CN115094478A - Titanium dioxide/graphite oxide composite material and preparation method and application thereof - Google Patents
Titanium dioxide/graphite oxide composite material and preparation method and application thereof Download PDFInfo
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- CN115094478A CN115094478A CN202210818508.7A CN202210818508A CN115094478A CN 115094478 A CN115094478 A CN 115094478A CN 202210818508 A CN202210818508 A CN 202210818508A CN 115094478 A CN115094478 A CN 115094478A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 297
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 141
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 85
- 239000010439 graphite Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 238000001354 calcination Methods 0.000 claims abstract description 52
- 239000002243 precursor Substances 0.000 claims abstract description 50
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010936 titanium Substances 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- UHWHMHPXHWHWPX-UHFFFAOYSA-J dipotassium;oxalate;oxotitanium(2+) Chemical compound [K+].[K+].[Ti+2]=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHWHMHPXHWHWPX-UHFFFAOYSA-J 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000002159 nanocrystal Substances 0.000 abstract description 13
- 239000011230 binding agent Substances 0.000 abstract description 12
- 230000005540 biological transmission Effects 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 10
- 239000002149 hierarchical pore Substances 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 37
- 230000003197 catalytic effect Effects 0.000 description 15
- 239000003822 epoxy resin Substances 0.000 description 14
- 229920000647 polyepoxide Polymers 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011148 porous material Substances 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000002120 nanofilm Substances 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AZCUJQOIQYJWQJ-UHFFFAOYSA-N oxygen(2-) titanium(4+) trihydrate Chemical compound [O-2].[O-2].[Ti+4].O.O.O AZCUJQOIQYJWQJ-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000013079 quasicrystal Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/27—Ammonia
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a titanium dioxide/graphite oxide composite material and a preparation method and application thereof, wherein the preparation method of the titanium dioxide/graphite oxide composite material comprises the following steps: soaking the pillared polymer template in a titanium dioxide precursor solution, performing solid-liquid separation, and then drying and calcining to obtain the titanium dioxide/graphite oxide composite material; the titanium dioxide precursor solution is obtained by mixing a titanium source and a solvent. The titanium dioxide precursor is adsorbed, hydrolyzed and condensed on the surface of the polymer skeleton, the use of a binder is avoided by the preparation method of in-situ growth, the dispersibility of the titanium dioxide nanocrystal is improved while the growth of the titanium dioxide nanocrystal is limited by the graphite oxide, and the transmission performance of the material is improved by the mutually communicated hierarchical pore structure.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to a titanium dioxide/graphite oxide composite material and a preparation method and application thereof.
Background
Currently, the demand for energy is sharply increased, and the search for clean renewable energy is imminent. The ammonia has higher energy density, so the ammonia can be widely used as an energy carrier. The method for synthesizing ammonia by reducing nitrogen through electrocatalysis adopts nitrogen and water as raw materials, and is an important way for realizing green and sustainable production of ammonia, however, the development of an efficient electrocatalyst for synthesizing ammonia by reducing nitrogen becomes a key for restricting the technical development.
Titanium dioxide is a common transition metal oxide, and can be used for preparing electrode materials due to the unique electronic structure and photoelectric property, but the traditional electrode preparation process for synthesizing ammonia by nitrogen reduction adopts a drop coating process, in the process, a catalyst is adhered to carbon paper by virtue of a binder, a part of a catalytic active site is covered, the accessibility of a catalytic active center is reduced, and the catalytic activity is reduced; on the other hand, the binder also increases an electron conduction interface, resulting in an increase in electron conduction resistance.
In the prior art, a micro-nano processing technology is adopted, a titanium dioxide array electrode is prepared on a titanium plate, and although the use of a binder can be effectively avoided, the defects of low specific surface area of a titanium dioxide array, low effective utilization rate of an active center and the like exist.
CN 114574900A discloses a Co-N-C composite material with a self-supporting multi-stage structure, a preparation method and an application thereof, wherein the prepared self-supporting electrode takes functionalized carbon paper as a substrate, and a Co-MOF electrode material growing on the carbon paper in situ is obtained by carrying out hydrothermal reaction on cobalt salt and a nitrogen-containing ligand. Although the invention avoids the use of a binder, only Co-MOF has a hierarchical pore structure, the diffusion and transmission of substances are still limited to the carbon paper substrate, and the improvement of the accessibility of the catalytic active sites is limited.
CN 110783526A discloses a self-supporting electrode, which mainly comprises, by mass, 2-20% of an ultralong carbon nanotube, 2-20% of graphene, 4-20% of a solid electrolyte, and 40-92% of a positive electrode/negative electrode active material. The graphene can play a role in linking and supporting the whole electrode plate, and has good conductivity; the ultra-long carbon nanotubes can form a conductive network in the electrode plate, so that the use of a binder and a current collector is omitted. However, the invention does not have a multi-level pore structure, and the diffusion and transmission capability of the substance still need to be further improved.
In view of the deficiencies of the prior art, it is desirable to provide a composite material that can improve the diffusion and transport capabilities of substances and thus improve the catalytic performance.
Disclosure of Invention
The invention aims to provide a titanium dioxide/graphite oxide composite material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a titanium dioxide/graphite oxide composite material, comprising the steps of:
soaking the pillared polymer template in a titanium dioxide precursor solution, performing solid-liquid separation, and then drying and calcining to obtain the titanium dioxide/graphite oxide composite material;
the titanium dioxide precursor solution is obtained by mixing a titanium source and a solvent.
The preparation method takes the pillared polymer as a template, the titanium dioxide/graphite oxide composite material is prepared by adsorption, hydrolysis and polycondensation of a titanium dioxide precursor on the surface of a polymer framework and calcination, the use of a binder is avoided in the preparation method of in-situ growth, the dispersibility of the graphite oxide is improved while the growth of titanium dioxide nanocrystals is limited, more active sites are exposed on the surface of a pore channel, the accessibility of the active sites is improved, and the transmission performance of substances is improved by the mutually-communicated micropore-mesopore-macropore structure; the titanium dioxide/graphite oxide composite material can meet the requirements of serving as a working electrode by adjusting and controlling the concentration of the raw materials, the calcining temperature and the calcining time.
Preferably, the concentration of the titanium source in the titanium dioxide precursor solution is 0.1-0.8g/mL, and may be, for example, 0.1g/mL, 0.2g/mL, 0.3g/mL, 0.4g/mL, 0.5g/mL, 0.6g/mL, 0.7g/mL, or 0.8g/mL, but is not limited to the recited values, and other values within the range are equally applicable.
The mechanical stability of the self-supporting electrode can be regulated by regulating the concentration of a titanium source in the titanium dioxide precursor solution, and the stability is adversely affected by overhigh or overlow concentration.
Preferably, the titanium source comprises tetrabutyl titanate and/or potassium titanium oxalate.
Preferably, the solvent comprises cyclohexane.
Preferably, the temperature of the mixing is 15-50 ℃, for example 15 ℃, 20 ℃, 30 ℃, 40 ℃ or 50 ℃, but not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
Preferably, the mixing time is 10-120min, for example 10min, 30min, 50min, 80min, 100min or 120min, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the mass ratio of the pillared polymer template to the titanium dioxide precursor solution is (0.02-0.2):1, and may be, for example, 0.02:1, 0.05:1, 0.08:1, 0.1:1, 0.15:1, or 0.2:1, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the pillared polymer template comprises an epoxy polymer.
The epoxy resin polymer is a macroporous epoxy resin polymer, is favorable for constructing a micropore-mesopore-macropore hierarchical pore structure, and provides a material transmission performance.
Preferably, the impregnation temperature is 10-60 ℃, for example 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃ or 60 ℃, but not limited to the recited values, other values not recited in the numerical range are equally applicable.
Preferably, the impregnation time is from 2 to 72h, for example 2h, 10h, 20h, 30h, 40h, 50h, 60h or 72h, but is not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the drying temperature is 20-30 ℃, for example 20 ℃, 22 ℃, 25 ℃, 28 ℃ or 30 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the drying time is 46 to 50 hours, for example 46 hours, 47 hours, 48 hours, 49 hours or 50 hours, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the calcination temperature is 400-1200 deg.C, such as 400 deg.C, 500 deg.C, 600 deg.C, 700 deg.C, 800 deg.C, 900 deg.C, 1000 deg.C, 1100 deg.C or 1200 deg.C, but not limited to the recited values, and other values within the range are equally applicable, preferably 800-1100 deg.C.
Preferably, the calcination time is 30-240min, for example 30min, 60min, 100min, 150min, 200min or 240min, but is not limited to the recited values, and other values not recited in the range of values are equally applicable, preferably 60-150 min.
The invention can regulate and control the crystalline phase of titanium oxide by regulating and controlling the calcining temperature and time, thereby influencing the concentration of oxygen vacancy and changing the catalytic performance; the mass ratio of titanium dioxide and graphite oxide in the composite material can be changed by regulating and controlling the calcining temperature, the specific surface area of the composite material can be increased by reasonable calcining temperature, and the reaction of an electrode interface is ensured to be fully carried out.
Preferably, the temperature increase rate of the calcination is 4-6 deg.C/min, and may be, for example, 4 deg.C/min, 4.5 deg.C/min, 5 deg.C/min, 5.5 deg.C/min, or 6 deg.C/min, but is not limited to the values recited, and other values not recited in the range of values are also applicable.
Preferably, the calcination is carried out in a protective atmosphere.
Preferably, the gas used for the protective atmosphere comprises nitrogen and/or argon.
As a preferable technical solution of the preparation method according to the first aspect of the present invention, the preparation method comprises the steps of:
soaking the pillared polymer template in titanium dioxide precursor liquid for 2-72h at 10-60 ℃, drying for 46-50h at 20-30 ℃ after solid-liquid separation, heating to 400-1200 ℃ at 4-6 ℃/min, and calcining for 30-240min to obtain the titanium dioxide/graphite oxide composite material;
the mass ratio of the pillared polymer template to the titanium dioxide precursor solution is (0.02-0.2): 1; the calcination is carried out in a protective atmosphere; the titanium dioxide precursor solution is obtained by mixing a titanium source and a solvent at 15-50 ℃ for 10-120 min; the concentration of the titanium source in the titanium dioxide precursor liquid is 0.1-0.8 g/mL.
In a second aspect, the invention provides a titanium dioxide/graphite oxide composite material, which is prepared by the preparation method in the first aspect.
According to the titanium dioxide/graphite oxide composite material provided by the invention, the titanium dioxide nanocrystal is combined with the graphite oxide nano film in a covalent bond mode to form a three-dimensional network pore channel structure with communicated micropores, mesopores and macropores, and the titanium dioxide/graphite oxide composite material has abundant oxidation/reduction active sites. Wherein the titanium dioxide nanocrystals provide catalytically active sites; the graphite oxide nano film can limit the growth of titanium dioxide nano crystals and improve the dispersibility of the titanium dioxide nano crystals on one hand, and can effectively improve the electrochemical activity and the conductivity on the other hand;
the titanium dioxide/graphite oxide composite material has the advantages that the multi-level pore channel structure can improve the material transmission performance to a greater extent, the larger specific surface area improves the interface contact area of gas-liquid-solid three phases, the full contact between electrolyte and an electrode interface is ensured, and the full reaction is promoted. The self-supporting structure constructed by the nano film avoids the use of a binder, reduces the electron transmission resistance and effectively improves the catalytic oxidation reduction performance of the composite material.
In a third aspect, the present invention provides the use of a titania/graphite oxide composite material as described in the second aspect for the electrocatalytic nitrogen reduction synthesis of ammonia.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the titanium dioxide precursor is adsorbed, hydrolyzed and condensed on the surface of the polymer template framework, and the titanium dioxide/graphite oxide composite material is prepared by calcining, so that the use of a binder is avoided in the preparation mode of in-situ growth, the dispersibility of the graphite oxide is improved while the growth of titanium dioxide nanocrystals is limited, and the material transmission performance is improved by the mutually-communicated hierarchical pore structure;
(2) the invention can effectively improve the quality of the titanium by regulating and controlling the concentration of the titanium source, the calcining temperature and the calcining timeThe titanium dioxide/graphite oxide composite material is used for catalyzing nitrogen to reduce and synthesize ammonia, and the optimal yield can reach 20.68 mu g.h -1 ·cm -2 The preparation process is simple, the cost is low, and the method is suitable for industrial production;
(3) the titanium dioxide/graphite oxide composite material provided by the invention has a three-dimensional network pore channel structure with mutually communicated micropores, mesopores and macropores, avoids the use of a binder, reduces the electron transmission resistance, effectively improves the catalytic oxidation reduction performance of the composite material, and provides a new idea for preparing a self-supporting hierarchical pore structure/graphite oxide composite.
Drawings
FIG. 1 is an XRD pattern of the titanium dioxide/graphite oxide composites provided in examples 1, 2 and 4;
FIG. 2 is an XRD pattern of the titanium dioxide/graphite oxide composites provided in examples 1, 8 and 9;
FIG. 3 is a K-edge X-ray absorption fine structure spectrum of titanium in the titanium dioxide/graphite oxide composite materials provided in examples 1, 8 and 9;
FIG. 4 is an SEM image of the titanium dioxide/graphite oxide composite provided in example 1;
FIG. 5 is a TEM image of the titanium dioxide/graphite oxide composite provided in example 1;
FIG. 6 is a DTA-TG plot of the titanium dioxide/graphite oxide composite provided in example 1;
FIG. 7 is a plot of the nitrogen adsorption desorption isotherm of the titanium dioxide/graphite oxide composite provided in example 1;
FIG. 8 is a graph of the pore size distribution of the titanium dioxide/graphite oxide composite provided in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a titanium dioxide/graphite oxide composite material, and a preparation method of the titanium dioxide/graphite oxide composite material comprises the following steps:
soaking an epoxy resin polymer template in a titanium dioxide precursor solution for 24 hours at 30 ℃, performing solid-liquid separation, drying for 48 hours at 25 ℃, heating to 1000 ℃ at a speed of 5 ℃/min in argon, and calcining for 120 minutes to obtain the titanium dioxide/graphite oxide composite material;
the mass ratio of the epoxy resin polymer template to the titanium dioxide precursor solution is 0.1: 1; the titanium dioxide precursor solution is obtained by mixing tetrabutyl titanate and cyclohexane at 30 ℃ for 50 min; the concentration of tetrabutyl titanate in the titanium dioxide precursor solution is 0.6 g/mL.
As can be seen from fig. 4, the titanium dioxide/graphite oxide composite material has a macro size of 2 × 0.7cm, the sample has abundant disordered macropores, and the support framework of the material is a film-shaped material;
as can be seen from fig. 5, the titanium dioxide/graphite oxide composite material has the characteristics of a thin film, wherein the thin film is formed by inlaying titanium dioxide nanocrystals into graphite oxide, the nanocrystals show an ordered crystal plane structure, and the support thin film has a curled stripe structure; the graphite oxide is formed by calcining and converting an epoxy resin polymer at high temperature in an inert atmosphere, and the monodispersity of the titanium dioxide nanocrystal is improved while the growth of the titanium dioxide nanocrystal is controlled;
as can be seen from fig. 6, the mass ratios of graphite oxide and titanium dioxide in the titanium dioxide/graphite oxide composite material are 31% and 69%, respectively; as can be seen from FIG. 7, the titanium dioxide/graphite oxide composite material had a specific surface area of 280.45m 2 (ii)/g; as can be seen from fig. 8, the pore diameter of the micropores in the titanium dioxide/graphite oxide composite material is 1.9nm, and the pore diameter of the mesopores is 3-5nm, which indicates that the material has a three-stage pore structure of micropore-mesopore-macropore, wherein the macropore and mesopore are helpful for diffusion and transmission of reactants or products, and the micropore and mesopore are helpful for increasing the specific surface area of the material, exposing more catalytic activity centers, enhancing gas-liquid-solid three-phase contact, and improving the catalytic activity of the material.
Example 2
The embodiment provides a titanium dioxide/graphite oxide composite material, and a preparation method of the titanium dioxide/graphite oxide composite material comprises the following steps:
dipping an epoxy resin polymer template in a titanium dioxide precursor solution for 48h at 20 ℃, carrying out solid-liquid separation, drying for 49h at 22 ℃, heating to 800 ℃ at 4.5 ℃/min in argon, and calcining for 120min to obtain the titanium dioxide/graphite oxide composite material;
the mass ratio of the epoxy resin polymer template to the titanium dioxide precursor solution is 0.05: 1; the titanium dioxide precursor solution is obtained by mixing tetrabutyl titanate and cyclohexane at 20 ℃ for 80 min; the concentration of tetrabutyl titanate in the titanium dioxide precursor solution is 0.3 g/mL.
Example 3
The embodiment provides a titanium dioxide/graphite oxide composite material, and a preparation method of the titanium dioxide/graphite oxide composite material comprises the following steps:
dipping an epoxy resin polymer template in a titanium dioxide precursor solution at 45 ℃ for 12h, carrying out solid-liquid separation, drying at 28 ℃ for 47h, heating to 1100 ℃ at the speed of 5.5 ℃/min in argon, and calcining for 120min to obtain the titanium dioxide/graphite oxide composite material;
the mass ratio of the epoxy resin polymer template to the titanium dioxide precursor solution is 0.15: 1; the titanium dioxide precursor solution is obtained by mixing tetrabutyl titanate and cyclohexane at 40 ℃ for 30 min; the concentration of tetrabutyl titanate in the titanium dioxide precursor solution is 0.7 g/mL.
Example 4
The embodiment provides a titanium dioxide/graphite oxide composite material, and a preparation method of the titanium dioxide/graphite oxide composite material comprises the following steps:
dipping an epoxy resin polymer template in a titanium dioxide precursor solution at 10 ℃ for 72h, carrying out solid-liquid separation, drying at 20 ℃ for 50h, heating to 400 ℃ at a speed of 4 ℃/min in argon, and calcining for 120min to obtain the titanium dioxide/graphite oxide composite material;
the mass ratio of the epoxy resin polymer template to the titanium dioxide precursor solution is 0.02: 1; the titanium dioxide precursor solution is obtained by mixing tetrabutyl titanate and cyclohexane at 15 ℃ for 120 min; the concentration of tetrabutyl titanate in the titanium dioxide precursor solution is 0.1 g/mL.
Example 5
The embodiment provides a titanium dioxide/graphite oxide composite material, and a preparation method of the titanium dioxide/graphite oxide composite material comprises the following steps:
dipping an epoxy resin polymer template in a titanium dioxide precursor solution for 2h at 60 ℃, carrying out solid-liquid separation, drying for 46h at 30 ℃, heating to 1200 ℃ at the speed of 6 ℃/min in argon, and calcining for 120min to obtain the titanium dioxide/graphite oxide composite material;
the mass ratio of the epoxy resin polymer template to the titanium dioxide precursor solution is 0.2: 1; the titanium dioxide precursor solution is obtained by mixing tetrabutyl titanate and cyclohexane at 50 ℃ for 10 min; the concentration of tetrabutyl titanate in the titanium dioxide precursor solution is 0.8 g/mL.
Example 6
This example provides a titanium dioxide/graphite oxide composite material, which is the same as in example 1 except that the temperature for raising the temperature in the preparation process was adjusted to 300 ℃.
Example 7
This example provides a titanium dioxide/graphite oxide composite material, which is the same as in example 1 except that the temperature for raising the temperature in the preparation process was adjusted to 1300 ℃.
Example 8
This example provides a titanium dioxide/graphite oxide composite material, which is the same as example 1 except that the calcination time in the preparation method was adjusted to 60 min.
Example 9
This example provides a titanium dioxide/graphite oxide composite material, which is the same as example 1 except that the calcination time in the preparation process was adjusted to 150min, unlike example 1.
Example 10
This example provides a titanium dioxide/graphite oxide composite material, which is the same as example 1 except that the calcination time in the preparation process was adjusted to 30min, unlike example 1.
Example 11
This example provides a titanium dioxide/graphite oxide composite material, which is different from example 1 in that it is the same as example 1 except that the calcination time in the preparation method is adjusted to 240 min.
Example 12
This example provides a titanium dioxide/graphite oxide composite material, which is the same as example 1 except that the calcination time in the preparation method was adjusted to 10min, unlike example 1.
Example 13
This example provides a titanium dioxide/graphite oxide composite material, which is the same as example 1 except that the calcination time in the preparation method was adjusted to 250min, unlike example 1.
Example 14
This example provides a titanium dioxide/graphite oxide composite material, which is different from example 1 in that the titanium dioxide precursor solution is adjusted to have a tetrabutyl titanate concentration of 0.05g/mL in the preparation method, and the rest is the same as example 1.
Example 15
This example provides a titanium dioxide/graphite oxide composite material, which is different from example 1 in that the titanium dioxide precursor solution is adjusted to have a tetrabutyl titanate concentration of 1g/mL in the preparation method, and the rest is the same as example 1.
Comparative example 1
This comparative example provides a titanium dioxide/carbon-based composite material, which is different from example 1 in that the epoxy resin polymer template in the preparation method is replaced with commercially available carbon paper, and the rest is the same as example 1.
Comparative example 2
The comparative example provides a titanium dioxide/graphene composite material, and the preparation method comprises the following steps: mixing a graphene aqueous solution and a titanium dioxide precursor solution at 30 ℃ for 24h, then sequentially centrifuging, drying and precipitating at 25 ℃ for 48h, heating to 1000 ℃ at a speed of 5 ℃/min in argon, and calcining for 120min to obtain the titanium dioxide/graphene composite material;
the mass ratio of the graphene aqueous solution to the titanium dioxide precursor solution is 0.2: 1; the titanium dioxide precursor solution is obtained by mixing tetrabutyl titanate and cyclohexane at 30 ℃ for 50 min; the concentration of tetrabutyl titanate in the titanium dioxide precursor solution is 0.6 g/mL.
Comparative example 3
The present comparative example provides a molybdenum oxide/graphite oxide composite material, which is different from example 1 in that tetrabutyl titanate in the preparation method is replaced by potassium molybdate, and the molybdenum oxide/graphite oxide composite material is adaptively obtained, and the rest is the same as example 1.
The titania/graphite oxide composites provided in examples 1-15 and comparative examples 1-3 were subjected to an electrocatalytic nitrogen reduction ammonia test: an H-type electrolytic cell was used as a reactant, a 0.1M KOH aqueous solution was used as an electrolyte, the titanium dioxide/graphite oxide composite materials provided in examples 1-15 and comparative examples 1-3 were used as a working electrode, an Hg/HgO electrode was used as a reference electrode, and a graphite rod electrode was used as a counter electrode. Electrochemical test is carried out by adopting a chronoamperometry, the applied voltage is-0.3V vs RHE, the electrifying time is 3600s, and the obtained test results are shown in Table 1.
TABLE 1
| Ammonia yield (. mu.g.h) -1 ·cm -2 ) | |
| Example 1 | 20.68 |
| Example 2 | 11.87 |
| Example 3 | 12.05 |
| Example 4 | 11.38 |
| Example 5 | 10.05 |
| Example 6 | 7.98 |
| Example 7 | 9.31 |
| Example 8 | 7.68 |
| Example 9 | 2.3 |
| Example 10 | 1.01 |
| Example 11 | 1.56 |
| Example 12 | 0.78 |
| Example 13 | 2.10 |
| Example 14 | 16.90 |
| Example 15 | 18.80 |
| Comparative example 1 | 2.93 |
| Comparative example 2 | 3.67 |
| Comparative example 3 | 8.94 |
As can be seen from Table 1, by comparing example 1 with examples 2 to 5, the titanium dioxide/graphite oxide composite material obtained by regulating and controlling reasonable preparation process parameters has better catalytic performance; as can be seen from fig. 1, the phase structure of titanium oxide has a direct relationship with the calcination temperature, and when the calcination temperature is lower than 800 ℃, the titanium dioxide in the prepared titanium dioxide/graphite oxide composite material is anatase phase; when the calcining temperature is raised to 1000 ℃, all anatase phases are converted into rutile phases; the conversion process of anatase phase to rutile phase is carried out at the temperature of between 800-1000 ℃; as is clear from comparison of examples 1, 6 and 7, the calcination temperature was too low, and the oxide was anatase-phase titanium dioxide, and the catalytic activity was greatly reduced; the calcination temperature is too high, the crystal structure of the titanium oxide is changed, the titanium pentoxide is generated, and the catalytic activity is still obviously reduced;
from the comparison between example 1 and examples 8-13, the calcination time can be adjusted and controlled to control the crystal phase of titanium oxide, the concentration of oxygen vacancy is influenced, the catalytic performance is changed, the preferred calcination time range has higher ammonia yield, and the rutile phase TiO phase increases to 150min when the calcination time is combined with the graph of FIG. 2 2 Ti transformed into orthorhombic system 3 O 5 The ammonia yield is reduced; referring to FIG. 3, the same can be seen in the rutile phaseTiO quasicrystal 2 In contrast, when the calcination time was gradually increased, the peak at 0.15nm shifted to the right, indicating that the coordination state of the titanium atom changed as the calcination time was extended; in addition, as the calcination time was extended, the peak intensity decreased, indicating that the concentration of oxygen vacancies in the sample increased and the lattice distortion became stronger as the calcination time was extended;
as is clear from comparison of example 1 with example 14 and example 15, the titanium dioxide precursor solution has too low or too high a tetrabutyl titanate concentration, and the product yield is not greatly reduced, but the mechanical stability of the electrode is adversely affected;
as can be seen from the comparison between example 1 and comparative examples 1-3, the yield of the ammonia synthesized by electrocatalytic nitrogen reduction using the template or the impregnation solution of the prior art applied to the composite material prepared by the present invention is reduced.
In conclusion, the titanium dioxide precursor is adsorbed, hydrolyzed and condensed on the surface of the polymer template framework, and the titanium dioxide/graphite oxide composite material is prepared by calcining, the preparation method of in-situ growth avoids the use of a binder, the graphite oxide improves the dispersibility of the titanium dioxide while limiting the growth of the titanium dioxide nanocrystals, and the mutually-communicated hierarchical pore structure improves the material transmission performance;
the invention can effectively improve the electrocatalytic performance of the composite material by regulating and controlling the concentration of the titanium source, the calcining temperature and the calcining time, and the optimum yield can reach 20.68 mu g.h by utilizing the titanium dioxide/graphite oxide composite material to catalyze nitrogen to reduce and synthesize ammonia -1 ·cm -2 The preparation process is simple, the cost is low, and the method is suitable for industrial production;
the titanium dioxide/graphite oxide composite material provided by the invention has a three-dimensional network pore channel structure with communicated micropores, mesopores and macropores, avoids the use of a binder, reduces the electron transmission resistance, effectively improves the catalytic oxidation reduction performance of the composite material, and provides a new idea for preparing a self-supporting hierarchical pore structure/graphite oxide composite.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. The preparation method of the titanium dioxide/graphite oxide composite material is characterized by comprising the following steps:
soaking the pillared polymer template in a titanium dioxide precursor solution, performing solid-liquid separation, and then drying and calcining to obtain the titanium dioxide/graphite oxide composite material;
the titanium dioxide precursor solution is obtained by mixing a titanium source and a solvent.
2. The method according to claim 1, wherein the concentration of the titanium source in the titanium dioxide precursor solution is 0.1 to 0.8 g/mL;
preferably, the titanium source comprises tetrabutyl titanate and/or potassium titanium oxalate;
preferably, the solvent comprises cyclohexane;
preferably, the temperature of the mixing is 15-50 ℃;
preferably, the mixing time is 10-120 min.
3. The preparation method according to claim 1 or 2, wherein the mass ratio of the pillared polymer template to the titanium dioxide precursor solution is (0.02-0.2): 1;
preferably, the pillared polymer template comprises an epoxy polymer.
4. The method for preparing a composite material according to any one of claims 1 to 3, wherein the temperature of the impregnation is 10 to 60 ℃;
preferably, the time of the impregnation is 2 to 72 hours.
5. The method according to any one of claims 1 to 4, wherein the drying temperature is 20 to 30 ℃;
preferably, the drying time is 46-50 h.
6. The method according to any one of claims 1 to 5, wherein the temperature of the calcination is 400-1200 ℃, preferably 800-1100 ℃;
preferably, the calcination time is 30-240min, preferably 60-150 min;
preferably, the temperature rise rate of the calcination is 4-6 ℃/min.
7. The method according to any one of claims 1 to 6, wherein the calcination is carried out in a protective atmosphere;
preferably, the gas used for the protective atmosphere comprises nitrogen and/or argon.
8. The production method according to any one of claims 1 to 7, characterized by comprising the steps of:
soaking the pillared polymer template in titanium dioxide precursor liquid for 2-72h at 10-60 ℃, drying for 46-50h at 20-30 ℃ after solid-liquid separation, heating to 400-1200 ℃ at 4-6 ℃/min, and calcining for 30-240min to obtain the titanium dioxide/graphite oxide composite material;
the mass ratio of the pillared polymer template to the titanium dioxide precursor solution is (0.02-0.2) to 1; the calcination is carried out in a protective atmosphere; the titanium dioxide precursor solution is obtained by mixing a titanium source and a solvent for 10-120min at 15-50 ℃; the concentration of the titanium source in the titanium dioxide precursor liquid is 0.1-0.8 g/mL.
9. A titanium dioxide/graphite oxide composite material, characterized in that it is produced by the production method according to any one of claims 1 to 8.
10. Use of the titanium dioxide/graphite oxide composite material according to claim 9 for the electrocatalytic reduction of nitrogen to ammonia.
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