CN108671939A - 一种花状四氧化三钴纳米微球负载双金属催化剂及其用于hmf氢解制备dmf反应的方法 - Google Patents
一种花状四氧化三钴纳米微球负载双金属催化剂及其用于hmf氢解制备dmf反应的方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 30
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 11
- 239000011806 microball Substances 0.000 title description 3
- 239000002105 nanoparticle Substances 0.000 claims abstract description 34
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- 239000004005 microsphere Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000001509 sodium citrate Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910000510 noble metal Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
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- 239000002245 particle Substances 0.000 claims description 8
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- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 229910000531 Co alloy Inorganic materials 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims description 3
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 3
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
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- 238000006555 catalytic reaction Methods 0.000 claims description 2
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- 239000010970 precious metal Substances 0.000 claims description 2
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- 239000012266 salt solution Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000003426 co-catalyst Substances 0.000 abstract 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 24
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 24
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 235000011083 sodium citrates Nutrition 0.000 description 7
- 241000245665 Taraxacum Species 0.000 description 6
- 235000005187 Taraxacum officinale ssp. officinale Nutrition 0.000 description 6
- -1 cobalt porphyrin Chemical class 0.000 description 6
- 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 6
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 5
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical class O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 239000011943 nanocatalyst Substances 0.000 description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical class [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 229910017816 Cu—Co Inorganic materials 0.000 description 3
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- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical class CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- HBAHZZVIEFRTEY-UHFFFAOYSA-N 2-heptylcyclohex-2-en-1-one Chemical compound CCCCCCCC1=CCCCC1=O HBAHZZVIEFRTEY-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920001367 Merrifield resin Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 238000002407 reforming Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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Abstract
本发明提供了一种花状Co3O4纳米微球负载双金属催化剂及其制备方法和用于HMF氢解制备DMF反应的方法。本发明通过简单的一步封装水热‑焙烧法合成MOx‑Co3O4杂化催化剂前体，再经过还原得到高分散的具有蒲公英针状分级花状结构Co3O4微球负载型的双金属M‑Co催化剂(M‑Co/Co3O4)，M＝Ru,Pd，Pt，Cu,Ni。将制备的催化剂应用于高效HMF选择性氢解制备DMF反应中，HMF的转化率和对DMF的选择性分别可达到90％～100％和89％～100％。该负载型双金属催化剂M‑Co/Co3O4，结构独特新颖，表面活性位丰富，稳定性强，具有广泛的应用前景。
Description
技术领域
本发明属于催化剂技术领域，具体来说，涉及一种花状Co3O4纳米微球负载的M-Co双金属(M＝Ru，Pd，Pt，Cu，Ni)催化剂及其制备方法和催化剂用于5-羟甲基糠醛氢解制备2,5-二甲基呋喃反应的方法。
背景技术
5-羟甲基糠醛(HMF)是生物质转化领域重要的平台分子之一，可由生物质衍生的糖类得到。同时，HMF能被转化为多种重要的化学品，如2,5-呋喃二甲酸(FDCA)、2,5-二甲酰基呋喃(DFF)、2,5-二羟甲基呋喃(BHMF)、2,5-二羟甲基四氢呋喃(DHMTHF)、以及非常有前景的液态燃料2,5-二甲基呋喃(DMF)[L.C.Gao,K.J.Deng,J.D.Zheng,B.Liu,Z.H.Zhang,Efficient oxidation of biomass derived 5-into 2,5-furandicarboxylic acidcatalyzed by Merrifield resin supported cobalt porphyrin,Chem.Eng.J.2015,270:444–449]。DMF因具有独特的性质，包括：高的能量密度、高的辛烷值和低的沸点，相比于乙醇DMF是更为合适和有前景的可再生液态燃料。
催化剂表面的几何和电子结构会对催化反应有很重要的影响[J.Anton,J.Nebel,H.Q.Song,C.Froese,P.Weide,H.Ruland,M.Muhler,S.Kaluza,The effect of sodium onthe structure–activity relationships of cobalt-modified Cu/ZnO/Al2O3catalystsapplied in the hydrogenation of carbon monoxide to higher alcohols,J.Catal.2016,335:175-186]。表面缺陷很容易与反应物分子相互作用，从而促进它的活化。因此，精细调控载体的微观结构有望实现高性能负载型催化剂的制备。双金属纳米催化剂对比单金属催化剂其独特的协同效应往往能够诱导出优良特性。除了能够降低催化剂的成本，在贵金属催化剂中引入非贵金属成分还能够产生独特的活性位，它来源于两个金属之间独特的电子和几何效应。对于HMF选择性氢解制备DMF反应，氢需要选择性与羰基和羟基反应，而不能深度加氢或开呋喃环。
发明内容
为解决上述技术问题，本发明提供了一种花状Co3O4纳米微球负载双金属催化剂及其制备方法和用于HMF氢解制备DMF反应的方法。
本发明所述的花状Co3O4纳米微球负载双金属催化剂是高分散的具有分级花状结构Co3O4微球负载型的M-Co双金属催化剂，其中M为Cu,Ni,Pt,Ru,Pd或Rh中的任意一种。其中M的质量百分含量为1～5％，M-Co合金纳米粒子的平均粒径大小为2～10nm。
所述的催化剂微球的大小为2～5μm，比表面积为80～160m2/g。
本发明所述的花状Co3O4纳米微球负载双金属催化剂的制备方法是通过一步封装水热-焙烧法制备出金属M氧化物与Co3O4杂化催化剂前体，进一步通过还原得到高分散的具有分级花状结构催化剂M-Co/Co3O4，其中M为Ru，Pd，Pt，Cu或Ni中的任意一种。
所述的花状Co3O4纳米微球负载双金属催化剂的制备方法，包括以下具体步骤：
1)用去离子水配制硫酸钴、尿素、柠檬酸钠以及贵金属物种或非贵金属盐混合溶液，将配好的溶液进行水热晶化，晶化温度为120～250℃，时间为48～72h；将所得沉淀使用去离子水和乙醇洗涤到中性，干燥；
2)将所得到的固体置于马弗炉中焙烧得到金属M氧化物与Co3O4杂化催化剂前体，其中M为Ru，Pd，Pt，Cu或Ni中的任意一种；
3)用氢气和氮气的混合气在气氛炉中还原杂化催化剂前体得到花状Co3O4纳米微球负载双金属催化剂。
步骤1)中，硫酸钴的浓度为0.05mol/L～0.25mol/L,尿素的浓度为0.1mol/L～0.3mol/L,柠檬酸钠的浓度为0.01mol/L～0.05mol/L,贵金属的浓度为0.5～6.0mmol/L,非贵金属盐浓度为2.0～10mmol/L。
步骤1)中，贵金属物种为H2PtCl6,RuCl3或H2PdCl4中的任意一种，非贵金属为Cu或Ni中的一种,非贵金属盐为硫酸盐或硝酸盐中的一种，钴与贵金属或者非贵金属的摩尔浓度比为100～25:1。
步骤2)中，升温速率为2～5℃ min-1，从室温升温到350～550℃，之后在恒温温度下保温4～6h进行焙烧；
步骤3)中，还原条件为：以2～5℃ min-1的升温速率从室温升温到300～600℃，并在恒温温度下保温3～6h。
对得到的M-Co双金属(M＝Ru，Pd，Pt，Cu，Ni)催化剂进行扫描电镜(SEM)表征，显示出带有针刺表面的蒲公英花状微球形貌。X-射线衍射(XRD)、高分辨投射电镜(HRTEM)和高角度暗场扫描投射电镜-能量散射X射线光谱(HAADF-STEM)表征出高分散的纳米合金粒子。
一种花状Co3O4纳米微球负载双金属催化剂用于HMF氢解制备DMF反应。其具体步骤为：将HMF溶于1,4-二氧六环，加入上述的催化剂于反应釜中，反应温度设为150-250℃，氢气气氛中反应1-3h。
产物使用Agilent GC7890B气相色谱进行分析，HMF的转化率和对DMF的选择性分别可达到90％～100％和89％～100％。
本发明的技术优势在于：
(1)通过一步封装水热法合成了蒲公英状Co3O4纳米微球负载的M-Co双金属(M＝Ru，Pd，Pt，Cu，Ni)催化剂；
(2)一步封装法可以有效提高金属M与Co3O4载体的相互作用，利用表面形成高稳定的M-Co双金属纳米粒子；
(3)催化剂独特的蒲公英状形貌以有利于双金属纳米粒子分散，同时有利于反应物和表面活性位的紧密接触；
(4)双金属钴基纳米催化剂的双金属协同效应，表面丰富的氧空位以及催化剂的高稳定性，用于HMF选择性氢解制备DMF反应，显示出高的性能，能够克服严苛的反应条件，如高的催化剂用量、高的反应温度或长的反应时间等问题，显示出较高的活性，且催化剂具有高稳定性和重复性，前景非常广泛。
附图说明
图1为实施例1制备的蒲公英状Ru-Co/Co3O4双金属RuCo纳米催化剂的XRD谱图；其中(a)Ru/Co3O4，(b)Co/Co3O4，(c)RuCo/Co3O4。
图2为实施例1制备的蒲公英状Ru-Co/Co3O4双金属RuCo纳米催化剂的SEM(a,b和c)及Ru、Co、O元素的面扫谱图。
图3为实施例1制备的蒲公英状Ru-Co/Co3O4双金属RuCo纳米催化剂的HRTEM(a,b,c)，HAADF-STEM谱图(d1)，Co-K、O-K和Ru-K的EDX面扫(d2，d3，d4)，Co-K、O-K和Ru-K沿着e图中红线的线扫(f)。
图4为实施例1制备的Ru-Co/Co3O4催化剂用于HMF选择性氢解随反应时间HMF的转化率以及DMF的选择性变化曲线图。
具体实施方式
下面结合具体的实施例对本发明所述的一种花状Co3O4纳米微球负载双金属催化剂及其制备方法和用于HMF氢解制备DMF反应的方法做进一步说明，但是本发明的保护范围并不限于此。
实施例1
称量1.968g七水合硫酸钴CoSO4·7H2O，0.63g的CO(NH2)2,0.41g柠檬酸钠Na3C6H5O7·2H2O，称取0.33mmol RuCl3溶解在80mL去离子水中超声溶解形成红色溶液。将上面所得到的溶液转移到聚四氟乙烯水热釜，放入烘箱中180℃水热晶化48小时。所得沉淀使用去离子水和乙醇洗涤到中性，70℃干燥12h。将所得到的固体置于马弗炉中焙烧，升温速率为2℃ min-1，从室温升温到500℃，之后在恒温温度下保温5h，焙烧得到样品RuO2-Co3O4杂化催化剂前体。用体积比为1:9的氢气和氮气混合气在气氛炉中还原杂化催化剂前体，以2℃ min-1的升温速率从室温升温到300℃，并在恒温温度下保温4h，得到Co3O4纳米微球负载的Ru-Co双金属(Ru-Co/Co3O4)催化剂。其中Ru的质量百分含量为2.2％；催化剂微球的大小为2.5μm，比表面积为96m2/g，Ru-Co合金纳米粒子的平均粒径大小为3.9nm。
在100mL高压反应釜中加入0.1g催化剂、10mL1,4-二氧六环，4mmol HMF，充入0.5MPa H2，在常压下升温至200℃，进行反应，反应进行到120min时，HMF的转化率为97.9％，DMF的选择性为98.5％。其中BHMF和MFA为其他副产。
实施例2
称量2.3616g七水合硫酸钴CoSO4·7H2O，0.756g的CO(NH2)2，0.492g柠檬酸钠Na3C6H5O7·2H2O，称取0.76mmol H2PdCl4溶解在80mL去离子水中超声溶解形成溶液。将上面所得到的溶液转移到聚四氟乙烯水热釜，放入烘箱中160℃水热晶化54小时。所得沉淀使用去离子水和乙醇洗涤到中性，70℃干燥12h。将所得到的固体置于马弗炉中焙烧，升温速率为2℃ min-1，从室温升温到300℃，之后在恒温温度下保温6h，焙烧得到样品PdO-Co3O4杂化催化剂前体。用体积比为1:9的氢气和氮气混合气在气氛炉中还原杂化催化剂前体，以2℃min-1的升温速率从室温升温到400℃，并在恒温温度下保温3h，得到Co3O4纳米微球负载的Pd-Co双金属(Pd-Co/Co3O4)催化剂。其中Pd的质量百分含量为4.1％；催化剂微球的大小为3.0μm，比表面积为105m2/g，Pd-Co合金纳米粒子的平均粒径大小为4.6nm。
在100mL高压反应釜中加入0.1g催化剂、10mL1,4-二氧六环，4mmol HMF，充入0.5MPa H2，在常压下升温至200℃，进行反应，反应进行到120min时，HMF的转化率为95.4％，DMF的选择性为93.1％。
实施例3
称量2.952g七水合硫酸钴CoSO4·7H2O，0.945g的CO(NH2)2,0.615g的柠檬酸钠Na3C6H5O7·2H2O，称取0.13mmol H2PtCl6溶解在120mL去离子水中超声溶解形成溶液。将上面所得到的溶液转移到聚四氟乙烯水热釜，放入烘箱中180℃水热晶化48小时。所得沉淀使用去离子水和乙醇洗涤到中性，70℃干燥12h。将所得到的固体置于马弗炉中焙烧，升温速率为5℃ min-1，从室温升温到500℃，之后在恒温温度下保温5h，焙烧得到样品PtO2-Co3O4杂化催化剂前体。用体积比为1:9的氢气和氮气混合气在气氛炉中还原杂化催化剂前体，以2℃ min-1的升温速率从室温升温到400℃，并在恒温温度下保温3h，得到Co3O4纳米微球负载的Pt-Co双金属(Pt-Co/Co3O4)催化剂。其中Pt的质量百分含量为1.3％；催化剂微球的大小为3.8μm，比表面积为125m2/g，Pt-Co合金纳米粒子的平均粒径大小为2.7nm。
在100mL高压反应釜中加入0.1g催化剂、10mL1,4-二氧六环，4mmol HMF，充入0.5MPa H2，在常压下升温至200℃，进行反应，反应进行到120min时，HMF的转化率为90.5％，DMF的选择性为89.1％。
实施例4
称量3.5424g七水合硫酸钴CoSO4·7H2O，1.134g的CO(NH2)2,0.738g柠檬酸钠Na3C6H5O7·2H2O和0.3117g的Cu(NO3)2·3H2O溶解在80mL去离子水中超声溶解。将上面所得到的溶液转移到聚四氟乙烯水热釜，放入烘箱中150℃水热晶化60小时。所得沉淀使用去离子水和乙醇洗涤到中性，70℃干燥12h。将所得到的固体置于马弗炉中焙烧，升温速率为5℃min-1，从室温升温到350℃，之后在恒温温度下保温5h，焙烧得到样品CuO-Co3O4杂化催化剂前体。用体积比为1:9的氢气和氮气混合气在气氛炉中还原杂化催化剂前体，以5℃ min-1的升温速率从室温升温到550℃，并在恒温温度下保温4h，得到Co3O4纳米微球负载的Cu-Co双金属(Cu-Co/Co3O4)催化剂。其中Cu的质量百分含量为2.8％；催化剂微球的大小为4.1μm，比表面积为130m2/g，Cu-Co合金纳米粒子的平均粒径大小为8.2nm。
在100mL高压反应釜中加入0.1g催化剂、10mL1,4-二氧六环，4mmol HMF，充入0.5MPa H2，在常压下升温至200℃，进行反应，反应进行到120min时，HMF的转化率为92.8％，DMF的选择性为92.1％。
实施例5
称量3.936g七水合硫酸钴CoSO4·7H2O，1.26g的尿素CO(NH2)2,0.82g柠檬酸钠Na3C6H5O7·2H2O和0.75g的Ni(NO3)2·3H2O溶解在160mL去离子水中超声溶解。将上面所得到的溶液转移到聚四氟乙烯水热釜，放入烘箱中120℃水热晶化72小时。所得沉淀使用去离子水和乙醇洗涤到中性，70℃干燥12h。将所得到的固体置于马弗炉中焙烧，升温速率为5℃min-1，从室温升温到500℃，之后在恒温温度下保温3h，焙烧得到样品NiO-Co3O4杂化催化剂前体。用体积比为1:9的氢气和氮气混合气在气氛炉中还原杂化催化剂前体，以5℃min-1的升温速率从室温升温到600℃，并在恒温温度下保温3h，得到Co3O4纳米微球负载的Ni-Co双金属(Ni-Co/Co3O4)催化剂。其中Ni的质量百分含量为4.5％；催化剂微球的大小为3.1μm，比表面积为157m2/g，Ni-Co合金纳米粒子的平均粒径大小为5.4nm。
在100mL高压反应釜中加入0.1g催化剂、10mL1,4-二氧六环，4mmol HMF，充入0.5MPa H2，在常压下升温至200℃，进行反应，反应进行到120min时，HMF的转化率为91.5％，DMF的选择性为90.3％。
Claims (10)
1.一种花状Co3O4纳米微球负载双金属催化剂，其特征在于，
是高分散的具有分级花状结构Co3O4微球负载型的M-Co双金属催化剂，其中M为Cu,Ni,Pt,Ru,Pd或Rh中的任意一种。
2.根据权利要求1中所述的花状Co3O4纳米微球负载双金属催化剂，其特征在于，催化剂微球的大小为2～5μm，比表面积为80～160m2/g。
3.根据权利要求1或2中所述的花状Co3O4纳米微球负载双金属催化剂，其特征在于，其中M的质量百分含量为1～5％，M-Co合金纳米粒子的平均粒径大小为2～10nm。
4.一种花状Co3O4纳米微球负载双金属催化剂的制备方法，其特征在于，通过一步封装水热-焙烧法制备出金属M氧化物与Co3O4杂化催化剂前体，进一步通过还原得到高分散的具有分级花状结构催化剂M-Co/Co3O4，其中M为Ru，Pd，Pt，Cu或Ni中的任意一种。
5.根据权利要求4中所述的花状Co3O4纳米微球负载双金属催化剂的制备方法，其特征在于，包括以下具体步骤：
1)用去离子水配制硫酸钴、尿素、柠檬酸钠以及贵金属物种或非贵金属盐混合溶液，将配好的溶液进行水热晶化，晶化温度为120～250℃，时间为48～72h；将所得沉淀使用去离子水和乙醇洗涤到中性，干燥；
2)将所得到的固体置于马弗炉中焙烧得到金属M氧化物与Co3O4杂化催化剂前体，其中M为Ru，Pd，Pt，Cu或Ni中的任意一种；
3)用氢气和氮气的混合气在气氛炉中还原杂化催化剂前体得到花状Co3O4纳米微球负载双金属催化剂。
6.根据权利要求5中所述的花状Co3O4纳米微球负载双金属催化剂的制备方法，其特征在于，步骤1)中，硫酸钴的浓度为0.05mol/L～0.25mol/L,尿素的浓度为0.1mol/L～0.3mol/L,柠檬酸钠的浓度为0.01mol/L～0.05mol/L,贵金属的浓度为0.5～6.0mmol/L,非贵金属盐浓度为2.0～10mmol/L。
7.根据权利要求5或6中所述的花状Co3O4纳米微球负载双金属催化剂的制备方法，其特征在于，步骤1)中，贵金属物种为H2PtCl6,RuCl3或H2PdCl4中的任意一种，非贵金属为Cu或Ni中的一种,非贵金属盐为硫酸盐或硝酸盐中的一种，钴与贵金属或者非贵金属的摩尔浓度比为100～25:1。
8.根据权利要求7中所述的花状Co3O4纳米微球负载双金属催化剂的制备方法，其特征在于，步骤2)中，升温速率为2～5℃ min-1，从室温升温到350～550℃，之后在恒温温度下保温4～6h进行焙烧；
步骤3)中，还原条件为：以2～5℃ min-1的升温速率从室温升温到300～600℃，并在恒温温度下保温3～6h。
9.一种花状Co3O4纳米微球负载双金属催化剂催化HMF氢解制备DMF的应用。
10.根据权利要求9所述的应用，其特征在于，所述花状Co3O4纳米微球负载双金属催化剂催化HMF氢解制备DMF的方法为：将HMF溶于1,4-二氧六环，加入权利要求3所述的催化剂于反应釜中，反应温度设为150-250℃，氢气气氛中反应1-3h。
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