach to improve ZIF-8 Lewis basicity, combined with heterogeneous NaHCO3 as the dehydrating agent, which is beneficial for glycerol carboxylation using CO2 as a feedstock.
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