CN110064387A - A method of oxidation restores the catalyst that preparation surface Pd and PdO coexist - Google Patents
A method of oxidation restores the catalyst that preparation surface Pd and PdO coexist Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 36
- 230000003647 oxidation Effects 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 155
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 79
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 64
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 64
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 64
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 64
- 239000000047 product Substances 0.000 claims abstract description 55
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 42
- 235000019441 ethanol Nutrition 0.000 claims abstract description 42
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000004090 dissolution Methods 0.000 claims abstract description 19
- 238000003763 carbonization Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000000460 chlorine Substances 0.000 claims abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000012467 final product Substances 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000005530 etching Methods 0.000 claims abstract 2
- 229910001868 water Inorganic materials 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 15
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 11
- 239000002105 nanoparticle Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 8
- 239000000693 micelle Substances 0.000 claims description 8
- -1 polyoxyethylene Polymers 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 210000002969 egg yolk Anatomy 0.000 claims description 7
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 6
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 5
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 5
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 5
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 4
- 150000005215 alkyl ethers Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011807 nanoball Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 229920004890 Triton X-100 Polymers 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000002077 nanosphere Substances 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 13
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- ASRSBXRMOCLKQC-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)-n-methoxyacetamide Chemical compound CONC(=O)COC1=CC=C(Cl)C=C1C ASRSBXRMOCLKQC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PHBJOSRFHASOAQ-UHFFFAOYSA-N benzene-1,3-diol;hydrate Chemical compound O.OC1=CC=CC(O)=C1 PHBJOSRFHASOAQ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction 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
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/398—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
-
- 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
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/029—Preparation from hydrogen and oxygen
Abstract
The invention discloses a kind of methods that oxidation restores the catalyst that preparation surface Pd and PdO coexist, include the following steps: (1) using the mixture of alkane and alcohol reagent as oily phase, polyethyleneglycol margaron etc. is used as surfactant, is mixed dissolution, obtains A product;(2) KBr addition chlorine palladium acid solution is obtained into B product;(3) NaBH is added4NH is added in solution3·H2TEOS is added in O, and ethyl alcohol is added, most obtains Pd through ethyl alcohol centrifuge washing afterwardsKBr@SiO2Catalyst;(4)PdKBr@SiO2It is distributed in deionized water and alcohol mixeding liquid, CTAB is added and obtains C product;(5) resorcinol, formaldehyde are added into C product, obtains PdKBr@SiO2@RF/CTAB;(6) by PdKBr@SiO2Final product Pd is obtained after restoring after@RF/CTAB carbonization, etching, initial oxidationKBr@HSC.Pd of the inventionKBrSmall, the uniform and not easily to fall off feature of the active component size of@HSC catalyst.
Description
Technical field
The present invention relates to a kind of hydrogen peroxide catalyzed dose of preparation method, especially a kind of oxidation restores preparation surface Pd
With the method for the PdO catalyst coexisted.
Background technique
Hydrogen-oxygen producing hydrogen peroxide by direct synthesis method is in hydrogen peroxide manufacture method, and with simple process, operating cost is low, produces
The advantages that product clean, Atom economy is strong, but H2O2Selectivity and yield it is but very low, industrial requirement is far not achieved.It urges
Agent catalytic activity is with it to H2O2Selectivity be influence hydrogen-oxygen producing hydrogen peroxide by direct synthesis method key factor.Currently, to hydrogen
The research of oxygen producing hydrogen peroxide by direct synthesis catalyst focuses primarily upon loading type Pd base catalyst, and this catalyst has selectivity
Problem low, cyclic utilization rate is low, main cause are that active component Pd disperses unevenly on carrier, amount of activated component Pd group
It is poly- to make full use of;Meanwhile a part of Pd is undersized, generates more unsaturated sites, these unsaturated sites make
It reacts and is carried out to side reaction direction, reduce catalyst choice.In addition, catalyst is in use, active component can be from load
It falls off on body, causes catalyst recycling rate low.Therefore, design preparation active component size uniformity and Gao Xuan not easily to fall off
Selecting property catalyst has a very important significance.
Summary of the invention
The object of the present invention is to provide a kind of methods that oxidation restores the catalyst that preparation surface Pd and PdO coexist.
Pd of the inventionKBr@HSC catalyst has H2O2Selective high-activity component size uniformity and feature not easily to fall off.
Technical solution of the present invention: a method of oxidation restores the catalyst that preparation surface Pd and PdO coexist, including
Following steps:
(1) with hexamethylene, normal heptane or isooctane and n-octyl alcohol, ethyl alcohol, propyl alcohol, n-butanol, the tert-butyl alcohol, n-amyl alcohol, different
The mixture of amylalcohol, n-hexyl alcohol or n-heptanol is as oily phase, polyoxyethylene alkyl ether, Triton X100, nonyl
Phenol polyethenoxy ether or lauryl sodium sulfate are mixed dissolution, obtain A product as surfactant;
(2) by KBr, NaBr or NH3˙Br is added in chlorine palladium acid solution as functional molecular, and conduct in A product is added after dissolution
Water phase forms reversed micelle, obtains B product;
(3) B product are stirring evenly and then adding into NaBH4Solution continuously adds NH after reaction3·H2O, to NH3·H2O sufficiently divides
TEOS is added after being dispersed in around Pd nano particle to be reacted, ethyl alcohol is then added, most obtains Pd through ethyl alcohol centrifuge washing afterwardsKBr@
SiO2Catalyst;
(4) with PdKBr@SiO2Catalyst is distributed in deionized water and alcohol mixeding liquid as template, is stirred evenly,
CTAB is added and stirs to CTAB and is completely dispersed dissolution, obtains C product;
(5) resorcinol then is added into C product, until formaldehyde and ammonium hydroxide is added after being completely dissolved in resorcinol, then passes through
Ethyl alcohol centrifuge washing obtains PdKBr@SiO2@RF/CTAB, by PdKBr@SiO2@RF/CTAB is dried for standby;
(6) by the Pd of dryingKBr@SiO2@RF/CTAB carbonization, by the product Pd of carbonizationKBr@SiO2@C is scattered in H2In O, add
Enter HF solution etches, removes SiO2Obtain PdKBrThe yolk shell structural nano ball of@HCS, by PdKBr@HCS is prior under air atmosphere
Roasting oxidation obtains final product Pd after then restoring under hydrogen atmosphereKBr@HSC。
The method that oxidation above-mentioned restores the catalyst that preparation surface Pd and PdO coexist, the specific steps are as follows:
(1) with 35-45ml hexamethylene, normal heptane or isooctane and 5-15ml n-octyl alcohol, ethyl alcohol, propyl alcohol, n-butanol, tertiary fourth
The oily phase of mixture conduct of alcohol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol or n-heptanol, 8-9g polyoxyethylene alkyl ether, polyoxyethylene are different
Octyl phenyl ether, nonylphenol polyoxyethylene ether or lauryl sodium sulfate are as surfactant, at 30-40 DEG C after being mixed
Dissolution, obtains A product;
(2) by 0.02-0.04g KBr, NaBr or NH3˙It is 0.13-0.17M's that 1ml concentration, which is added, as functional molecular in Br
It in chlorine palladium acid solution, is added in A product after dissolution and is used as water phase, formed reversed micelle, obtain B product;
(3) NaBH that 250-350 μ L concentration is 10wt% is added after B product being stirred 1-3h4Solution, after reacting 5-15min
Continuously add 2-4ml NH3·H2O, to NH3·H2O is added dropwise TEOS and carries out instead after being well dispersed in around Pd nano particle
5-7h is answered, 40-60ml ethyl alcohol is then added, most obtains Pd through ethyl alcohol centrifuge washing afterwardsKBr@SiO2Catalyst;
(4) with Pd made from step (3)KBr@SiO2Catalyst as template, be distributed to 60-80ml deionized water and
In the mixed liquor of 30-40ml ethyl alcohol composition, in 30-40 DEG C of stirring 5-15min, 2-3g CTAB is added, and stir at 30-40 DEG C
It is completely dispersed dissolution to CTAB, obtains C product;
(5) 0.3-0.4g resorcinol is then added into C product, until formaldehyde and ammonia is added after being completely dissolved in resorcinol
Water stirs reaction 10-15h, then obtains Pd through ethyl alcohol centrifuge washingKBr@SiO2@RF/CTAB, by PdKBr@SiO2@RF/CTAB is in 45-
55 DEG C are dried for standby;
(6) by Pd made from step (5)KBr@SiO2@RF/CTAB carbonization, by the product PdKBr@SiO of carbonization2@C is scattered in
30-40ml H2In O, 3-7ml HF solution is added, etches 10-15h in room temperature, removes SiO2Obtain PdKBrThe yolk shell knot of@HCS
Structure nanosphere, by PdKBrRoasting oxidation 1-3h under prior to 200-300 DEG C air atmosphere of@HCS, then in 200-300 DEG C of hydrogen
Final product Pd is obtained under atmosphere after reductase 12-3hKBr@HSC。
Oxidation above-mentioned restores the method for catalyst that preparation surface Pd and PdO coexist, in the step (1), be by
40ml hexamethylene, 10ml n-octyl alcohol and 8.72g polyethyleneglycol margaron are mixed at 35 DEG C.
Oxidation above-mentioned restores the method for catalyst that preparation surface Pd and PdO coexist, in the step (2), be by
0.03g KBr is added in the chlorine palladium acid solution that 1ml concentration is 0.15M as functional molecular.
Oxidation above-mentioned restores the method for catalyst that preparation surface Pd and PdO coexist, and is by B in the step (3)
The NaBH that 300 μ L concentration are 10wt% is added after product stirring 2h4Solution continuously adds 3ml NH after reacting 10min3·H2O, to
NH3·H2O is added dropwise TEOS and carries out reaction 6h after being well dispersed in around Pd nano particle, 50ml ethyl alcohol is then added.
Oxidation above-mentioned restores the method for catalyst that preparation surface Pd and PdO coexist, in the step (4), PdKBr@
SiO2Catalyst be through ultrasonic disperse into mixed liquor.
Oxidation above-mentioned restores the method for catalyst that preparation surface Pd and PdO coexist, in the step (4), be by
PdKBr@SiO2Catalyst is distributed in the mixed liquor of 70ml deionized water and 35ml ethyl alcohol composition, in 35 DEG C of stirring 10min, is added
Enter 2.3g CTAB, and is completely dispersed dissolution in 35 DEG C of stirrings to CTAB.
Oxidation above-mentioned restores the method for catalyst that preparation surface Pd and PdO coexist, and is to C in the step (5)
0.35g resorcinol is added in product, until ammonium hydroxide is added in resorcinol after being completely dissolved, formaldehyde reaction 12h is added after stirring 1h.
Oxidation above-mentioned restores the method for catalyst that preparation surface Pd and PdO coexist, described in the step (6)
Carbonization is to be raised to 140-160 DEG C in a nitrogen atmosphere with 5 DEG C/min heating rate, and keep the temperature 0.5-1.5h at such a temperature, with
It is warming up to 550-650 DEG C with 5 DEG C/min heating rate afterwards, and keeps the temperature 1.5-2.5h.
Oxidation above-mentioned restores the method for catalyst that preparation surface Pd and PdO coexist, in the step (6), carbonization
Product PdKBr@SiO2@C is dispersed in 35ml H2In O, 5ml HF solution is added, etches 12h in room temperature.
Beneficial effects of the present invention
The present invention passes through the hollow catalyst with core-casing structure Pd that addition bromide is that functional molecular is preparedKBr@HSC, application
In hydrogen-oxygen producing hydrogen peroxide by direct synthesis, compared with traditional hydrogen-oxygen direct, have the advantage that
1, it uses porous carbon for shell, prevents the reunion of active component Pd in the follow-up process, active component utilization rate is high;
2, active component is coated in porous carbon shell, keeps active component Pd not easily to fall off in use, raising is urged
Agent reuses efficiency;
3, keep active component surface reduction state metal Pd and oxidation state PdO total in the preparation method of reduction using initial oxidation
It deposits, while guaranteeing conversion ratio, improves catalyst to hydrogen peroxide selectivity.
Detailed description of the invention
Fig. 1 is the flow chart of the method for the present invention;
(a), (b) and (c) are followed successively by Pd in Fig. 2KBrTEM figure, partial size statistical chart and the shell thickness statistical chart of@HCS;
Fig. 3 is Pd of the present inventionKBrThe XPS spectrum figure of@HCS;
Fig. 4 is Pd of the present inventionKBrThe activity rating figure of@HCS.
With Pd it can be seen from Fig. 2 (a)KBr@SiO2For hard template, phenolic resin (RF) is carbon source, passes through self-assembly method
The hollow catalyst with core-casing structure Pd that size is more uniform, covered effect is good can successfully be preparedKBr@HCS.Fig. 2 (b) it is found that
PdKBrFor the particle diameter distribution of@HCS in 60nm~100nm, average grain diameter is only 72.46 ± 9.84nm, shows its, ruler small with partial size
The advantages that very little uniform;By scheming (c) it is found that PdKBrNot only thickness is uniform for the shell of@HCS, and is less than 10nm, and average thickness is only
7.90 ± 1.31nm, thin shell are not only able to prevent Pd nanometers of active component of reunion and loss, and can also reduce reaction
Object and product pass in and out the obstruction of the microreactor, improve catalytic activity.
As seen from Figure 3, catalyst PdKBr@HCS contains reduction-state Pd and oxidation state PdO in surface simultaneously.
From fig. 4, it can be seen that catalyst PdKBrThe H of@HCS2Conversion ratio, yield, selectivity respectively 34%, 30.1%,
88.5%, there is excellent activity to hydrogen-oxygen producing hydrogen peroxide by direct synthesis, yield reaches 2014mmol (gPd.h)-1.In active component
It measures in identical situation, the active surface that the Pd particle of small size exposes is more, so that active component Pd utilization rate is high, to hydrogen
Gas conversion ratio reaches 50%, while the addition of Br effectively inhibits catalyst to H2O2Decomposition and hydrogenation activity so that catalyst
76% is reached to the selectivity of hydrogen peroxide.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated, but is not intended as the foundation limited the present invention.
The embodiment of the present invention
Embodiment 1
(1) Pd is preparedKBr@SiO2: using hexamethylene (40mL), n-octyl alcohol (10mL) as oily phase, polyethyleneglycol margaron
(Brij56) (8.72g) is used as surfactant, the mixed dissolution at 35 DEG C;0.03g KBr is dense as functional molecular addition 1mL
It spends in the chlorine palladium acid solution of 0.15M, is added dropwise after dissolution in above-mentioned oil-phase solution as water phase, forms reversed micelle.Due to
Water phase is mutually incompatible with oil, will form the very strong rigid film of rigidity at two-phase interface, so water phase will form an independence
Nanoscale microreactor (Fig. 1-I).The NaBH of 300 μ L is added after above-mentioned solution stirring 2h4(10wt%) solution, divalent state
Palladium ion (Pd2+) by NaBH4It is reduced into Pd nano particle (Fig. 1-II) rapidly.3mlNH is added dropwise after reaction 10min3·
H2O provides the TEOS alkaline environment of hydrolysis, TEOS is added dropwise after ammonium hydroxide is well dispersed in around Pd nano particle later,
TEOS can hydrolyze to form SiO under alkaline condition2.In water phase microreactor, the SiO that hydrolyzes to form2It can Coated with Palladium nanoparticle
Son.It reacts and 50mL ethyl alcohol is added after 6h, ethyl alcohol can dissolve Brij56 and abolish rigid film (demulsification) between water phase and oily phase, later
Through ethyl alcohol centrifuge washing, Pd is finally obtainedKBr@SiO2Catalyst.
(2) Pd is preparedKBr@SiO2@RF: the Pd being prepared by reversed micelle methodKBr@SiO2Catalyst is super as template
Sound is distributed in 70mL deionized water and 30mL ethyl alcohol, stirs 10min at 35 DEG C;2.3gCTAB is added, under the conditions of 35 DEG C
Persistently stirring 30min waits for that CTAB is completely dispersed dissolution.In this course due in water phase, PdKBr@SiO2SiO2Layer surface
Negatively charged, CTAB dissociates the quaternary ammonium ion to be formed (CTMA+) since electrostatic interaction is adsorbed on SiO2Surface (Fig. 1-IV), thus
Prevent their reunion.Then 0.35g resorcinol is added, be added after resorcinol is completely dissolved after 30min formaldehyde and
Ammonium hydroxide;Ammonium hydroxide provides resorcinol and formaldehyde condensation polymer forms the alkaline environment of phenolic resin (RF).Resorcinol and formaldehyde are in alkali
Polycondensation reaction under the conditions of property is slower, in this course, the formation of intermediate product hydroxymethyl substitutions can be diffused by
In the silica particle surface of the electrostatic interaction with quaternary ammonium ion, and the condensation reaction of these species can surround SiO2Grain
The nano-pore of son forms a RF polymer layer.Pd is obtained through ethyl alcohol centrifuge washing 3 times after reaction 12hKBr@SiO2@RF/CTAB, will
PdKBr@SiO2@RF/CTAB is dried for standby in 50 DEG C.
(3) Pd is preparedKBr@HSC:PdKBr@SiO2The carbonization of@RF is raised to 150 DEG C from room temperature in a nitrogen atmosphere, and at this
At a temperature of keep the temperature 1h, be then warming up to 600 DEG C, and keep the temperature 2h, remove CTAB in this course, and phenolic resin is by charcoal
Change.The product Pd of pyrolysisKBr@SiO2@C is scattered in 35ml H2O, and 5mlHF solution room temperature is added and etches 12h, removes SiO2It obtains
PdKBrThe yolk shell structural nano ball of@HCS.PdKBrRoasting oxidation 2h under prior to 250 DEG C air atmospheres of@HCS, then in 250 DEG C
Hydrogen atmosphere under reductase 12 .5h obtain final product PdKBr@HSC。
Embodiment 2
(1) using the mixture of 35ml normal heptane and 5ml propyl alcohol as oily phase, 6g nonylphenol polyoxyethylene ether is living as surface
Property agent, after being mixed 30 DEG C dissolve, obtain A product;
(2) by 0.02g NH3˙Br is added in the chlorine palladium acid solution that 1ml concentration is 0.13M as functional molecular, is added after dissolution
Enter in A product as water phase, forms reversed micelle, obtain B product;
(3) NaBH that 250 μ L concentration are 10wt% is added after B product being stirred 1h4Solution continuously adds after reacting 5min
2ml NH3·H2O, to NH3·H2O is added dropwise TEOS and carries out reaction 5h after being well dispersed in around Pd nano particle, then plus
Enter 40ml ethyl alcohol, most obtains Pd through ethyl alcohol centrifuge washing afterwardsKBr@SiO2Catalyst;
(4) with Pd made from step (3)KBr@SiO2Catalyst is distributed to 60ml deionized water and 30ml as template
In the mixed liquor of ethyl alcohol composition, in 30 DEG C of stirring 5min, 2g CTAB is added, and be completely dispersed dissolution in 30 DEG C of stirrings to CTAB,
Obtain C product;
(5) 0.3g resorcinol is then added into C product, until ammonium hydroxide is added in resorcinol after being completely dissolved, stirs 0.5h
Formaldehyde is added afterwards and reacts 10h, then obtains Pd through ethyl alcohol centrifuge washingKBr@SiO2@RF/CTAB, by PdKBr@SiO2@RF/CTAB in
55 DEG C are dried for standby;
(6) by Pd made from step (5)KBr@SiO2@RF/CTAB carbonization, by the product Pd of carbonizationKBr@SiO2@C is scattered in
30ml H2In O, 3ml HF solution is added, etches 10h in room temperature, removes SiO2Obtain PdKBrThe yolk shell structural nano of@HCS
Ball, by PdKBrRoasting oxidation 3h under prior to 200 DEG C air atmospheres of@HCS is obtained after then restoring 3h under 200 DEG C of hydrogen atmosphere
To final product PdKBr@HSC。
Embodiment 3
(1) using the mixture of 45ml isooctane and 15ml n-heptanol as oily phase, 9g lauryl sodium sulfate is as surface
Activating agent dissolves at 40 DEG C after being mixed, obtains A product;
(2) it is added in the chlorine palladium acid solution that 1ml concentration is 0.17M using 0.04g NaBr as functional molecular, adds after dissolution
Enter in A product as water phase, forms reversed micelle, obtain B product;
(3) NaBH that 350 μ L concentration are 10wt% is added after B product being stirred 3h4Solution continuously adds after reacting 15min
4ml NH3·H2O, to NH3·H2O is added dropwise TEOS and carries out reaction 7h after being well dispersed in around Pd nano particle, then plus
Enter 60ml ethyl alcohol, most obtains Pd through ethyl alcohol centrifuge washing afterwardsKBr@SiO2Catalyst;
(4) with Pd made from step (3)KBr@SiO2Catalyst is distributed to 80ml deionized water and 40ml as template
In the mixed liquor of ethyl alcohol composition, in 40 DEG C of stirring 15min, 3g CTAB is added, and stir to CTAB at 40 DEG C be completely dispersed it is molten
Solution, obtains C product;
(5) 0.4g resorcinol is then added into C product, until ammonium hydroxide is added in resorcinol after being completely dissolved, stirs 1.5h
Formaldehyde is added afterwards and reacts 15h, then obtains Pd through ethyl alcohol centrifuge washingKBr@SiO2@RF/CTAB, by PdKBr@SiO2@RF/CTAB in
45 DEG C are dried for standby;
(6) by Pd made from step (5)KBr@SiO2@RF/CTAB carbonization, by the product Pd of carbonizationKBr@SiO2@C is scattered in
40ml H2In O, 7ml HF solution is added, etches 15h in room temperature, removes SiO2Obtain PdKBrThe yolk shell structural nano of@HCS
Ball, by PdKBrThen roasting oxidation 1h under prior to 300 DEG C air atmospheres of@HCS is obtained after reductase 12 h under 300 DEG C of hydrogen atmosphere
To final product PdKBr@HSC。
Claims (10)
1. a kind of method that oxidation restores the catalyst that preparation surface Pd and PdO coexist, which is characterized in that including walking as follows
It is rapid:
(1) with hexamethylene, normal heptane or isooctane and n-octyl alcohol, ethyl alcohol, propyl alcohol, n-butanol, the tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol,
The mixture of n-hexyl alcohol or n-heptanol is as oily phase, polyoxyethylene alkyl ether, Triton X100, polyoxyethylene nonyl phenyl
Vinethene or lauryl sodium sulfate are mixed dissolution, obtain A product as surfactant;
(2) by KBr, NaBr or NH3˙Br is added in chlorine palladium acid solution as functional molecular, is added in A product after dissolution and is used as water phase,
Reversed micelle is formed, B product are obtained;
(3) B product are stirring evenly and then adding into NaBH4Solution continuously adds NH after reaction3·H2O, to NH3·H2O is well dispersed in
TEOS is added after around Pd nano particle to be reacted, ethyl alcohol is then added, most obtains Pd through ethyl alcohol centrifuge washing afterwardsKBr@SiO2
Catalyst;
(4) with PdKBr@SiO2Catalyst is distributed in deionized water and alcohol mixeding liquid as template, is stirred evenly, and is added
CTAB is simultaneously stirred and to CTAB is completely dispersed dissolution, obtains C product;
(5) resorcinol then is added into C product, until formaldehyde and ammonium hydroxide is added after being completely dissolved in resorcinol, then through ethyl alcohol
Centrifuge washing obtains PdKBr@SiO2@RF/CTAB, by PdKBr@SiO2@RF/CTAB is dried for standby;
(6) by the Pd of dryingKBr@SiO2@RF/CTAB carbonization, by the product Pd of carbonizationKBr@SiO2@C is scattered in H2In O, HF is added
Solution etches remove SiO2Obtain PdKBrThe yolk shell structural nano ball of@HCS, by PdKBr@HCS under air atmosphere prior to roasting
Oxidation obtains final product Pd after then restoring under hydrogen atmosphereKBr@HSC。
2. the method that oxidation according to claim 1 restores the catalyst that preparation surface Pd and PdO coexist, feature exist
In, the specific steps are as follows:
(1) with 35-45ml hexamethylene, normal heptane or isooctane and 5-15ml n-octyl alcohol, ethyl alcohol, propyl alcohol, n-butanol, the tert-butyl alcohol,
The oily phase of mixture conduct of n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol or n-heptanol, 8-9g polyoxyethylene alkyl ether, polyoxyethylene are different pungent
Base phenyl ether, nonylphenol polyoxyethylene ether or lauryl sodium sulfate are molten at 30-40 DEG C after being mixed as surfactant
Solution, obtains A product;
(2) by 0.02-0.04g KBr, NaBr or NH3˙The chlorine palladium that 1ml concentration is 0.13-0.17M is added as functional molecular by Br
It in acid solution, is added in A product after dissolution and is used as water phase, formed reversed micelle, obtain B product;
(3) NaBH that 250-350 μ L concentration is 10wt% is added after B product being stirred 1-3h4Solution continues to add after reacting 5-15min
Enter 2-4ml NH3·H2O, to NH3·H2O is added dropwise TEOS and carries out reaction 5-7h after being well dispersed in around Pd nano particle,
Then 40-60ml ethyl alcohol is added, most obtains Pd through ethyl alcohol centrifuge washing afterwardsKBr@SiO2Catalyst;
(4) with Pd made from step (3)KBr@SiO2Catalyst is distributed to 60-80ml deionized water and 30-40ml as template
In the mixed liquor of ethyl alcohol composition, in 30-40 DEG C of stirring 5-15min, 2-3g CTAB is added, and complete to CTAB in 30-40 DEG C of stirring
Full dispersing and dissolving obtains C product;
(5) 0.3-0.4g resorcinol is then added into C product, until formaldehyde and ammonium hydroxide is added after being completely dissolved in resorcinol, stirs
Reaction 10-15h is mixed, then obtains Pd through ethyl alcohol centrifuge washingKBr@SiO2@RF/CTAB, by PdKBr@SiO2@RF/CTAB is in 45-55
It DEG C is dried for standby;
(6) by Pd made from step (5)KBr@SiO2@RF/CTAB carbonization, by the product PdKBr@SiO of carbonization2@C is scattered in 30-
40ml H2In O, 3-7ml HF solution is added, etches 10-15h in room temperature, removes SiO2Obtain PdKBrThe yolk shell structure of@HCS
Nanosphere, by PdKBrRoasting oxidation 1-3h under prior to 200-300 DEG C air atmosphere of@HCS, then in 200-300 DEG C of hydrogen gas
Final product Pd is obtained under atmosphere after reductase 12-3hKBr@HSC。
3. the method that oxidation according to claim 2 restores the catalyst that preparation surface Pd and PdO coexist, feature exist
In: it is to mix 40ml hexamethylene, 10ml n-octyl alcohol and 8.72g polyethyleneglycol margaron at 35 DEG C in the step (1).
4. the method that oxidation according to claim 2 restores the catalyst that preparation surface Pd and PdO coexist, feature exist
In: it in the step (2), is added in the chlorine palladium acid solution that 1ml concentration is 0.15M using 0.03g KBr as functional molecular.
5. the method that oxidation according to claim 2 restores the catalyst that preparation surface Pd and PdO coexist, feature exist
In: it is that the NaBH that 300 μ L concentration are 10wt% is added after B product to be stirred to 2h in the step (3)4Solution, after reacting 10min
Continuously add 3ml NH3·H2O, to NH3·H2O is added dropwise TEOS after being well dispersed in around Pd nano particle and is reacted
Then 50ml ethyl alcohol is added in 6h.
6. the method that oxidation according to claim 2 restores the catalyst that preparation surface Pd and PdO coexist, feature exist
In: in the step (4), PdKBr@SiO2Catalyst be through ultrasonic disperse into mixed liquor.
7. the method that oxidation according to claim 2 restores the catalyst that preparation surface Pd and PdO coexist, feature exist
In: it is by Pd in the step (4)KBr@SiO2Catalyst is distributed to the mixed liquor of 70ml deionized water and 35ml ethyl alcohol composition
In, in 35 DEG C of stirring 10min, 2.3g CTAB is added, and be completely dispersed dissolution in 35 DEG C of stirrings to CTAB.
8. the method that oxidation according to claim 2 restores the catalyst that preparation surface Pd and PdO coexist, feature exist
In: it is the addition 0.35g resorcinol into C product in the step (5), until ammonium hydroxide is added in resorcinol after being completely dissolved, stirring
Formaldehyde is added after 1h and reacts 12h.
9. the method that oxidation according to claim 2 restores the catalyst that preparation surface Pd and PdO coexist, feature exist
In: in the step (6), the carbonization is to be raised to 140-160 DEG C in a nitrogen atmosphere with 5 DEG C/min heating rate, and at this
At a temperature of keep the temperature 0.5-1.5h, be then warming up to 550-650 DEG C with 5 DEG C/min heating rate, and keep the temperature 1.5-2.5h.
10. the method that oxidation according to claim 2 restores the catalyst that preparation surface Pd and PdO coexist, feature
It is: in the step (6), the product Pd of carbonizationKBr@SiO2@C is dispersed in 35ml H2In O, 5ml HF solution is added, normal
Temperature etching 12h.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102019431A (en) * | 2010-09-30 | 2011-04-20 | 大连理工大学 | Metallic nano cluster/silicon dioxide hollow nuclear shell structured nanoparticles and preparation method thereof |
KR20160149971A (en) * | 2015-06-18 | 2016-12-28 | 고려대학교 산학협력단 | Nanoparticle catalysis for synthesis of hydrogen peroxide and method of synthesis of hydrogen peroxide using said catalysis |
KR20170097461A (en) * | 2016-02-18 | 2017-08-28 | 고려대학교 산학협력단 | Nanoparticle catalysis for synthesis of hydrogen peroxide and method of synthesis of hydrogen peroxide using the same |
US20180056277A1 (en) * | 2016-08-30 | 2018-03-01 | Korea University Research And Business Foundation | Nanocatalyst with mesoporous shell for hydrogen peroxide production and methodfor hydrogen peroxide production using the same |
CN107754826A (en) * | 2017-11-06 | 2018-03-06 | 贵州大学 | A kind of producing hydrogen peroxide by direct synthesis hollow core shell structure Pd catalyst and preparation method thereof |
-
2019
- 2019-03-19 CN CN201910208306.9A patent/CN110064387A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102019431A (en) * | 2010-09-30 | 2011-04-20 | 大连理工大学 | Metallic nano cluster/silicon dioxide hollow nuclear shell structured nanoparticles and preparation method thereof |
KR20160149971A (en) * | 2015-06-18 | 2016-12-28 | 고려대학교 산학협력단 | Nanoparticle catalysis for synthesis of hydrogen peroxide and method of synthesis of hydrogen peroxide using said catalysis |
KR20170097461A (en) * | 2016-02-18 | 2017-08-28 | 고려대학교 산학협력단 | Nanoparticle catalysis for synthesis of hydrogen peroxide and method of synthesis of hydrogen peroxide using the same |
US20180056277A1 (en) * | 2016-08-30 | 2018-03-01 | Korea University Research And Business Foundation | Nanocatalyst with mesoporous shell for hydrogen peroxide production and methodfor hydrogen peroxide production using the same |
CN107754826A (en) * | 2017-11-06 | 2018-03-06 | 贵州大学 | A kind of producing hydrogen peroxide by direct synthesis hollow core shell structure Pd catalyst and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
ZHENG CHEN ET AL.: "The modification of Pd core-silica shell catalysts by functional molecules (KBr, CTAB, SC) and their application to the direct synthesis of hydrogen peroxide from hydrogen and oxygen", 《CATALYSIS SCIENCE & TECHNOLOGY》 * |
张新生: "核壳结构纳米Ag@SiO2的制备及其杀菌、防腐和应用性能研究", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113707895A (en) * | 2021-08-26 | 2021-11-26 | 浙江大学 | Preparation method and application of heterostructure catalyst with rich interface active sites |
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