Direct ethyl acetate synthesis from ethanol over amorphous-, monoclinic-, tetragonal ZrO2 supported copper catalysts prepared from the same zirconium source
Direct ethyl acetate synthesis from ethanol over amorphous-, monoclinic-, tetragonal ZrO2 supported copper catalysts prepared from the same zirconium source
复制标题
在相同锆源制备的无定形、单斜、四方 ZrO2 负载铜催化剂上直接从乙醇合成乙酸乙酯
DOI：
10.1016/j.apcatb.2023.122433
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Tone Taketo
中科院分区：
文献类型：
--
作者：
Yamamoto Takashi;Mine Hirotaka;Katada Shoki;Tone Taketo
采用负载型 Cu 催化剂对各种酸碱金属氧化物、可用的 ZrO2 基氧化物以及由相同 Zr 源制备的自制无定形、单斜晶和四方氧化锆进行了由乙醇直接合成乙酸乙酯的研究。进行了 XRD、XAFS、TG-DTA 表征和表面积测量。基于收率和产物比（乙酸乙酯与C4醇和醛的总和）讨论了ZrO2载体的晶相对选择性乙酸乙酯生产的影响。基于29种自制催化剂的催化性能，发现在没有任何表面修饰的情况下，非晶型ZrO2本质上是最适合选择性生成乙酸乙酯的ZrO2相。单斜晶型ZrO2催化剂表面的酸性位可能促进了不利的乙醛缩合反应，但添加Na+进行中毒可以提高乙酸乙酯形成的选择性。讨论了新鲜催化剂和废催化剂中铜物种的配位环境。
Direct ethyl acetate synthesis from ethanol was examined by supported Cu catalysts on various kinds of acid-base metal oxides, available ZrO2-based oxides, and homemade amorphous-, monoclinic- and tetragonal zirconia prepared from the same Zr source. XRD, XAFS, TG-DTA characterization and surface area measurement were performed. Effects of crystalline phase of ZrO2support on selective ethyl acetate production was discussed based on the yields and products ratio (ethyl acetate to sum of C4-alcohols and aldehydes). Based on catalytic performance by 29 kinds of homemade catalysts, amorphous-type ZrO2was found to be essentially the most suitable ZrO2phase for the selective ethyl acetate formation in cases without any surface modifications. The acid site on the surface of monoclinic-type ZrO2catalysts possibly promoted unfavorable acetaldehyde condensation reaction, but addition of Na+for poisoning could increase selectivity of ethyl acetate formation. Coordination environment of Cu species for fresh and spent catalysts were discussed.