CN109433262A - POMs@lipid(n)/CeO2双分子层纳米纤维氧化5-HMF的方法 - Google Patents
POMs@lipid(n)/CeO2双分子层纳米纤维氧化5-HMF的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title abstract description 6
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- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 1
- 239000000232 Lipid Bilayer Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- QRSFFHRCBYCWBS-UHFFFAOYSA-N [O].[O] Chemical compound [O].[O] QRSFFHRCBYCWBS-UHFFFAOYSA-N 0.000 description 1
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- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- SVEUVITYHIHZQE-UHFFFAOYSA-N n-methylpyridin-2-amine Chemical compound CNC1=CC=CC=N1 SVEUVITYHIHZQE-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
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Abstract
一种用于氧化5‑羟甲基糠醛(5‑HMF)的方法，涉及含有CeO2和多金属氧酸盐的双分子层纳米纤维催化剂在氧化5‑羟甲基糠醛的用途。催化剂为POMs@lipid(n)/CeO2双分子层纳米纤维，将多酸固载到双分子层修饰的CeO2纳米纤维表面，以此为催化剂加入含有5‑HMF的溶液中，并通入氧气，一定的温度和时间下，5‑HMF的转化率可以达到80～100％，生成2，5‑二甲酰基呋喃的产率可以达到50～90％。
Description
技术领域：
本发明涉及含多金属氧酸盐H5PMo10V2O40负载在CeO2纳米纤维的用途，尤其涉及氧化5-羟甲基糠醛技术领域中，生成重要的平台化合物2，5-二甲酰基呋喃。
技术背景:
生物平台化合物5-羟甲基糠醛(5-HMF)是一种重要的化学燃料中间体，被美国科学院评为TOP10的生物质基可再生平台化合物。其活泼的官能团使其具有高的活性以及产物的多样性，将其选择性氧化为一种或几种产物是人们追求的目标。5-HMF最重要的化学转化是利用选择性氧化反应，制备不同的衍生物，包括选择性氧化呋喃环2,5位置上的醛基和羟基，得到一系列的产物如2,5-呋喃二甲酸(FDCA)、2,5-双(羟甲基)-四氢呋喃(HMTHF)、二甲基呋喃(DMF)、2,5-呋喃二甲醛、乙酰丙酸。其中，DFF是一种潜在的运输燃料，具有较高的沸点，与乙醇和石油相比具有更好的相溶性。
目前，5-HMF的选择性氧化常采用将贵金属固载到不同的载体上，在O2或H2O2作用下定向转化为2,5-二甲酰基呋喃(DFF)、5-羟甲基-2-喃甲酸(HMFCA)和2,5-呋喃二甲酸(FDCA)，其转化效率以及产物选择性和反应条件、催化剂的组成、载体的酸碱性及亲疏水性有直接的关系。为了避免贵金属的使用，非贵金属体系特别是丰产元素的体系亟待开发。多金属氧酸盐是一类强氧化型催化剂，在生物质定向氧化转化中有着广泛的应用。同时组成POMs的均为我国的丰产元素，在替代贵金属的生物质氧化转化中也备受关注。但POMs在反应中极易溶于水及其他有机溶剂、催化剂重复使用困难，同时POMs的比表面积低，极大地限制其利用。均相POMs的固相化是多酸催化应用领域的关键技术。
本专利通过静电纺丝技术制备CeO2纳米纤维，并以共价键对其表面进行修饰，在修饰的同时原位固载多金属氧酸盐，制备出H5PMo10V2O40@lipid(n)/CeO2(wt％)POMs/CeO2类脂双分子层结构的纳米纤维，用于5-羟甲基糠醛选择性氧化转化中。利用 H5PMo10V2O40@lipid(n)/CeO2(wt％)复合物纳米纤维在氧气氧化5-HMF定向转化DFF的应用可以解决很多技术性问题：
(1)H5PMo10V2O40@lipid(n)/CeO2系列催化剂可以通过调节CeO2与H5PMo10V2O40的配比控制合成不同酸性、Lewis碱性及氧化还原性的复合催化剂，可以满足5- HMF选择性氧化及定向转化为DFF的需要；同时双分子层具有亲油性，在水中可以一方面富集有机底物，另一方面保护生成的DFF不被进一步，提高反应性；调节n的长度可以调节复合催化剂的亲疏水性，选择性地吸附反应底物。
(2)三中心的H5PMo10V2O40@lipid(n)/CeO2作用于5-HMF的选择性氧化反应的不同位点：H5PMo10V2主要作用于5-HMF氧气氧化；CeO2碱中心活化羟基；酸中心有利于制备DFF。
(3)温和条件下，催化活性最高，5-HMF转化率达到100％，DFF产率达到90％。
(4)催化剂可以被重复使用10次以上而保持很好的催化活性，其良好的循环使用性来源于催化剂良好的稳定性。
发明内容
本发明的目的是提供一种含钼、钒和氧化铈的双分子层结构的纳米纤维在氧气氧化5- 羟甲基糠醛的新方法。
本发明涉及提供的一种H5PMo10V2O40@lipid(n)/CeO2双分子层结构的纳米纤维催化剂是具有以下的组成H5PMo10V2O40@lipid(n)/CeO2(wt％)(n＝2，4，6，8，10；wt＝5～30)：
本发明提供的H5PMo10V2O40@lipid(n)/CeO2的合成方法如下：
通过静电纺丝合成CeO2纳米纤维，将1-5g CeO2纳米纤维经超声分散，缓慢滴加到100- 300mg的聚丙烯酸的二甘醇混合溶液(10-50mL)中加热到180℃搅拌3h后，分离出固体产物，用水和乙醇洗涤3次，40℃干燥得到羧基修饰的CeO2(CeO2-COOH)。1-4g CeO2- COOH置于20-100mL N，N-二甲基甲酰胺/甲醇/三氯甲烷(v/v/v＝2:1:1)溶液超声1h后，将20-50mL乙二胺(丁二胺、己二胺、辛二安、癸二胺)，6g 4-二甲氨基吡啶(DMAP)和4g 1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐(EDCI)加入混合溶液中，冰水浴超声1h，超声结束后50℃加热搅拌48h。反应结束冷却至室温，通过离心分离出固体产物，用甲醇/三氯甲烷(v/v＝1:1)的混合溶液洗涤3次，得到氨基化的CeO2-NH2(n＝2，4，6，8，10)。按化学计量比1：0.05～0.3：0.05～0.3将CeO2-NH2(n)和H5PMo10V2O40以及1-溴正癸烷加入到10-100mL甲苯溶液中超声1h后在110℃下搅拌24h。反应结束冷却至室温，通过离心分离出固体产物，并用乙醇洗涤3-5次，40℃干燥得到H5PMo10V2O40@lipid(n)/CeO2(wt％)。
用本发明提供的催化剂氧化5-HMF的方法如下：
按照质量比1:0.01～10称取5–HMF和H5PMo10V2O40@lipid(n)/CeO2，至于20倍的二甲基亚砜(DMSO)混合后放入聚四氟乙烯内衬的高压反应釜中。当反应温度达到100-150℃时，缓慢通入O2，在转速800rpm/min下反应2-10h。反应停止后，体系冷却到室温，离心分离催化剂与反应液，5-HMF的转化率80～100％，生成2，5-二甲酰基呋喃的产率达到50 ～90％。
具体实施方式
实施例1
通过静电纺丝合成CeO2纳米纤维，将2.5g CeO2纳米纤维经超声分散，缓慢滴加到300 mg的聚丙烯酸的二甘醇混合溶液(25mL)中加热到180℃搅拌3h后，分离出固体产物，用水和乙醇洗涤3次，40℃干燥得到羧基修饰的CeO2(CeO2-COOH)。2.5g CeO2-COOH置于 100mLN，N-二甲基甲酰胺/甲醇/三氯甲烷(v/v/v＝2:1:1)溶液超声1h后，将20mL乙二胺，6g 4-二甲氨基吡啶(DMAP)和4g 1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐(EDCI) 加入混合溶液中，冰水浴超声1h，超声结束后50℃加热搅拌48h。反应结束冷却至室温，通过离心分离出固体产物，用甲醇/三氯甲烷(v/v＝1:1)的混合溶液洗涤3次，得到氨基化的CeO2-NH2(n＝2)。按化学计量比1：0.05：0.3将CeO2-NH2(2)和H5PMo10V2O40以及1-溴正癸烷加入到100mL甲苯溶液中超声1h后在110℃下搅拌24h。反应结束冷却至室温，通过离心分离出固体产物，并用乙醇洗涤5次，40℃干燥得到H5PMo10V2O40@lipid(n)/CeO2 (5％)。
实施例2
按照质量比1:0.01称取5–HMF和H5PMo10V2O40@lipid(n)/CeO2，至于20倍的二甲基亚砜(DMSO)混合后放入聚四氟乙烯内衬的高压反应釜中。当反应温度达到120℃时，缓慢通入O2，在转速800rpm/min下反应6h。反应停止后，体系冷却到室温，离心分离催化剂与反应液，5-HMF的转化率100％，生成2，5-二甲酰基呋喃的产率达到90％。
Claims (2)
1.一种用于氧化5-羟甲基糠醛的POMs(POMs)双分子层纳米纤维催化剂，具有以下通式：
H5PMo10V2O40@lipid(n)/CeO2(wt％)(n＝2，4，6，8，10代表双分子层lipid的碳链长度；wt＝5～30；为H5PMo10V2O40的含量)。
2.如权利要求1所述的一种用于催化氧化5-羟甲基糠醛的POMs双分子层纳米纤维POMs@lipid(n)/CeO2催化剂，所述的双分子层纳米纤维催化剂优选为：
H5PMo10V2O40@lipid(n)/CeO2(5％)(n＝2，4，6，8，10；wt＝15～30)。
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