CN111821978B - Preparation method of carbon layer protection elemental metal loaded titanium dioxide nano material - Google Patents
Preparation method of carbon layer protection elemental metal loaded titanium dioxide nano material Download PDFInfo
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- CN111821978B CN111821978B CN202010584868.6A CN202010584868A CN111821978B CN 111821978 B CN111821978 B CN 111821978B CN 202010584868 A CN202010584868 A CN 202010584868A CN 111821978 B CN111821978 B CN 111821978B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 51
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 23
- 239000002184 metal Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 16
- 150000001412 amines Chemical class 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- -1 transition metal salt Chemical class 0.000 claims abstract description 9
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 47
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000002923 metal particle Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012754 barrier agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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Classifications
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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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
-
- 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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- 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—
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- 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 provides a preparation method of a carbon layer protection elemental metal loaded titanium dioxide nano material, which comprises the following steps: adding a transition metal salt into an organic amine solution to obtain a metal-organic amine precursor; adding amorphous titanium dioxide into an alkali solution for hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying to obtain a titanate carrier; and adding the prepared titanate carrier into the prepared metal-organic amine precursor to perform ion exchange reaction, centrifuging, washing, drying and calcining in nitrogen or argon atmosphere after the reaction is finished to obtain the carbon layer protected simple substance metal loaded titanium dioxide nano material. The preparation method provided by the invention has the advantages of simple process, convenience in operation, high yield, high efficiency and easiness in large-scale production.
Description
Technical Field
The invention relates to the technical field of heterogeneous catalysis, in particular to a preparation method of a titanium dioxide nano material loaded with carbon layer protection simple substance metal.
Background
In recent years, simple substance metal nano materials are widely applied to the fields of heterogeneous catalysis, sensing detection, electrochemistry, biomedicine and the like due to unique optical characteristics, catalytic activity and obvious quantum effect. Generally, elemental metal particle activity is inversely related to its particle size. The surface energy of the elemental particles can increase significantly as the size of the elemental metal particles decreases, resulting in severe agglomeration of the elemental particles, which greatly attenuates their activity. Some researchers have taken a load approach to alleviate the above problems. However, there is still room for improvement in the preparation method, load uniformity and stability of such nanomaterials. In addition, the elemental metal is easily corroded by acid, alkali, oxygen and the like in the reaction environment due to high activity, surface energy and the like, so that the activity and stability are weakened. Research shows that the stability of the simple substance metal can be effectively improved by combining the simple substance metal particles with the carbon material, for example, limiting the area in the carbon nano tube. However, it is still challenging to develop a simple and efficient material preparation method and construct a high-stability carbon material to protect the elemental metal-loaded nanomaterial.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a carbon layer protection elemental metal loaded titanium dioxide nano material, so as to make up for the defects of the current materials in preparation, and meet the wide requirements in the fields of heterogeneous catalysis and the like.
The invention provides a preparation method of a carbon layer protection elemental metal loaded titanium dioxide nano material, which comprises the following steps:
s1, adding a transition metal salt into the organic amine solution to obtain a metal-organic amine precursor;
s2, adding amorphous titanium dioxide into an alkali solution for hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying to obtain a titanate carrier;
s3, adding the titanate carrier prepared in the step S2 into the metal-organic amine precursor prepared in the step S1 to perform ion exchange reaction, centrifuging, washing, drying after the reaction is finished, and calcining in a nitrogen or argon atmosphere to obtain the carbon layer protected elemental metal loaded titanium dioxide nano material.
Further, in step S1, the transition metal salt is a soluble salt of nickel, copper, cobalt, or silver, and may be any one of nickel chloride, copper chloride, cobalt chloride, nickel nitrate, copper nitrate, cobalt nitrate, silver nitrate, nickel acetate, copper acetate, cobalt acetate, or silver acetate; the organic amine is selected from ethylenediamine or triethylamine; the mass ratio of the transition metal salt to the organic amine is 1: (2-4).
Further, in step S2, the alkali solution is selected from sodium hydroxide, ammonia, ethylenediamine, triethylamine, or other organic amine solutions.
Further, in step S2, the hydrothermal reaction temperature was 120 ℃ and the reaction time was 12 hours.
Further, the mass ratio of amorphous titanium dioxide to transition metal salt is 1: (0.2-10), the reaction temperature of the ion exchange reaction is 25-30 ℃, and the time is 12 hours.
Further, in step S3, the rotation speed of the centrifuge during centrifugation is 8000rpm, the centrifugation time is 3min, the drying temperature is 60 ℃, and the drying time is 12 h.
Further, in step S3, the calcination temperature is 500 ℃, the calcination time is 2h, and the temperature rise rate during the calcination process is 2.5 ℃/min.
The invention also provides the titanium dioxide nano material loaded with the elemental metal and protected by the carbon layer, which is prepared by the preparation method.
The prepared nano material is in a monodisperse flower ball shape, a thin layer of carbon is uniformly covered on the surface of the material, and the elemental metal is uniformly embedded in the carbon layer.
The carbon layer protection simple substance metal loaded titanium dioxide nano material prepared by the preparation method can be used for catalytic reduction of 4-nitrophenol.
The technical scheme provided by the invention has the beneficial effects that: the preparation method provided by the invention has the advantages of simple process, convenience in operation, high efficiency, large yield and easiness in large-scale production, no additional reducing agent is required to be introduced in the preparation process, the metal-organic amine precursor not only serves as a barrier agent and a carbon layer source, but also serves as a reducing agent in the nitrogen or argon atmosphere, the simple substance metal is rapidly reduced and finally exists in the form of thin-layer carbon, and the thin-layer carbon not only plays a role in protecting the simple substance metal, but also is beneficial to anchoring simple substance metal particles and enhancing the stability of the simple substance metal particles; strong metal-carrier interaction exists between the titanium dioxide carrier and the elemental metal, and the activity and the stability of the material are further improved.
Drawings
Fig. 1 is a schematic flow chart of preparing a titanium dioxide nanomaterial loaded with elemental Ni for protecting a carbon layer in embodiment 1 of the present invention.
Fig. 2 is a scanning electron microscope image of the titanium dioxide nanomaterial loaded with the elemental Ni for protecting the carbon layer prepared in example 1 of the present invention.
Fig. 3 is a transmission electron microscope image of the titanium dioxide nanomaterial loaded with the elemental Ni for protecting the carbon layer prepared in example 1 of the present invention.
FIG. 4 is a transmission electron microscope image of the elemental Ni-loaded titanium dioxide nanomaterial prepared in comparative example 1 of the present invention.
FIG. 5 is a comparison graph of the performance of the elemental Ni-loaded titanium dioxide nanomaterial prepared in example 1 of the present invention and the elemental Ni-loaded titanium dioxide nanomaterial prepared in comparative example 1 for the catalytic reduction of nitrophenol.
FIG. 6 is a comparison graph of catalytic stability of elemental Ni-loaded titania nanomaterials prepared in example 1 of the present invention and comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be further described with reference to the following examples and accompanying drawings.
Example 1:
2.37g of NiCl was weighed2·6H2Adding O into ethylenediamine with concentration of 0.3mol/L to prepare Ni-ethylenediamine solution with total volume of 100mL and concentration of 0.1mol/L for later use, wherein NiCl is added2·6H2The mass ratio of O to ethylenediamine was about 1: 3; weighing 200mg of amorphous titanium dioxide, adding the amorphous titanium dioxide into 90mL of ammonia water with the concentration of 1mol/L, reacting for 12h at the temperature of 120 ℃, centrifuging for 3min at the rotating speed of 8000rpm after the reaction is finished, washing with deionized water, and drying for 12h at the temperature of 60 ℃ to obtain a titanate carrier; the obtained titanate carrier was added to the above Ni-ethylenediamine solution (Ni (en))2 2+) Performing ion exchange at normal temperature, centrifuging at 8000rpm for 3min after 12h, washing with deionized water, drying at 60 deg.C for 12h, placing in a nitrogen high-temperature furnace, calcining at 500 deg.C for 2h, and setting the temperature rise rate of the high-temperature furnace to 2.5 deg.C/min to obtain carbon layer protected simple substance nickel loaded titanium dioxide nano material (Ni/C-fTiO)2And f represents a flower shape).
The process flow diagram of the above preparation process is shown in figure 1.
Scanning electron microscope characterization is performed on the carbon layer protecting elemental nickel-loaded titanium dioxide nano material prepared in the embodiment 1, as shown in fig. 2, the material shows morphology characteristics of uniform dispersion and spherical flower shape, and the special morphology mainly comes from etching action of amorphous titanium dioxide under an alkaline condition, so that the specific surface area is favorably increased, and more loading sites are provided.
Transmission electron microscope analysis is performed on the elemental nickel-loaded titanium dioxide nanomaterial protected by a carbon layer prepared in example 1, as shown in fig. 3, in a low-power scanning result, the whole material is uniform and semitransparent in color, and no obvious dark spot exists, which may be the reason that the particles of elemental nickel are small. Further, according to the result of the high-power scanning, it can be clearly seen that an obvious carbon thin layer exists in the edge region of the material, particles with clear lattice stripes are inlaid on the surface of the material, the spacing between the particles is 0.240nm and corresponds to the (110) crystal face of the simple substance Ni, and clear lattice stripes can be observed in the material, the spacing between the particles is 0.352nm and corresponds to the (101) crystal face of the anatase titanium dioxide.
Comparative example 1:
2.37g of NiCl was weighed2·6H2O is added with water to prepare Ni with the total volume of 100mL and the concentration of 0.1mol/L2+Solution for later use; weighing 200mg of amorphous titanium dioxide, adding the amorphous titanium dioxide into 90mL of ammonia water with the concentration of 1mol/L, reacting for 12h at 120 ℃, centrifuging for 3min at the rotating speed of 8000rpm after the reaction is finished, washing with deionized water, and drying for 12h at 60 ℃ to obtain a titanate carrier; adding the obtained titanate carrier into the Ni2+Performing ion exchange in the solution at normal temperature, centrifuging at 8000rpm for 3min after 12 hr, washing with deionized water, drying at 60 deg.C for 12 hr, and placing in H2Fully calcining for 2 hours at 500 ℃ in an/Ar high-temperature furnace, and setting the heating rate of the high-temperature furnace to be 2.5 ℃/min to obtain the elemental nickel-loaded titanium dioxide nano material (Ni-fTiO) without the protection of a carbon layer2)。
The nano material obtained in comparative example 1 was characterized by transmission electron microscopy, and as shown in fig. 4, it was clearly seen that black spots appeared on the translucent base material, which is the result after the elemental nickel was loaded, and the elemental nickel particles were large and very non-uniform due to the blocking and dispersing effects of no ligand.
The titanium dioxide nano material (Ni/C-fTiO) loaded with the carbon layer protection simple substance nickel prepared in the example 12) Elemental nickel-supported titanium dioxide nanomaterial (Ni-fTiO) without carbon layer protection prepared in comparative example 12) The method is applied to an experiment for reducing 4-nitrophenol (4-NP) by catalyzing sodium borohydride (experimental conditions are as follows: the total volume of the reaction solution was 10mL, 2mL of 5 mmol/L4-NP solution and 3mL of 0.2mol/L NaBH4The solution, 5mL of deionized water, 5mg of catalyst material added, and the experimental temperature 25 deg.C) gave the results shown in FIG. 5. When only 4-NP exists in the reaction system, the concentration of the 4-NP does not change obviously with the time, and the 4-NP is proved to have higher stability; when sodium borohydride is used alone to reduce 4-NP, the efficiency is very low, and the concentration change of 4-NP is only slightly reduced; when only 4-NP and Ni/C-fTiO are present in the reaction system2When in use, the concentration of the 4-NP is slightly reduced because the larger specific surface area of the material generates smaller adsorption effect on the 4-NP; when 4-NP, sodium borohydride and a catalyst material exist in the system at the same time, the concentration of the 4-NP is obviously reduced, and the carbon layer protects the elemental nickel-loaded titanium dioxide nano material (Ni/C-fTiO)2) Complete reduction of 4-NP was achieved in about 2 min. Efficient catalytic activity benefits from smaller sized elemental nickel particles, as well as the protection of the carbon layer. In contrast, elemental nickel-supported titanium dioxide nanomaterial (Ni-fTiO) without carbon layer protection2) When the reduction rate reaches 100%, the time required exceeds 20 min.
To further demonstrate the important role of thin carbon, the carbon layer prepared in example 1 protects the elemental nickel-loaded titanium dioxide nanomaterial (Ni/C-fTiO)2) Elemental nickel-supported titanium dioxide nanomaterial (Ni-fTiO) without carbon layer protection prepared in comparative example 12) The stability evaluation test was performed by air exposure and acid soaking, and the results are shown in fig. 6. Wherein, no matter the titanium dioxide nano material is exposed in the air for 1 month or is soaked in acid liquor (the acid liquor is 0.01mol/L HCl solution), the carbon layer protects the simple substance nickel loaded titanium dioxide nano material (Ni/C-fTiO)2) Still shows higher catalytic activity. However, noneElemental nickel-loaded titanium dioxide nano material (Ni-fTiO) protected by carbon layer2) After 1 month of exposure to air, its catalytic activity decayed greatly. In addition, after acid leaching treatment, Ni/C-fTiO2Almost completely deactivated.
Example 2:
1.71g of CuCl was weighed2·2H2Adding O into ethylenediamine with the concentration of 0.3mol/L to prepare a Cu-ethylenediamine solution with the total volume of 100mL and the concentration of 0.1mol/L for later use, wherein the Cu-ethylenediamine solution is CuCl2·2H2The mass ratio of O to ethylenediamine was about 1: 3; weighing 200mg of amorphous titanium dioxide, adding the amorphous titanium dioxide into 90mL of ethylenediamine with the concentration of 1mol/L, reacting for 12h at the temperature of 120 ℃, centrifuging for 3min at the rotating speed of 8000rpm after the reaction is finished, washing with deionized water, and drying for 12h at the temperature of 60 ℃ to obtain a titanate carrier; adding the obtained titanate carrier into the Cu-ethylenediamine solution for ion exchange at normal temperature, centrifuging at 8000rpm for 3min after 12h, washing with deionized water, drying at 60 ℃ for 12h, then placing in a nitrogen high-temperature furnace for fully calcining at 500 ℃ for 2h, and setting the temperature rise rate of the high-temperature furnace to be 2.5 ℃/min, thus obtaining the carbon layer protection elemental copper loaded titanium dioxide nano material (Cu/C-fTiO)2)。
Example 3:
weighing 1.7g of silver nitrate, adding the silver nitrate into ethylenediamine with the concentration of 0.3mol/L, and preparing an Ag-ethylenediamine solution with the total volume of 100mL and the concentration of 0.1mol/L for later use, wherein the mass ratio of the silver nitrate to the ethylenediamine is about 1: 3; weighing 200mg of amorphous titanium dioxide, adding the amorphous titanium dioxide into 90mL of triethylamine with the concentration of 1mol/L, reacting for 12h at the temperature of 120 ℃, centrifuging for 3min at the rotating speed of 8000rpm after the reaction is finished, washing with deionized water, and drying for 12h at the temperature of 60 ℃ to obtain a titanate carrier; placing the obtained titanate carrier in the Ag-ethylenediamine solution for ion exchange at normal temperature, centrifuging at 8000rpm for 3min after 12h, washing with deionized water, drying at 60 ℃ for 12h, then placing in a nitrogen high-temperature furnace for fully calcining at 500 ℃ for 2h, and setting the temperature rise rate of the high-temperature furnace to be 2.5 ℃/min to obtain the carbon layer protection simple substance silver loaded titanium dioxide nano material (Ag/C-fTiO)2)。
The features of the embodiments and embodiments described herein above may be combined with each other without conflict.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. A preparation method of a carbon layer protection elemental metal loaded titanium dioxide nano material is characterized by comprising the following steps:
s1, adding a transition metal salt into the organic amine solution to obtain a metal-organic amine precursor;
s2, adding amorphous titanium dioxide into an alkali solution for hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying to obtain a titanate carrier;
s3, adding the titanate carrier prepared in the step S2 into the metal-organic amine precursor prepared in the step S1 for ion exchange reaction, centrifuging, washing, drying after the reaction is finished, and calcining in a nitrogen or argon atmosphere to obtain the carbon layer protected simple substance metal loaded titanium dioxide nano material;
in step S1, the transition metal salt is a soluble salt of nickel, copper, cobalt, or silver, the organic amine is ethylenediamine or triethylamine, and the mass ratio of the transition metal salt to the organic amine is 1: (2-4);
in step S2, the aqueous alkali is selected from sodium hydroxide, ammonia, ethylenediamine or triethylamine; the mass ratio of the amorphous titanium dioxide to the transition metal salt is 1: (0.2-10);
in step S3, the temperature of the calcination was 500 ℃.
2. A titanium dioxide nanomaterial loaded with elemental metal and protected by a carbon layer, which is prepared by the preparation method of claim 1.
3. The application of the carbon layer-protected elemental metal-loaded titanium dioxide nanomaterial prepared by the preparation method of claim 1, wherein the carbon layer-protected elemental metal-loaded titanium dioxide nanomaterial is used for catalytic reduction of 4-nitrophenol.
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