CN108187739A - 一种葡萄干面包式金-二氧化硅纳米催化剂及其制备和应用 - Google Patents
一种葡萄干面包式金-二氧化硅纳米催化剂及其制备和应用 Download PDFInfo
- Publication number
- CN108187739A CN108187739A CN201810019063.XA CN201810019063A CN108187739A CN 108187739 A CN108187739 A CN 108187739A CN 201810019063 A CN201810019063 A CN 201810019063A CN 108187739 A CN108187739 A CN 108187739A
- Authority
- CN
- China
- Prior art keywords
- sio
- nano
- gold
- particles
- catalyst
- 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.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 39
- 235000001537 Ribes X gardonianum Nutrition 0.000 title claims abstract description 23
- 235000001535 Ribes X utile Nutrition 0.000 title claims abstract description 23
- 235000016919 Ribes petraeum Nutrition 0.000 title claims abstract description 23
- 244000281247 Ribes rubrum Species 0.000 title claims abstract description 23
- 235000002355 Ribes spicatum Nutrition 0.000 title claims abstract description 23
- 235000008429 bread Nutrition 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 40
- 229910052737 gold Inorganic materials 0.000 claims abstract description 27
- 235000013339 cereals Nutrition 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 17
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 17
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 17
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 17
- 239000011246 composite particle Substances 0.000 claims abstract description 15
- 239000008187 granular material Substances 0.000 claims abstract description 14
- 239000002114 nanocomposite Substances 0.000 claims abstract description 14
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 10
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 239000010931 gold Substances 0.000 claims description 44
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 17
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 239000011800 void material Substances 0.000 claims description 6
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 150000002828 nitro derivatives Chemical class 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000011065 in-situ storage Methods 0.000 abstract description 9
- 230000001603 reducing effect Effects 0.000 abstract description 9
- 239000011943 nanocatalyst Substances 0.000 abstract description 5
- 229920001296 polysiloxane Polymers 0.000 abstract description 5
- 230000001681 protective effect Effects 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- -1 silica polyphenol Chemical class 0.000 abstract 1
- 230000012010 growth Effects 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- 229910004042 HAuCl4 Inorganic materials 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- CURNJKLCYZZBNJ-UHFFFAOYSA-M sodium;4-nitrophenolate Chemical compound [Na+].[O-]C1=CC=C([N+]([O-])=O)C=C1 CURNJKLCYZZBNJ-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- BRSVJNYNWNMJKC-UHFFFAOYSA-N [Cl].[Au] Chemical compound [Cl].[Au] BRSVJNYNWNMJKC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0209—Esters of carboxylic or carbonic acids
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
本发明属于纳米材料制备和催化应用领域,具体涉及一种葡萄干面包式的金‑二氧化硅纳米催化剂及其制备和应用,所述的纳米催化剂为Au‑SiO2‑TA‑Fe组成的葡萄干面包式形貌的纳米复合颗粒。所述的催化剂是由Au的前驱物溶液与二氧化硅‑多酚金属纳米颗粒混合反应而制得的Au‑SiO2‑TA‑Fe纳米复合颗粒,复合颗粒粒径为80‑100 nm,Au在复合颗粒中的含量为2.07~2.51 wt%,Au的粒径为2~5 nm。该方法无需使用任何有机溶剂、特殊的仪器或强还原性试剂,仅利用硅羟基及多酚羟基即可原位还原获得单分散的Au纳米颗粒,合成方法绿色环保,简单易行。所制备的Au‑SiO2‑TA‑Fe复合颗粒可应用于催化及生物医学等领域。
Description
技术领域
本发明属于纳米材料制备和催化应用领域,具体涉及一种葡萄干面包式的金-二氧化硅纳米催化剂及其制备和应用。
背景技术
小尺寸金纳米颗粒被广泛应用于有机合成领域中,是新一代具有良好应用前景的催化剂。对负载型金属催化剂来说,颗粒尺寸越小,表面暴露原子数目增加,其催化活性也会增加。但小尺寸的纳米金颗粒在使用过程中易发生团聚,导致其催化稳定性及催化效率会随催化反应时间增长而降低。目前解决这一问题的思路是利用其它热稳定性良好的载体材料固定金纳米颗粒,增强其颗粒的单分散性及稳定性。比如常见的硅材料负载纳米金的制备方法有两种:一种是先将金纳米颗粒从其前驱物中还原出来,再通过巯基或氨基的配位作用负载到硅材料上;另一种是将金属的前驱物溶液浸渍在硅材料中,利用强还原剂溶剂(如NaBH4)将其原位还原在硅材料的孔道中或是中空结构内部。前一种方法由于载体与金之间相互作用力较弱,引入的纳米颗粒含量较低,导致催化活性不高;后一种方法采用原位还原生长Au颗粒,易获得单分散的纳米颗粒;但由于反应过程中使用强还原剂NaBH4,反应速度较快,反应条件不可控,易获得大尺寸的Au颗粒。因此,研发一种绿色环保,简单易行的负载型金纳米催化剂的合成方法极具研究价值。
本实验室所研发的二氧化硅-多酚金属纳米颗粒是多孔隙空心结构,具有较大的比表面积,均一的粒径,且在颗粒内部和表面含有大量的酚羟基,上述这些因素都有利于Au的原位还原生长。因此,本发明拟通过将Au的前驱物溶液与二氧化硅-多酚金属纳米颗粒混合,利用硅羟基及酚羟基的弱还原性原位还原可控生长纳米金。其中,二氧化硅-多酚金属纳米颗粒中所具有的高比例硅羟基及酚羟基不仅可起到弱还原剂作用,同时可起到“铆钉”作用,将获得的Au纳米颗粒牢牢固定在颗粒表面和内部孔隙,起到限制颗粒进一步长大及团聚的作用。
发明内容
本发明的目的在于提供一种葡萄干面包式的金-二氧化硅纳米催化剂及其制备和应用。在本发明的催化剂中,Au纳米颗粒是原位还原生长,且均匀分散于SiO2-TA-Fe纳米颗粒的表面和内部孔隙中。所述制备方法绿色环保,简单易行,能可控生长纳米金。
为实现上述目的,本发明采用如下技术方案:
一种葡萄干面包式的金-二氧化硅纳米催化剂,是由Au的前驱物溶液与二氧化硅-多酚金属纳米颗粒混合反应而制得的Au-SiO2-TA-Fe纳米复合颗粒,Au在复合颗粒中的含量为2.07~2.51wt%,Au的粒径为2~5 nm。复合颗粒粒径为80~100 nm,电位为-27±5 mV。TA是多酚单宁酸的缩写。所述的复合颗粒中,Au纳米颗粒是均匀分散于SiO2-TA-Fe纳米颗粒的表面和内部孔隙中。其原理为:利用二氧化硅球表面羟基及内掺杂的多酚羟基的还原性在SiO2-TA-Fe纳米颗粒表面和内部孔隙原位还原氯金酸,使金纳米颗粒局限在复合颗粒表面及内部,限制了金纳米粒子的团聚及生长,最终得到形貌为葡萄干面包式的金-二氧化硅复合纳米催化剂。
一种制备如上所述的葡萄干面包式的金-二氧化硅纳米催化剂的方法:将SiO2-TA-Fe纳米颗粒与氯金酸溶液混合后,连续超声1-10 min,取出混合液,在60℃水浴中反应6~12 h,反应完成后,离心处理,所得沉淀用超纯水清洗两遍,即得到Au-SiO2-TA-Fe纳米复合颗粒。
反应中SiO2-TA-Fe纳米颗粒与氯金酸的质量比为0.19~0.38:1。
所述的SiO2-TA-Fe纳米颗粒的制备方法为:将430 μL TEOS和8.66 mg TA加入到体积比为60:1的乙醇-水溶液中,搅拌10 min使其混合均匀;逐滴加入0.5 mL的氨水,在25℃条件下反应0.5 h,获得内含多酚低聚体的初级SiO2;然后再加入0.27 mg FeCl3·6H2O,继续在25℃水浴下反应5.5 h,反应完成后,离心处理,用无水乙醇清洗沉淀两遍,再用超纯水清洗两遍,得SiO2-TA-Fe纳米颗粒。
一种如上所述的葡萄干面包式Au-SiO2-TA-Fe纳米颗粒的应用:作为硝基化合物的选择性加氢催化反应的催化剂。
与其他Au催化体系相比,本发明的显著优点在于:
(1)本发明所述的葡萄干面包式Au-SiO2-TA-Fe纳米复合颗粒的制备方法简单,合成过程绿色环保,整个合成过程无需任何有机溶剂、特殊的仪器或强还原性试剂,实现了真正意义上的简单易操作。
(2)本发明利用二氧化硅-多酚金属纳米颗粒富含的硅羟基及酚羟基的弱还原性原位还原生长纳米金,无需添加其他还原剂。其中,二氧化硅-多酚金属纳米颗粒中所具有的高比例硅羟基及酚羟基不仅可起到弱还原剂作用,还可起到“铆钉”作用,将获得的Au纳米颗粒牢牢固定在颗粒表面和内部孔隙,起到限制Au颗粒进一步长大及团聚的作用,同时也提高了纳米金颗粒的催化稳定性。
附图说明
图1中(A)为SiO2-TA-Fe纳米颗粒的TEM图;(B)Au-SiO2-TA-Fe纳米颗粒的TEM图;
图2 Au-SiO2-TA-Fe纳米颗粒的XRD谱图;
图3 Au-SiO2-TA-Fe纳米颗粒催化还原对硝基苯酚的紫外-可见光谱图;
图4 Au-SiO2-TA-Fe纳米颗粒催化还原对硝基苯酚的循环催化柱状图;
图5 Au-SiO2-TA-Fe纳米颗粒催化还原对硝基苯酚的动力学直线变化图。
具体实施方式
下面以具体实施示例对本发明的技术方案做进一步说明,但是不能以此限制本发明的范围。
实施例1
一种葡萄干面包式的金-二氧化硅纳米催化剂的制备方法,包括如下步骤:
1)SiO2-TA-Fe纳米颗粒
将430 μL TEOS和8.66 mg TA加入到体积比为60:1的乙醇-水混合溶液中,搅拌10 min使其混合均匀;逐滴加入0.5 mL浓氨水,在25℃条件下反应0.5 h,获得内含多酚低聚体的初级SiO2;然后再加入0.27 mg FeCl3·6H2O,继续在25℃水浴下反应5.5 h,反应完成后,离心处理沉淀清洗两遍,得到SiO2-TA-Fe纳米颗粒。
2)Au-SiO2-TA-Fe纳米复合颗粒
取250 μL(0.3 mg/mL)的SiO2-TA-Fe纳米颗粒溶液,10000 rpm 离心处理10 min后取出上清液,在超声情况下加入500 μL(1mM HAuCl4·3H2O),即SiO2-TA-Fe纳米颗粒与氯金酸的质量比为0.38:1,连续超声10 min,取出反应液置于60℃水浴中反应12 h。反应完成后,离心处理,沉淀用超纯水清洗两遍,得到Au-SiO2-TA-Fe纳米复合颗粒。将得到的Au-SiO2-TA-Fe纳米复合颗粒利用王水酸化,进行ICP-AES元素分析,结果显示金纳米颗粒在复合颗粒中的比重为2.07%。
实施例2
一种葡萄干面包式的金-二氧化硅纳米催化剂的制备方法,包括如下步骤:
1)依照实施例1(1)合成SiO2-TA-Fe纳米颗粒
2)Au-SiO2-TA-Fe纳米复合颗粒
取250 μL(0.3 mg/mL)的SiO2-TA-Fe纳米颗粒溶液,10000 rpm 离心处理10 min后取出上清液,在超声情况下加入500 μL(1mM HAuCl4·3H2O),即SiO2-TA-Fe纳米颗粒与氯金酸的质量比为0.38:1,连续超声1 min,取出反应液置于60℃水浴中反应12 h。反应完成后,离心处理,沉淀用超纯水清洗两遍,得到Au-SiO2-TA-Fe纳米复合颗粒。将得到的Au-SiO2-TA-Fe纳米复合颗粒利用王水酸化,进行ICP-AES元素分析,结果显示金纳米颗粒在复合颗粒中的比重为2.07%。
实施例3
一种葡萄干面包式的金-二氧化硅纳米催化剂的制备方法,包括如下步骤:
1)依照实施例1(1)合成SiO2-TA-Fe纳米颗粒
2)Au-SiO2-TA-Fe纳米复合颗粒
取250 μL(0.3 mg/mL)的SiO2-TA-Fe纳米颗粒溶液,10000 rpm 离心处理10 min后取出上清液,在超声情况下加入500 μL(2 mM HAuCl4·3H2O),即SiO2-TA-Fe纳米颗粒与氯金酸的质量比为0.19:1,连续超声10 min,取出反应液置于60℃水浴中反应12 h。反应完成后,离心处理,沉淀用超纯水清洗两遍,得到Au-SiO2-TA-Fe纳米复合颗粒。将得到的Au-SiO2-TA-Fe纳米复合颗粒利用王水酸化,进行ICP-AES元素分析,结果显示金纳米颗粒在复合颗粒中的比重为2.50%。
应用实施例1
室温下,在石英小瓶中加入0.1 mL(5 mM)对硝基苯酚水溶液以及1 mL(0.1 mol/L)刚配制的硼氢化钠溶液,加水补齐溶液体积为4 mL,搅拌10 min使其混合均匀后;将实施例1制得的Au-SiO2-TA-Fe纳米颗粒,取0.1 mL(1 mg/mL)加入到石英小瓶中,进行催化还原反应,每隔3 min记录下反应液的紫外-可见吸收数据。
性能检测:
1、将实施例1制得纳米颗粒水溶液滴在铜网上,晾干后进行TEM扫描,结果见图1所示。从图1 的A中可以看出SiO2-TA-Fe颗粒为中空月牙状的球形结构,平均粒径约为90 ±10nm;从图1 的B可以看出Au-SiO2-TA-Fe形貌为葡萄干面包式的球形结构,复合颗粒大小为90 ±10 nm,说明金颗粒的原位生长并未改变SiO2-TA-Fe颗粒的结构。复合颗粒上的金纳米颗粒清晰可见,均匀单分散,粒径为2-5 nm,金纳米颗粒分布在复合颗粒的内部孔道以及颗粒表面,结构稳定,说明可以通过本方法合成结构为葡萄干面包式的金-二氧化硅纳米催化剂。
2、将实施例1制得Au-SiO2-TA-Fe纳米颗粒进行XRD表征,在XRD谱图中,20-30度之间较宽的衍射峰是无定形骨架二氧化硅的弥散峰。38度显示的峰,是面心立方结构金的111晶面的衍射峰,利用谢乐公式计算样品中Au晶粒大小为4-5 nm,这与我们的TEM表征结果基本一致。在XRD图谱上能找到(111)、(220)、(200)、(311)四个Au晶面衍射峰,这说明金颗粒很好的在二氧化硅上原位生长了,结晶度良好。
3、记录应用实施例1的反应液的紫外-可见吸收值,每3 min记录一次,在加入硼氢化钠后,溶液由浅黄色变为黄色,并且在400 nm处可以发现对硝基苯酚钠的吸收峰;加入Au-SiO2-TA-Fe纳米颗粒后,随着反应时间的增加,对硝基苯酚钠逐渐转换为对氨基苯酚,这时可以在305 nm处观察到对氨基苯酚的吸收峰。反应18 min后,可从图中很明显看出400nm的峰吸收值逐渐降低,而305 nm的峰吸收值逐渐增高,说明对硝基苯酚逐渐转变为对氨基苯酚,也说明合成的复合颗粒具有高效的催化活性。经过5次循环催化后金-二氧化硅纳米催化剂的催化效率仍保持在95%以上,说明纳米Au颗粒在复合颗粒中的结构及性能很稳定,有利于保持Au的催化活性。ln(C/C0)是用于说明对硝基苯酚被还原的动力学速度的,K值(动力学一次系数)为0.095 min-1。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (7)
1.一种葡萄干面包式的金-二氧化硅纳米催化剂,其特征在于:所述的催化剂是由Au的前驱物溶液与二氧化硅-多酚-金属纳米颗粒混合反应而制得的Au-SiO2-TA-Fe纳米复合颗粒,Au在复合颗粒中的含量为2.07~2.51wt%,Au的粒径为2~5 nm。
2.根据权利要求1所述的葡萄干面包式的金-二氧化硅纳米催化剂,其特征在于:复合颗粒粒径为80~100 nm,电位为-27±5 mV。
3.根据权利要求1所述的葡萄干面包式的金-二氧化硅纳米催化剂,其特征在于:所述的复合颗粒中,Au纳米颗粒是均匀分散于SiO2-TA-Fe纳米颗粒的表面和内部孔隙中。
4.一种制备如权利要求1-3任一项所述的葡萄干面包式的金-二氧化硅纳米催化剂的方法,其特征在于:将SiO2-TA-Fe纳米颗粒与氯金酸溶液混合后,连续超声1-10 min,取出混合液,在60℃水浴中反应6~12h,反应完成后,离心处理,所得沉淀用超纯水清洗两遍,即得到Au-SiO2-TA-Fe纳米复合颗粒。
5.根据权利要求4所述的制备葡萄干面包式的金-二氧化硅纳米颗粒的方法,其特征在于:反应中SiO2-TA-Fe纳米颗粒与氯金酸的质量比为0.19~0.38:1。
6.根据权利要求4所述的制备葡萄干面包式的金-二氧化硅纳米颗粒的方法,其特征在于:所述的SiO2-TA-Fe纳米颗粒的制备方法为:将430 μL TEOS和8.66 mg TA加入到体积比为60:1的乙醇-水混合溶液中,搅拌10 min使其混合均匀;逐滴加入0.5 mL浓氨水,在25℃条件下反应0.5 h,获得内含多酚低聚体的初级SiO2;然后再加入0.27 mg FeCl3·6H2O,继续在25℃水浴下反应5.5 h,反应完成后,离心处理,沉淀清洗两遍,得SiO2-TA-Fe纳米颗粒。
7.一种如权利要求1-3任一项所述的葡萄干面包式Au-SiO2-TA-Fe纳米颗粒的应用,其特征在于:作为硝基化合物的选择性加氢催化反应的催化剂。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810019063.XA CN108187739B (zh) | 2018-01-09 | 2018-01-09 | 一种葡萄干面包式金-二氧化硅纳米催化剂及其制备和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810019063.XA CN108187739B (zh) | 2018-01-09 | 2018-01-09 | 一种葡萄干面包式金-二氧化硅纳米催化剂及其制备和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108187739A true CN108187739A (zh) | 2018-06-22 |
CN108187739B CN108187739B (zh) | 2019-12-17 |
Family
ID=62588878
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810019063.XA Active CN108187739B (zh) | 2018-01-09 | 2018-01-09 | 一种葡萄干面包式金-二氧化硅纳米催化剂及其制备和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108187739B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109967125A (zh) * | 2019-03-20 | 2019-07-05 | 浙江大学 | 单分散的金属-单宁酸包覆活化碳布的催化剂及其制备方法和应用 |
CN111202091A (zh) * | 2020-01-08 | 2020-05-29 | 华南理工大学 | 一种纳米银负载介孔二氧化硅抗菌材料及其制备方法与应用 |
CN115365493A (zh) * | 2022-08-01 | 2022-11-22 | 武汉纺织大学 | 室温条件下Au@Ag纳米复合粒子的制备方法及应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102600822A (zh) * | 2012-02-17 | 2012-07-25 | 鲁东大学 | 碳掺杂的二氧化硅-二氧化钛复合光催化剂及其制备方法 |
CN107381580A (zh) * | 2017-07-13 | 2017-11-24 | 福州大学 | 一种内掺杂多酚‑金属网状物可降解二氧化硅颗粒的制备方法 |
CN107522239A (zh) * | 2017-08-02 | 2017-12-29 | 四川大学 | 一种基于没食子酸‑金属离子配位化学调控纳米四氧化三铁分散度及粒径的方法 |
-
2018
- 2018-01-09 CN CN201810019063.XA patent/CN108187739B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102600822A (zh) * | 2012-02-17 | 2012-07-25 | 鲁东大学 | 碳掺杂的二氧化硅-二氧化钛复合光催化剂及其制备方法 |
CN107381580A (zh) * | 2017-07-13 | 2017-11-24 | 福州大学 | 一种内掺杂多酚‑金属网状物可降解二氧化硅颗粒的制备方法 |
CN107522239A (zh) * | 2017-08-02 | 2017-12-29 | 四川大学 | 一种基于没食子酸‑金属离子配位化学调控纳米四氧化三铁分散度及粒径的方法 |
Non-Patent Citations (3)
Title |
---|
SHENGCHAO HE等: ""Synthesis and catalytic activity of M@SiO2 (M = Ag, Au, and Pt) nanostructures via "core to shell" and "shell then core" approaches"", 《CHINESE JOURNAL OF CATALYSIS》 * |
张瑛洧: ""基于植物多酚一单宁酸诱导的贵金属纳米粒子/石墨烯复合材料的绿色可控合成及其应用研究"", 《中国化学会第十四届胶体与界面化学会议》 * |
王艳平等: ""二氧化硅接枝黑荆树单宁负载钯催化剂的制备及其性能"", 《化工进展》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109967125A (zh) * | 2019-03-20 | 2019-07-05 | 浙江大学 | 单分散的金属-单宁酸包覆活化碳布的催化剂及其制备方法和应用 |
CN109967125B (zh) * | 2019-03-20 | 2020-06-30 | 浙江大学 | 单分散的金属-单宁酸包覆活化碳布的催化剂及其制备方法和应用 |
CN111202091A (zh) * | 2020-01-08 | 2020-05-29 | 华南理工大学 | 一种纳米银负载介孔二氧化硅抗菌材料及其制备方法与应用 |
CN115365493A (zh) * | 2022-08-01 | 2022-11-22 | 武汉纺织大学 | 室温条件下Au@Ag纳米复合粒子的制备方法及应用 |
CN115365493B (zh) * | 2022-08-01 | 2024-03-26 | 武汉纺织大学 | 室温条件下Au@Ag纳米复合粒子的制备方法及应用 |
Also Published As
Publication number | Publication date |
---|---|
CN108187739B (zh) | 2019-12-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Konar et al. | Shape-dependent catalytic activity of CuO nanostructures | |
Zhan et al. | Facile solvothermal preparation of Fe 3 O 4–Ag nanocomposite with excellent catalytic performance | |
Mohanty et al. | A universal approach to the synthesis of noble metal nanodendrites and their catalytic properties | |
CN102753475B (zh) | 制造方法 | |
CN105731535B (zh) | 一种氧化锌/二氧化钛复合纳米材料的制备方法 | |
CN108187739A (zh) | 一种葡萄干面包式金-二氧化硅纳米催化剂及其制备和应用 | |
CN103599794B (zh) | Fe3O4-Au磁性纳米复合材料及其制备方法与应用 | |
CN102633307A (zh) | 一种水热制备单分散空心磁性纳米粒子的方法 | |
CN102672199B (zh) | 片带一体结构形貌的银颗粒的制备方法 | |
CN108658128B (zh) | 一种具有分级结构的MoS2微纳米球的制备方法 | |
CN108620601B (zh) | 一种室温条件下制备片状Cu纳米晶的方法 | |
Chavhan et al. | Urea and surfactant assisted hydrothermal growth of ceria nanoparticles | |
Li et al. | Synthesis of octahedral and cubic Cu 2 O microcrystals in sub-and super-critical methanol and their photocatalytic performance | |
JP7008373B2 (ja) | 複数の小サイズ触媒からなる複合触媒に基づいて高純度カーボンナノコイルを合成する方法 | |
Yan et al. | Synthesis of Cu 3 BiS 3 and AgBiS 2 crystallites with controlled morphology using hypocrellin template and their catalytic role in the polymerization of alkylsilane | |
CN108453265A (zh) | 一种二氧化硅纳米管限域镍纳米颗粒及其制备方法 | |
CN105127441A (zh) | 一种铂纳米微晶分散体系的制备方法 | |
CN1935662A (zh) | 纳米晶构筑的多孔氧化铜聚集体及制备方法 | |
Wang et al. | Controllable synthesis of metastable γ-Bi2O3 architectures and optical properties | |
CN109289856A (zh) | 一种多面体空心核壳结构MxM′3-xO4@CeO2复合材料及其制备方法 | |
CN107297510B (zh) | 一种银盐中间体分级还原制备纳米级银颗粒粉的方法 | |
CN103789834B (zh) | 微米/纳米级镓酸锌晶体、其制备方法及其用途 | |
Zhang et al. | Photocatalytic performance of Cu 2 O and Ag/Cu 2 O composite octahedra prepared by a propanetriol-reduced process | |
CN101214554A (zh) | 超声场下纳米铜胶体水溶液的一步法制备 | |
CN108971509A (zh) | 一种可控粒径的铁镍合金纳米材料的制备方法 |
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 |