CN110152664B - Preparation method and application of one-dimensional cuprous oxide/carbon nano composite catalyst - Google Patents
Preparation method and application of one-dimensional cuprous oxide/carbon nano composite catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 53
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 36
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 33
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229960001860 salicylate Drugs 0.000 claims abstract description 21
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000009830 intercalation Methods 0.000 claims abstract description 16
- 230000002687 intercalation Effects 0.000 claims abstract description 16
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000005750 Copper hydroxide Substances 0.000 claims abstract description 14
- 229910001956 copper hydroxide Inorganic materials 0.000 claims abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 14
- 239000007791 liquid phase Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 229960004025 sodium salicylate Drugs 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000002121 nanofiber Substances 0.000 claims description 3
- FRMWBRPWYBNAFB-UHFFFAOYSA-M potassium salicylate Chemical compound [K+].OC1=CC=CC=C1C([O-])=O FRMWBRPWYBNAFB-UHFFFAOYSA-M 0.000 claims description 3
- 229960003629 potassium salicylate Drugs 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 238000003746 solid phase reaction Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000013148 Cu-BTC MOF Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Images
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/647—
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
Abstract
The invention discloses a preparation method and application of a one-dimensional cuprous oxide/carbon nano composite catalyst. The invention utilizes the intercalation assembly function of the salicylate and metal ions to prepare the salicylate intercalation layered copper hydroxide with one-dimensional morphology, and then the one-dimensional cuprous oxide/carbon nano composite catalyst is prepared by two steps of solid-phase reaction of solid pyrolysis and low-temperature oxidation. The method takes cheap water-soluble salt as a reactant, does not need an organic solvent, a surfactant, an additional carrier, a template agent, a reducing agent and the like in the preparation process, and the prepared catalyst has uniform particle distribution, high purity and high crystallinity, and Cu nanoparticles form Cu with a hollow structure by utilizing the Kirkendall effect2And O. The catalyst synthesized by the method shows excellent catalytic performance and good circulation stability in the liquid phase hydrogenation reaction of p-nitrophenol.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to one-dimensional Cu2An O/C nano catalyst, a preparation method thereof and application thereof in p-nitrophenol hydrogenation reaction.
Background
Cuprous oxide (Cu)2O) is an important functional material, has the characteristics of no toxicity, low preparation cost, good environmental tolerance and the like, and has wide application prospects in catalysis, biocides, gas sensors, solar photovoltaic cells and lithium ion batteries. Carbon nanomaterials are considered to be good catalyst supports due to their large surface area, high electrical conductivity, and high mechanical strength. The cuprous oxide is loaded on the surface of the carbon nano material, so that the dispersibility of metal particles can be improved, and meanwhile, the electronic structural characteristics of the carbon nano material can promote the electron transfer in the catalytic reaction process, thereby being beneficial to improving the catalytic performance and having potential application prospect in the field of catalysis.
Currently, few reports about cuprous oxide/carbon nano composite catalysts exist. Document Huang et al [ Huang C et al, Acs Applied Materials&Interfaces,2014,6(16):14469-14476]Adding CuCl2Adding into a pre-prepared hexagonal boron nitride (h-BN) suspension, and adding CuCl with glucose2Reduction to Cu2O, octahedral Cu is obtained2O/h-BN. Li et al [ Li H et al, Advanced Energy Materials,2015,5(5):1401077]With CuSO4CQDs/Cu are synthesized by taking glucose, polyvinylpyrrolidone and the like as raw materials through an ultrasonic method2And O. Yang et al [ Ke Yang et al, Nanoscale,2018,10,17647-]With Cu (NO)3)2·3H2O and trimesic acid (H)3BTC) as a raw material, synthesizing Cu-BTC/GO by a hydrothermal method under the condition of additionally adding Graphene Oxide (GO), and roasting the Cu-BTC/GO to obtain Cu/Cu2O @ C. Patent CN106622236 discloses a method for preparing a cuprous oxide-carbon nanotube-graphene composite catalyst by depositing a copper salt on a previously prepared carbon nanotube-graphene porous support by a spray pyrolysis method. The existing synthesis method usually needs additional carriers, templates and reducing agents, and has high costThe composition, structure and dispersibility are difficult to control, so a new method is developed to prepare high-quality Cu with high catalytic activity2The O/C nano composite catalyst has important practical significance.
The layered hydroxide is an anionic clay material with a typical layered structure, has the characteristics of adjustable layered metal cations, adjustable interlayer intercalation anion types and quantity and the like, and can be divided into two types: one is Layered Double Hydroxide (LDHs) with the structural general formula of [ M2+ 1-xM3+ x·(OH)2]x+(An-)x/n·mH2O, in the formula M2+Is a divalent metal cation M in an octahedral sheet3+Is a trivalent metal cation, An-Is an interlayer anion to maintain overall charge balance. The other is a Layered hydroxide metal salts (LHSs), and the structural general formula is [ M2+(OH)2-x](An-)x/n·mH2And O. The metal cations in the interlayer plate in the layered hydroxide are orderly dispersed in atomic level, a series of metal, metal oxide, metal sulfide and carbon nano composite materials with adjustable components and uniform structures can be economically and efficiently prepared by taking the metal cations as precursors, and the nano composite materials have wide application prospects in the fields of catalytic hydrogenation, photocatalysis, electrocatalysis and the like.
Disclosure of Invention
The invention aims to provide a method for preparing a one-dimensional cuprous oxide/carbon nano composite catalyst and application thereof in p-nitrophenol hydrogenation.
The invention prepares the one-dimensional salicylate intercalation layered copper hydroxide by a simple self-assembly process, and prepares the one-dimensional cuprous oxide/carbon nano composite catalyst with a hollow structure and a low oxidation state by taking the one-dimensional salicylate intercalation layered copper hydroxide as a single precursor through two-step solid-phase reaction.
The one-dimensional cuprous oxide/carbon nano composite catalyst is of a one-dimensional structure, and the length of the nano fiber is 10 mu m, and the width of the nano fiber is 150 nm; the specific surface area of the nano composite catalyst is 20-200m2g-1The aperture is between 2 and 30 nm; carbon substrateIs obtained by thermal decomposition of organic carbon source, and has hollow cuprous oxide particles with size of 30-80nm uniformly embedded in carbon matrix.
The preparation method of the one-dimensional cuprous oxide/carbon nano composite catalyst comprises the following steps:
1) the concentration is 0.01 to 0.6 mol.L-1The concentration of the soluble cupric salt aqueous solution is 0.01-0.6 mol.L-1Adding the aqueous solution of the salicylate into a flask, and uniformly mixing, wherein the molar ratio of the divalent copper salt to the salicylate is 2: 1-8; using 0.1-1 mol. L-1Regulating the pH value of the sodium hydroxide solution to 4-7, keeping the reaction temperature at 60-100 ℃, crystallizing for 9-48h in the protection of inert atmosphere, naturally cooling to room temperature, centrifugally separating, washing to be neutral by using deionized water, and drying in a drying oven at constant temperature to obtain a one-dimensional salicylate intercalation layered copper hydroxide precursor;
2) roasting the precursor prepared in the step 1) for 0.5-4h at 900 ℃ in an inert atmosphere of 350-;
3) and (3) roasting the one-dimensional Cu/C nano composite material prepared in the step 2) for 1-60min at the temperature of 100-400 ℃ in an oxidizing atmosphere to finally obtain the one-dimensional cuprous oxide/carbon nano composite catalyst.
The soluble divalent copper salt in the step 1) is one of copper nitrate, copper chloride and copper sulfate.
The salicylate in the step 1) is sodium salicylate or potassium salicylate.
The oxidizing atmosphere in the step 3) is one or two of air and oxygen.
The one-dimensional cuprous oxide/carbon nano composite catalyst prepared by the method is applied to the liquid-phase hydrogenation reaction of p-nitrophenol. The specific reaction conditions are as follows: mixing p-nitrophenol solution with NaBH4Or KBH4Mixing the solutions, and then adding a one-dimensional cuprous oxide/carbon nano composite catalyst for reaction.
The invention utilizes the intercalation assembly function of the salicylate and metal ions to prepare the salicylate intercalation layered copper hydroxide with one-dimensional morphology, and then the salicylate intercalation layered copper hydroxide is subjected to two solid-phase reactions of solid pyrolysis and low-temperature oxidationThe one-dimensional cuprous oxide/carbon nano composite catalyst is prepared. The method takes cheap water-soluble salt as a reactant, does not need an organic solvent, a surfactant, an additional carrier, a template agent, a reducing agent and the like in the preparation process, and the prepared catalyst has uniform particle distribution, high purity and high crystallinity, and Cu nanoparticles form Cu with a hollow structure by utilizing the Kirkendall effect2And O. The catalyst synthesized by the method shows excellent catalytic performance and good circulation stability in the liquid phase hydrogenation reaction of p-nitrophenol. The rate activity parameter (k') was 6.74s-1mg-1Much higher than commercial Pt/C for 0.25s-1mg-1。
Drawings
FIG. 1 is a scanning electron micrograph of a layered copper hydroxide precursor.
FIG. 2 is Cu2The preparation of the O/C nano composite catalyst is shown schematically.
FIG. 3 is Cu2Transmission electron microscope and high resolution transmission electron microscope photographs of the O/C nano composite catalyst.
FIG. 4 is Cu2The nitrogen adsorption and desorption curve and the aperture distribution diagram of the O/C nano composite catalyst.
FIG. 5 is Cu2X-ray diffraction pattern of O/C nanocomposite catalyst.
FIG. 6 is Cu2XPS spectrum of the O/C nano composite catalyst.
FIG. 7 is Cu2An ultraviolet-visible spectrum chart for testing the liquid-phase hydrogenation performance of p-nitrophenol catalyzed by the O/C nano composite catalyst.
FIG. 8 is Cu2First order kinetic curves of the O/C nano composite catalyst and the commercial Pt/C in the catalytic hydrogenation reaction are compared.
FIG. 9 is Cu2And (3) recycling the absorption spectrum and the histogram of the O/C nano composite catalyst.
Detailed Description
The preparation process of the present invention is further illustrated with reference to the following specific examples, but the scope of the present invention is not limited thereto.
Example 1
1) 100mL of the solution was added to a reaction solution at a concentration of 0.2 mol. L-1The copper nitrate aqueous solution was mixed with 150mL of a 0.15 mol. L concentration solution-1The sodium salicylate solution is evenly mixed, and 0.5 mol.L is slowly added after stirring-1Adjusting the pH of the system to 7, reacting for 36h in a nitrogen atmosphere at 90 ℃, centrifuging, washing and drying the product to obtain a one-dimensional salicylate intercalation layered copper hydroxide precursor, wherein the scanning electron microscope picture is shown in figure 1;
2) and roasting the precursor prepared in the step at 400 ℃ for 30min in a nitrogen atmosphere to obtain the one-dimensional Cu/C nano composite material.
3) Roasting the one-dimensional Cu/C nano composite material prepared in the step 2) in an oxygen atmosphere at 100 ℃ for 30min to obtain a cuprous oxide/carbon nano composite catalyst, and marking as a catalyst Cu2O/C-1, scheme for preparation is shown in FIG. 2.
The cuprous oxide/carbon nano composite catalyst prepared by the method is used for catalyzing p-nitrophenol liquid-phase hydrogenation reaction: adding 2.5 mmol.L into a quartz cuvette in advance -1200 mu L of p-nitrophenol, 26 mmol. multidot.L-12.5mL of the aqueous solution of sodium borohydride was added thereto, and 1 mg. multidot.mL of the aqueous solution was added-1The reaction was carried out with 5. mu.L of the catalyst, and the change in the absorption intensity was recorded to indicate the catalytic activity of the catalyst.
Example 2
1) 100mL of the solution was added to a reaction solution at a concentration of 0.2 mol. L-1The copper chloride solution of (2) and 150mL of copper chloride solution with a concentration of 0.26 mol.L-1The sodium salicylate aqueous solution is evenly mixed, and 0.5 mol.L is slowly added after stirring-1Adjusting the pH value of the system to 6.5, reacting for 48 hours at 80 ℃ in an argon atmosphere, centrifuging, washing and drying the product to obtain a one-dimensional salicylate intercalation layered copper hydroxide precursor;
2) and roasting the precursor prepared in the step at 600 ℃ for 5min in a nitrogen atmosphere to obtain the one-dimensional Cu/C nano composite material.
3) Placing the nano composite material prepared in the step 2) in an oxygen atmosphere to roast for 0min at 200 ℃ to obtain a cuprous oxide/carbon nano composite material, and marking as a catalyst Cu2O/C-2, the characterization results are shown in FIGS. 3-6.
The liquid phase hydrogenation reaction process of the p-nitrophenol comprises the following steps: adding 2.5 mmol.L into a quartz cuvette in advance -1200 mu L of p-nitrophenol, 26 mmol. multidot.L-12.5mL of the aqueous solution of sodium borohydride was added thereto, and 1 mg. multidot.mL of the aqueous solution was added-1The reaction was carried out with 5. mu.L of the catalyst, and the change in the absorption intensity was recorded to indicate the catalytic activity of the catalyst. The results are shown in the figure. After 5 times of recycling (as shown in FIG. 9), the catalyst still has high catalytic activity.
Example 3
1) 100mL of the solution was added to a reaction solution at a concentration of 0.2 mol. L-1The copper sulfate aqueous solution is mixed with 150mL of 0.37 mol.L-1Uniformly mixing the potassium salicylate aqueous solution, stirring and slowly adding 1 mol.L-1Adjusting the pH value of the system to 5.5, reacting for 12h in a nitrogen atmosphere at 70 ℃, centrifuging, washing and drying the product to obtain a one-dimensional salicylate intercalation layered copper hydroxide precursor;
2) and roasting the precursor prepared in the step at 800 ℃ for 120min in an argon atmosphere to obtain the one-dimensional Cu/C nano composite material.
3) Placing the nano composite material prepared in the step 2) in an oxygen atmosphere to roast for 5min at 300 ℃ to obtain a cuprous oxide/carbon nano composite material, and marking as a catalyst Cu2O/C-3。
The liquid phase hydrogenation reaction process of the p-nitrophenol comprises the following steps: adding 2.5 mmol.L into a quartz cuvette in advance -1200 mu L of p-nitrophenol, 26 mmol. multidot.L-12.5mL of the aqueous solution of sodium borohydride was added thereto, and 1 mg. multidot.mL of the aqueous solution was added-1The reaction was carried out with 5. mu.L of the catalyst, and the change in the absorption intensity was recorded to indicate the catalytic activity of the catalyst.
Example 4
1) 100mL of the solution was added to a reaction solution at a concentration of 0.2 mol. L-1The copper nitrate aqueous solution was mixed with 150mL of a 0.26 mol/L concentration solution-1The sodium salicylate aqueous solution is evenly mixed, and is slowly added with 1 mol.L after being stirred-1Adjusting the pH of the system to 5.5, reacting for 24h at 90 ℃ in a nitrogen atmosphere, centrifuging, washing and drying the product to obtain a one-dimensional salicylate intercalation layered copper hydroxide precursor;
2) and roasting the precursor prepared in the step at 500 ℃ for 30min in an argon atmosphere to obtain the one-dimensional Cu/C nano composite material.
3) Placing the nano composite material prepared in the step 2) in an oxygen atmosphere to roast for 5min at 200 ℃ to obtain a cuprous oxide/carbon nano composite catalyst, and marking as a catalyst Cu2O/C-4。
The liquid phase hydrogenation reaction process of the p-nitrophenol comprises the following steps: adding 2.5 mmol.L into a quartz cuvette in advance -1200 mu L of p-nitrophenol, 26 mmol. multidot.L-12.5mL of the aqueous solution of sodium borohydride was added thereto, and 1 mg. multidot.mL of the aqueous solution was added-1The reaction was carried out with 5. mu.L of the catalyst, and the change in the absorption intensity was recorded to indicate the catalytic activity of the catalyst.
Example 5
1) 100mL of the solution was added to a reaction solution at a concentration of 0.2 mol. L-1The copper nitrate aqueous solution was mixed with 150mL of a 0.26 mol/L concentration solution-1The sodium salicylate aqueous solution is evenly mixed, and is slowly added with 1 mol.L after being stirred-1Adjusting the pH of the system to 4.5, reacting for 12h at 90 ℃ in a nitrogen atmosphere, centrifuging, washing and drying the product to obtain a one-dimensional salicylate intercalation layered copper hydroxide precursor;
2) and roasting the precursor prepared in the step at 700 ℃ for 30min in an argon atmosphere to obtain the one-dimensional Cu/C nano composite material.
3) Placing the nano composite material prepared in the step 2) in an oxygen atmosphere to roast for 5min at 200 ℃ to obtain a cuprous oxide/carbon nano composite catalyst, and marking as a catalyst Cu2O/C-5。
The liquid phase hydrogenation reaction process of the p-nitrophenol comprises the following steps: adding 2.5 mmol.L into a quartz cuvette in advance -1200 mu L of p-nitrophenol, 26 mmol. multidot.L-12.5mL of the aqueous solution of sodium borohydride was added thereto, and 1 mg. multidot.mL of the aqueous solution was added-1The reaction was carried out with 5. mu.L of the catalyst, and the change in the absorption intensity was recorded to indicate the catalytic activity of the catalyst.
Comparative example 1
1) The concentration of 100mL is 0.4 mol.L-1The copper nitrate aqueous solution was mixed with 150mL of a 0.26 mol/L concentration solution-1Sodium salicylateThe solution is evenly mixed, stirred and slowly added with 1 mol.L-1Adjusting the pH of the system to 6.5, reacting for 24h in a nitrogen atmosphere at 100 ℃, centrifuging, washing and drying the product to obtain a one-dimensional salicylate intercalation layered copper hydroxide precursor;
2) and roasting the precursor prepared in the step at 800 ℃ for 360min in an argon atmosphere to obtain the Cu/C nano composite catalyst, and recording the Cu/C nano composite catalyst as a catalyst Cu/C.
The liquid phase hydrogenation reaction process of the p-nitrophenol comprises the following steps: adding 2.5 mmol.L into a quartz cuvette in advance -1200 mu L of p-nitrophenol, 26 mmol. multidot.L-12.5mL of the aqueous solution of sodium borohydride was added thereto, and 1 mg. multidot.mL of the aqueous solution was added-1The reaction was carried out with 5. mu.L of the catalyst, and the change in the absorption intensity was recorded to indicate the catalytic activity of the catalyst. The results are shown in FIG. 7.
In addition, we used the commercial Pt/C purchased as the comparative catalyst, noted Pt/C.
The results of the catalytic performance evaluation showed that Cu2O/C-2 has a high rate activity parameter of 6.74s-1mg-1Much higher than 0.296s of Cu/C nano composite material-1mg-1And 0.25s for commercial Pt/C-1mg-1(see table 1, fig. 8). Indicating the catalytic activity with respect to three catalysts: cu2O/C > Cu/C > Pt/C, adding Cu2After the O/C nano composite catalyst is recycled, a good catalytic hydrogenation effect is still shown (as shown in figure 9).
TABLE 1
Claims (3)
1. The preparation method of the one-dimensional cuprous oxide/carbon nano composite catalyst is characterized in that the one-dimensional cuprous oxide/carbon nano composite catalyst is of a one-dimensional structure, and the nano fiber is 10 mu m long and 150nm wide; the specific surface area of the nano composite catalyst is 20-200m2g-1The aperture is between 2 and 30 nm; the carbon substrate is heated by an organic carbon sourceThe size of cuprous oxide particles with hollow structures obtained by decomposition is 30-80nm, and the cuprous oxide particles are uniformly embedded in a carbon matrix;
the preparation method comprises the following specific operation steps:
1) the concentration is 0.01 to 0.6 mol.L-1The concentration of the soluble cupric salt aqueous solution is 0.01-0.6 mol.L-1Adding the aqueous solution of the salicylate into a flask, and uniformly mixing, wherein the molar ratio of the divalent copper salt to the salicylate is 2: 1-8; using 0.1-1 mol. L-1Regulating the pH value of the sodium hydroxide solution to 4-7, keeping the reaction temperature at 60-100 ℃, crystallizing for 9-48h in the protection of inert atmosphere, naturally cooling to room temperature, centrifugally separating, washing to be neutral by using deionized water, and drying in a drying oven at constant temperature to obtain a one-dimensional salicylate intercalation layered copper hydroxide precursor;
2) roasting the precursor prepared in the step 1) for 0.5-4h at 900 ℃ in an inert atmosphere of 350-;
3) placing the one-dimensional Cu/C nano composite material prepared in the step 2) in oxygen, and roasting at the temperature of 100-400 ℃ for 1-60min to finally obtain the one-dimensional cuprous oxide/carbon nano composite catalyst;
the soluble divalent copper salt in the step 1) is one of copper nitrate, copper chloride and copper sulfate;
the salicylate in the step 1) is sodium salicylate or potassium salicylate.
2. The application of the one-dimensional cuprous oxide/carbon nano composite catalyst prepared by the method according to claim 1 in liquid-phase hydrogenation reaction of p-nitrophenol.
3. The use of claim 2, wherein the specific reaction conditions of the liquid phase hydrogenation of p-nitrophenol are as follows: mixing p-nitrophenol solution with NaBH4Or KBH4Mixing the solutions, and then adding a one-dimensional cuprous oxide/carbon nano composite catalyst for reaction.
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