Efficient and reusable catalysts were developed for one-pot reduction of 1,4-anhydroerythritol (1,4-AHERY), which is a promising biomass-derived C4 platform chemical, into 1,4-butanediol (1,4-BuD) with H₂. First, various ReO_x catalysts on oxide supports were tested for reductive conversion of 2,5-dihydrofuran (2,5-DHF) to 1,4-butanediol (1,4-BuD). ReO_x/WO₃–ZrO₂ showed the best performance, and ReO_x catalysts supported on other oxides were much less active in the isomerization of 2,5-DHF to 2,3-DHF which is the first step of the 2,5-DHF conversion to 1,4-BuD. The ReO_x/WO₃–ZrO₂ catalyst was combined with the ReO_x–Au/CeO₂ catalyst for deoxydehydration (DODH) of 1,4-AHERY into 2,5-DHF to develop a one-pot conversion system of 1,4-AHERY to 1,4-BuD. The highest 1,4-BuD yield of 55% from 1,4-AHERY was obtained. Even though the yield was lower than that obtained over the combination of ReO_x/C and ReO_x–Au/CeO₂ catalysts in our previous study, the regeneration of the combination of ReO_x/WO₃–ZrO₂ and ReO_x–Au/CeO₂ is possible: calcination at 573 for 3 h of the used catalyst mixture increased the activity to the fresh level. THF was the major by-product in both 1,4-AHERY and 2,5-DHF conversions, which was due to hydrogenation of DHF, disproportionation of DHF and/or dehydration of 1,4-BuD. The W amount in WO₃–ZrO₂ greatly affected the catalytic performance of ReO_x/WO₃–ZrO₂: too much W above the monolayer level on the ZrO₂ support sharply decreased the activity in 2,5-DHF isomerization. On the other hand, WO₃–ZrO₂ with a tetragonal ZrO₂ structure prepared by co-precipitation showed comparable performance to WO₃–ZrO₂ with a monoclinic ZrO₂ structure as the support of the ReO_x catalyst, demonstrating that the crystal structure of ZrO₂ has little effect on the catalytic performance. The Re species were suggested to be highly dispersed on the WO₃ (sub)monolayer on ZrO₂ based on the effect of the Re loading amount. The dispersed Re species on monolayer WO₃ species on ZrO₂ can be the active sites for 2,5-DHF disproportionation to 2,3-DHF.

中文翻译：

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钨-氧化锆负载的catalyst催化剂与脱氧脱水催化剂结合使用，可从1,4-脱水赤藓糖醇一锅法合成1,4-丁二醇

开发了一种高效且可重复使用的催化剂，用于将一氧化碳一锅还原1,4-脱水赤藓糖醇（1,4-AHERY）转化为1,4-丁二醇（1,4-BuD），这是一种有前途的生物质衍生的C4平台化学品。 H ₂。首先，测试了氧化物载体上的各种ReO _x催化剂将2，5-二氢呋喃（2,5-DHF）还原转化为1,4-丁二醇（1,4-BuD）。ReO _x / WO ₃ -ZrO ₂表现出最好的性能，负载在其他氧化物上的ReO _x催化剂在2,5-DHF异构化为2,3-DHF的过程中活性较低，这是2,5的第一步-DHF转换为1,4-BuD。ReO _x / WO ₃ –ZrO ₂催化剂与ReO _x –Au / CeO ₂催化剂结合使用，将1,4-AHERY脱氧脱水（DODH）转化为2,5-DHF，以开发一锅法将1,4-AHERY转化为1,4-BuD 。从1，4-AHERY获得最高的1，4-BuD产率55％。尽管收率低于我们先前研究中使用ReO _x / C和ReO _x –Au / CeO ₂催化剂获得的收率，但ReO _x / WO ₃ –ZrO ₂和ReO _x –Au组合的再生/ CeO ₂可能的是：在573煅烧3 h用过的催化剂混合物，将活性提高到新鲜水平。THF是1,4-AHERY和2,5-DHF转化的主要副产物，这是由于DHF的氢化，DHF的歧化和/或1,4-BuD的脱水引起的。WO ₃ -ZrO _2中的W量极大地影响了ReO _x / WO ₃ -ZrO ₂的催化性能：在ZrO ₂载体上单层水平以上的过多W大大降低了2,5-DHF异构化的活性。另一方面，通过共沉淀制得的具有四方ZrO ₂结构的WO ₃ -ZrO ₂具有与WO相当的性能。₃ -ZrO ₂具有单斜晶ZrO ₂结构为支撑的REO的_X催化剂，表明的ZrO的晶体结构₂具有对催化性能影响不大。根据Re负载量的影响，认为Re种类在ZrO ₂的WO ₃（亚）单层上高度分散。ZrO ₂上单层WO ₃物种上分散的Re物种可能是2,5-DHF歧化为2,3-DHF的活性位点。