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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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 24
- 239000002121 nanofiber Substances 0.000 title claims abstract description 18
- 238000001907 polarising light microscopy Methods 0.000 title claims abstract description 12
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- 238000007254 oxidation reaction Methods 0.000 title claims description 15
- 230000003647 oxidation Effects 0.000 title claims description 13
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims description 11
- 238000000034 method Methods 0.000 title abstract description 6
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
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- 238000006243 chemical reaction Methods 0.000 abstract description 19
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical class O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 abstract description 5
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- 238000002604 ultrasonography Methods 0.000 description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 4
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- 239000002028 Biomass Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 2
- SODQFLRLAOALCF-UHFFFAOYSA-N 1lambda3-bromacyclohexa-1,3,5-triene Chemical compound Br1=CC=CC=C1 SODQFLRLAOALCF-UHFFFAOYSA-N 0.000 description 2
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- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 2
- PCSKKIUURRTAEM-UHFFFAOYSA-N 5-hydroxymethyl-2-furoic acid Chemical compound OCC1=CC=C(C(O)=O)O1 PCSKKIUURRTAEM-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
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- 229910001882 dioxygen Inorganic materials 0.000 description 2
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- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 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
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 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
- 239000012188 paraffin wax Substances 0.000 description 1
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- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 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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