CN115445611B - 一种用于甘油选择性氧化制备二羟基丙酮的催化剂及其制备方法 - Google Patents
一种用于甘油选择性氧化制备二羟基丙酮的催化剂及其制备方法 Download PDFInfo
- Publication number
- CN115445611B CN115445611B CN202211170944.4A CN202211170944A CN115445611B CN 115445611 B CN115445611 B CN 115445611B CN 202211170944 A CN202211170944 A CN 202211170944A CN 115445611 B CN115445611 B CN 115445611B
- Authority
- CN
- China
- Prior art keywords
- ldhs
- catalyst
- solution
- alkali
- naoh
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 20
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 230000003647 oxidation Effects 0.000 title claims abstract description 13
- 229940120503 dihydroxyacetone Drugs 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 9
- 239000002028 Biomass Substances 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 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
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000006703 hydration reaction Methods 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract description 3
- 150000004692 metal hydroxides Chemical class 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- 235000011187 glycerol Nutrition 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供一种用于甘油选择性氧化制备二羟基丙酮的Au基催化剂及其制备方法。该Au基催化剂的化学式表示为M1(OH)x/Au/re‑LDHs,是以层状双金属氢氧化物为前驱体采用热致拓扑‑水合复原法构筑的。其中M1为Cu、Mg、Zn或Ca中的一种或多种,贵金属Au的负载量为0.5~5wt%,re‑LDHs为载体。该催化剂具有反转式金属氢氧化物簇‑贵金属,即M1(OH)x/Au界面结构。该催化剂在生物质醇甘油选择性氧化制备二羟基丙酮中具有优异的活性及选择性。
Description
技术领域:
本发明属于催化技术领域,具体涉及一种Au基催化剂的制备方法及其在生物质醇甘油选择性氧化制备二羟基丙酮中的应用。
背景技术:
化石能源的发现与利用极大促进了人类文明的进步与经济社会的发展。然而,以高碳能源为主的发展方式造成不可再生的化石能源日益枯竭,因此开发和利用可再生资源迫在眉睫。生物质能是指太阳能以化学能形式储存在通过光合作用形成的有机体内的能量,被视为代替传统化石燃料的新型能源之一。甘油是在碱性条件通过植物/动物油与醇分子之间的酯交换反应生产生物柴油的主要副产物,是12种优先开发与利用的生物质基平台化合物分子之一。甘油分子中含有伯、仲两种羟基基团,可以通过选择性催化氧化技术实现向下游含氧精细化学品的转化。其中,仲羟基氧化产物二羟基丙酮广泛应用于生命科学与有机合成等领域,具有用途广泛,附加值高,需求量大等特点。
目前,负载型贵金属催化剂在甘油选择性氧化中被广泛研究。其中,Au基催化剂具有较好的抗毒化能力,因此对于甘油分子中的仲羟基具有优异的选择性。然而,无碱条件下,Au基催化剂存在稳定性较差、催化活性较低等问题。目前,基于SMSI效应可实现高温条件下可还原载体部分还原并在活性金属表面进行迁移封装,从而构筑反转式MOx/金属界面结构并提高在特定反应中的催化性能。文献1Liu等人在Ultra-stable Au nanoparticleson titania through an encapsulation strategy under oxidative atmosphere中提出可利用三聚氰胺诱导可渗透性的TiOx层对Au纳米颗粒的封装,从而提高催化剂在CO氧化反应中的抗烧结性。文献2Zhang等人在Structure Sensitivity of Au-TiO2Strong Metal-Support Interactions中报道了在O2气氛下处理后的Au/TiO2催化剂表面具有超薄TiO2-x包覆层。TiO2-x薄层会向Au转移电子从而促进晶格氧的活化,因此表现出较高的CO氧化本征活性。然而,以上界面结构在醇类选择性氧化反应中鲜有报道。因此,亟需发展一种与醇分子及氧分子轨道匹配的新型的界面结构及其构筑方法,从而实现甘油选择性氧化制备二羟基丙酮的性能强化。
层状金属氢氧化物(Layered double hydroxides,LDHs),是一类典型的二维纳米材料,化学通式为[M2+ 1-x M3+ x(OH)2]x+(An-)x/n·yH2O。一方面,基于LDHs晶格定位及结构拓扑效应,可以将其作为前驱体可控构筑金属-MOx界面结构。另一方面,LDHs还具有水合复原特性,即当拓扑温度低于500℃时,混合金属氧化物晶相可以经过处理条件重新恢复至层状氢氧化物晶相,因此可实现金属-M(OH)x界面结构的精准构筑。与传统的金属-MOx界面结构相比,金属-M(OH)x界面结构对于醇分子及氧分子具有更强的化学亲和力,因此可实现甘油选择性氧化制备二羟基丙酮的性能强化。
发明内容:
本发明的目的是提供一种用于生物质基醇类选择性氧化反应的催化剂及其制备方法,该催化剂展现出优异的催化性能。
本发明提供的Au基催化剂的化学表示式为M1(OH)x/Au/re-LDHs,其中M1为Cu、Mg、Zn或Ca中的一种或多种,贵金属Au的负载量为0.5~5wt%,re-LDHs为载体,是由LDHs经热致拓扑-水合复原形成的;该催化剂具有反转式金属氢氧化物簇-贵金属的界面结构。
上述催化剂的具体制备步骤如下:
A.将可溶性M1 2+及M2 3+硝酸盐前驱体配制为混合溶液,其中金属离子的总物质的量浓度为0.1~0.3mol/L,M1 2+/M2 3+的摩尔比为1~5;将NaOH和Na2CO3配制为碱溶液,其中碱溶液的物质的量浓度为0.2~0.9mol/L,NaOH/Na2CO3的摩尔比为1~3。将上述盐溶液以1~3mL/min的速度滴加至碱溶液中,维持溶液pH为9~10。完成操作后将所得悬浊液于60~80℃晶化5~24h;洗涤并离心至上清液中性,于60~90℃下干燥得到LDHs载体。
所述M1 2+是Cu、Mg、Zn、Ca中的一种或多种,Mg和Zn较佳;M2 3+是Al、Fe、Ti中的一种或多种,Al和Fe较佳。
B.将步骤A制备而得的LDHs载体均匀分散到去离子水中,得到固含量为0.01~0.05g/mL的悬浊液;加入碱及Au金属盐,其中Au的负载量为0.5~5wt%,碱的物质的量为Au的物质的量的400~600倍。将所得悬浊液置于60~90℃中持续搅拌3~6h,洗涤至上清液为中性并干燥。将所得样品于气氛炉中以2~10℃/min的速度升温至200~500℃,保温2~4小时,得到M1Ox/Au/LDO前驱体。
所述Au盐为HAlCl4,Au(en)2Cl3中的一种;碱为NaOH或尿素中的一种;气氛为H2/N2,CO2/N2或者O2/N2混合气氛中的一种,其中混合气氛中H2、CO2、O2的体积分数为10-30%。
C.将步骤B所得M1Ox/Au/LDO前驱体分散至物质的量浓度为2~4mol/L的碱溶液中,常温下搅拌0.5-4h。在此过程中前驱体发生水合复原:其中LDO载体复原为re-LDHs,M1Ox/Au界面结构复原为M1(OH)x/Au界面结构,得到M1(OH)x/Au/re-LDHs催化剂。
所述碱溶液为NaOH、Na2CO3或尿素中的一种或多种。
将所述M1(OH)x/Au/re-LDHs催化剂应用于甘油氧化反应中,具体的反应条件为甘油/Au的摩尔比为1000:1~100:1,反应温度为60~90℃,氧气压力为0.1~0.5Mpa,反应时间为2~10h。
本发明的有益效果:
1、本发明的特征是首次发现基于LDHs热致拓扑-水合复原法制备具有反转式M(OH)x/Au的界面结构的负载型Au基催化剂。该方法简单易行,具有普适性。
2、该催化剂应用于以分子氧为氧化剂的甘油选择性氧化中,在无碱条件下对醇分子及氧分子具有高效的吸附及活化能力,因此展现出优异的活性、选择性及稳定性。
附图说明
图1为实施例1中系列样品的XRD图谱。
图2为实施例1中系列样品的FTIR图谱。
图3是实施例1中系列样品的CO-FTIR红外谱图。
以上三张图中,曲线a均为步骤A获得的LDHs载体,曲线b均为步骤BC获得的M1Ox/Au/-LDO前驱体,曲线c均为步骤C获得的M1(OH)x/Au/re-LDHs催化剂。
图4是实施例1中M1(OH)x/Au/re-LDHs催化剂的HRTEM照片及粒径统计分布图。
图5是实施例1中M1(OH)x/Au/re-LDHs催化剂界面处HRTEM照片。
图6为实施例1中M1(OH)x/Au/re-LDHs催化剂的循环使用测试结果。
具体实施方式:
下面结合实施例,对本发明进行进一步的详细说明,但不构成对本发明保护范围的限制。
实施例1:
A.使用共沉淀法制备MgAl-LDHs载体。将0.08molMg(NO3)2及0.04molAl(NO3)3金属前驱体盐溶解于100mL去离子水中得到溶液A,将0.015molNaOH与0.03mol Na2CO3溶解于100mL去离子水中得到溶液B。将溶液A以2.5mL/min的速度滴加至盛有100mL去离子水的反应器中,同时控制溶液B的滴加速度,使体系的pH控制在9.6±0.05。接着将反应器加热至60℃维持6h,结束后离心并洗涤至上清液pH=7并进一步干燥获得MgAl-LDHs。以此为载体,使用沉淀沉积法负载Au金属盐。将1g载体、1mL的H2AuCl4溶液(10mgAu·mL-1)及1.22g尿素均匀分散于50mL去离子水中,于80℃下持续搅拌6h,洗涤并离并干燥。将该样品置于15%的CO2/N2混合气中以5℃·min-1的升温速率加热至500℃并保温3h,待降至室温后取出得到MgOx/Au/LDO前驱体。取1g该前驱体置于50mL 2mol/L NaOH溶液中,搅拌1h,得到MgOx/Au/re-LDH催化剂。
B.将步骤A得到的MgOx/Au/re-LDH催化剂用于甘油选择性氧化反应中。反应条件为反应温度为60℃,氧气压力为0.3Mpa,甘油/Au的摩尔比=200:1。当反应时间达到4h后,收集液相产物并使用Shimadzu LC-20AT型号高压液相色谱进行分析,结果见表1。
实施例2:
A.同实施例1,使用共沉淀法制备ZnAl-LDHs载体,其中Zn/Al的摩尔比为2:1;使用沉淀沉积法制备Au/ZnAl-LDHs样品;在15%O2/N2气氛,500℃的条件下拓扑还原3h,得到ZnOx/Au/LDO前驱体;于碱溶液中复原得到ZnOx/Au/re-LDH催化剂。
B.同实施例1进行甘油选择性氧化反应性能评价及产物分析,结果见表1。
实施例2:
A.同实施例1,使用共沉淀法制备ZnTi-LDHs载体,其中Zn/Ti的摩尔比为3:1;使用沉淀沉积法制备Au/ZnTi-LDHs样品;在15%H2/N2气氛,500℃的条件下拓扑还原3h,得到ZnOx/Au/LDO前驱体,于碱溶液中复原得到ZnOx/Au/re-LDH催化剂。
B.同实施例1进行甘油选择性氧化反应性能评价及产物分析,结果见表1。
表1
Claims (1)
1.一种用于生物质醇甘油选择性氧化制备二羟基丙酮的Au基催化剂,其特征在于:其化学式表示为M1(OH)x/Au/re-LDHs,其中M1为Mg、Zn中的一种或多种,贵金属Au的负载量为0.5~5wt%,re-LDHs为载体;
制备方法步骤如下:
A.将可溶性M1 2+及M2 3+硝酸盐前驱体配制为混合溶液,其中金属离子的总物质的量浓度为0.1~0.3 mol/L,M1 2+/M2 3+的摩尔比为1~5;将NaOH和Na2CO3配制为碱溶液,其中碱溶液的物质的量浓度为0.2~0.9 mol/L,NaOH/Na2CO3的摩尔比为1~3;将上述盐溶液以1~3 mL/min的速度滴加至碱溶液中,维持溶液pH为9~10;完成操作后将所得悬浊液于60~80℃晶化5~24h;洗涤并离心至上清液中性,于60~90℃下干燥得到LDHs载体;
所述M1 2+是Mg、Zn中的一种或多种, M2 3+是Al、Ti中的一种或多种;
B.将步骤A制备而得的LDHs载体均匀分散到去离子水中,得到固含量为0.01~0.05 g/mL的悬浊液;加入碱及Au金属盐,其中Au的负载量为0.5~5wt%,碱的物质的量为Au的物质的量的400~600倍;将所得悬浊液置于60~90℃中持续搅拌3~6 h,洗涤至上清液为中性并干燥;将所得样品于气氛炉中以2~10 ℃/min的速度升温至200~500℃,保温2~4小时,得到M1Ox/Au/LDO前驱体;
所述Au盐为HAuCl4,Au(en)2Cl3中的一种;碱为NaOH或尿素中的一种;气氛为CO2/N2混合气氛,其中混合气氛中CO2的体积分数为10-30%;
C.将步骤B所得M1Ox/Au/LDO前驱体分散至物质的量浓度为2~4 mol/L的碱溶液中,搅拌0.5-4 h;得到M1(OH)x/Au/re-LDHs催化剂;
所述碱溶液为NaOH、Na2CO3或尿素中的一种或多种。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211170944.4A CN115445611B (zh) | 2022-09-23 | 2022-09-23 | 一种用于甘油选择性氧化制备二羟基丙酮的催化剂及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211170944.4A CN115445611B (zh) | 2022-09-23 | 2022-09-23 | 一种用于甘油选择性氧化制备二羟基丙酮的催化剂及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115445611A CN115445611A (zh) | 2022-12-09 |
CN115445611B true CN115445611B (zh) | 2024-01-26 |
Family
ID=84306617
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211170944.4A Active CN115445611B (zh) | 2022-09-23 | 2022-09-23 | 一种用于甘油选择性氧化制备二羟基丙酮的催化剂及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115445611B (zh) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102432445A (zh) * | 2011-09-30 | 2012-05-02 | 南京工程学院 | 一种利用双氧水选择性氧化甘油制备二羟基丙酮的方法 |
CN103007915A (zh) * | 2012-12-07 | 2013-04-03 | 中国科学院山西煤炭化学研究所 | 一种用于合成碳酸甘油酯的固体碱催化剂及制备方法和应用 |
CN108273502A (zh) * | 2018-03-28 | 2018-07-13 | 北京化工大学 | 一种由甘油制备1,3-二羟基丙酮用催化剂及其制备方法 |
CN110252298A (zh) * | 2019-06-26 | 2019-09-20 | 北京化工大学 | 一种金属氧化物负载金高效催化甘油制备dha的催化剂及其制备方法 |
CN110882701A (zh) * | 2019-12-13 | 2020-03-17 | 北京化工大学 | 甘油制二羟基丙酮用金基双金属/ZnO-CuO催化剂及其制备方法 |
-
2022
- 2022-09-23 CN CN202211170944.4A patent/CN115445611B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102432445A (zh) * | 2011-09-30 | 2012-05-02 | 南京工程学院 | 一种利用双氧水选择性氧化甘油制备二羟基丙酮的方法 |
CN103007915A (zh) * | 2012-12-07 | 2013-04-03 | 中国科学院山西煤炭化学研究所 | 一种用于合成碳酸甘油酯的固体碱催化剂及制备方法和应用 |
CN108273502A (zh) * | 2018-03-28 | 2018-07-13 | 北京化工大学 | 一种由甘油制备1,3-二羟基丙酮用催化剂及其制备方法 |
CN110252298A (zh) * | 2019-06-26 | 2019-09-20 | 北京化工大学 | 一种金属氧化物负载金高效催化甘油制备dha的催化剂及其制备方法 |
CN110882701A (zh) * | 2019-12-13 | 2020-03-17 | 北京化工大学 | 甘油制二羟基丙酮用金基双金属/ZnO-CuO催化剂及其制备方法 |
Non-Patent Citations (2)
Title |
---|
"Acid-base property of the supporting material controls the selectivity of Au catalyst for glycerol oxidation in base-free water";Zifei Yuan等;Chinese Journal of Catalysis;第36卷;第1543–1551页 * |
Zifei Yuan等."Acid-base property of the supporting material controls the selectivity of Au catalyst for glycerol oxidation in base-free water".Chinese Journal of Catalysis.2015,第36卷第1543–1551页. * |
Also Published As
Publication number | Publication date |
---|---|
CN115445611A (zh) | 2022-12-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zhao et al. | Cocatalysts from types, preparation to applications in the field of photocatalysis | |
Jia et al. | Mixed metal sulfides for the application of photocatalytic energy conversion | |
CN109569695B (zh) | 一种用于二氧化碳加氢的核壳结构催化剂的制备方法及其使用方法 | |
Jin et al. | Interface engineering: Synergism between S-scheme heterojunctions and Mo-O bonds for promote photocatalytic hydrogen evolution | |
CN107597119B (zh) | 抗积碳型钴基低温甲烷二氧化碳重整催化剂及其制备方法 | |
CN110013862B (zh) | 一种羟基氧化铁/硫化镉纳米带直接Z-scheme光催化剂及其制备方法 | |
CN113351210B (zh) | 一种Cu基催化剂及将其用于光催化水产氢-5-HMF氧化偶联反应 | |
CN110280281B (zh) | 铁酸锌/黑磷微球复合物的制备方法及其在光催化领域中的应用 | |
CN116139867B (zh) | 一种MOFs衍生的ZnO@CDs@Co3O4复合光催化剂及其制备方法和应用 | |
CN109364927A (zh) | 一种棱柱状氧化铜-氧化锌催化剂的制备方法 | |
CN111172559B (zh) | 一种超薄水滑石基复合光电极及其光电分解水耦合有机物氧化反应的应用 | |
CN112604690A (zh) | 利用农林废弃物制备稀土钙钛矿/生物炭复合材料的方法及其应用 | |
Jin et al. | Fabrication of a novel Ni 3 N/Ni 4 N heterojunction as a non-noble metal co-catalyst to boost the H 2 evolution efficiency of Zn 0.5 Cd 0.5 S | |
CN113649039B (zh) | 一种红磷/碳酸氧铋s型异质结光催化剂及其制备方法 | |
CN114377691A (zh) | 一种甜甜圈状空心多孔Pt-Ni纳米粒子负载氧化钛材料及其制备方法 | |
CN115445611B (zh) | 一种用于甘油选择性氧化制备二羟基丙酮的催化剂及其制备方法 | |
CN114100682B (zh) | 一种羽状叶异质结光催化剂及其制备方法 | |
CN113926480B (zh) | 一种金属合金修饰的层状钙钛矿结构光催化剂的制备方法 | |
CN113101946B (zh) | 一种NiMoO4基Z-型异质结光催化剂及制备与应用 | |
CN114534746A (zh) | 一种基于异质结光催化剂和甲醛水溶液的光催化制氢体系 | |
Huang et al. | Recent progress on photocatalytic hydrogen evolution reaction over metal sulfide cocatalyst-mediated carbon nitride system | |
CN116273180B (zh) | 一种有机锌配合物与硫化钼异质结构的催化剂、制法和应用 | |
CN116371425B (zh) | 富有硫空位的CdS-Vs/Co2RuS6复合催化剂的制备及其应用 | |
CN118529782A (zh) | 一种Mn掺杂Co3O4催化剂的制备方法及其应用 | |
CN116273010A (zh) | 一种氧化亚铜/氧化锌复合材料及其制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |