CN115770576B - Nickel-titanium composite catalyst and preparation method and application thereof - Google Patents
Nickel-titanium composite catalyst and preparation method and application thereof Download PDFInfo
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- CN115770576B CN115770576B CN202111038753.8A CN202111038753A CN115770576B CN 115770576 B CN115770576 B CN 115770576B CN 202111038753 A CN202111038753 A CN 202111038753A CN 115770576 B CN115770576 B CN 115770576B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910001000 nickel titanium Inorganic materials 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010936 titanium Substances 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 230000009467 reduction Effects 0.000 claims abstract description 12
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- 230000007547 defect Effects 0.000 claims abstract description 9
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- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
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- 238000011068 loading method Methods 0.000 claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 35
- 150000002815 nickel Chemical class 0.000 claims description 29
- 239000013086 titanium-based metal-organic framework Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 238000006555 catalytic reaction Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000012018 catalyst precursor Substances 0.000 claims description 10
- -1 n-propyl titanate Chemical compound 0.000 claims description 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
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- 239000000203 mixture Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
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- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 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 4
- 238000010304 firing Methods 0.000 claims description 4
- 239000012621 metal-organic framework Substances 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 238000004729 solvothermal method Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 claims description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical class OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002531 isophthalic acids Chemical class 0.000 claims description 2
- 229940102253 isopropanolamine Drugs 0.000 claims 1
- 150000003503 terephthalic acid derivatives Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
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- 230000031700 light absorption Effects 0.000 abstract description 6
- 238000001228 spectrum Methods 0.000 abstract description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract description 2
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 2
- 239000013384 organic framework Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 24
- 239000010453 quartz Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
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- 230000001976 improved effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- 230000008569 process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a nickel-titanium composite catalyst and a preparation method and application thereof. The nickel-titanium composite catalyst is represented by a chemical formula of Ni/TiO 2, wherein a catalyst carrier is TiO 2, and Ni element is uniformly dispersed on the catalyst carrier in a small-sized metallic nickel nanoparticle; the Ni and the TiO 2 have strong interaction, and the surface has rich oxygen defects; the loading amount of the Ni element on the carrier is 2-50wt%. According to the invention, nickel ions are uniformly adsorbed in the pore channels of the organic framework by utilizing the porous characteristic of the titanium-based organic metal framework, and the catalyst provided by the invention is obtained through baking and reduction, has more surface oxygen defects, and greatly improves the capability of adsorbing and activating CO 2 of the material. The catalyst can realize strong light absorption under the full spectrum, and can convert absorbed light energy into heat energy, and can realize high-efficiency CO 2 methanation without using an external heating device.
Description
Technical Field
The invention belongs to the field of catalyst preparation technology and application, and relates to a nickel-titanium composite catalyst and a preparation method and application thereof.
Background
Fossil energy is an essential main motive element for the current social and economic development of human beings, and great economic benefits are brought to the human beings due to the consumption of a large amount of fossil fuel, so that the living standard of the human beings is improved, but a large amount of CO 2 is also generated at the same time, and the greenhouse effect and the energy crisis are caused. The international committee on climate change predicts that by 2100 years the CO 2 content in the earth's atmosphere will be as high as 590ppm and the global average temperature will rise by 1.9 ℃, with the resultant global climate change leading to undesireable catastrophic results. In view of the severe impact of rising CO 2 concentrations in the atmosphere on global climate, the development of new technologies for CO 2 removal or conversion is not desirable.
The electrocatalytic technology directly degrades the substrate through electrode reaction under the action of an external electric field, or generates a large number of free radicals with strong oxidability to react with the substrate by utilizing the catalytic activity of the electrode or the catalytic material; the method has the advantages that the process is simple, can be carried out at normal temperature and normal pressure, has no secondary pollution, and needs to continuously supplement external energy; the thermal catalysis technology is to inject energy crossing thermodynamic potential barrier into a catalytic reaction system in the form of heat energy to drive the catalytic reaction to be carried out, and the technology is usually carried out at high temperature and high pressure, so that the great consumption of energy sources is also the biggest obstacle to the development of the technology; the basic principle of the photocatalysis technology is as follows: when the semiconductor photocatalyst is irradiated with light, if the energy of a photon is higher than the forbidden bandwidth of the semiconductor, valence band electrons of the semiconductor are transited from the valence band to the conduction band, and photo-generated electrons and holes are generated on the conduction band and the valence band, respectively. The holes have strong oxidizing ability, and the photo-generated electrons have strong reducing ability, so that the electron acceptors on the semiconductor surface are reduced. The advantage of this technique is, but is limited to, its own band limitation, that the currently used catalysts such as WO3(Journal of Materials Chemistry A,2018,6(15):6265-72.)、TiO2(Applied Catalysis B:Environmental,2017,210(131-40.)、ZnO(Journal of Materials Chemistry A,2019,7(27):16294-303.) are only able to respond to ultraviolet or ultraviolet and part of the visible light, which is only around 47% of the full spectrum, i.e. nearly 50% of the sunlight is wasted (Journal of MATERIALS CHEMISTRY A,2019,7 (19): 11985-95). Therefore, increasing the utilization rate of sunlight has become a research hotspot in the field of photocatalysis.
Considering the problems of low energy consumption of thermal catalysis and low sunlight utilization rate of the traditional photocatalytic system and insufficient catalytic reaction power, the heating effect of infrared light in the full-spectrum light source is utilized to drive the catalytic reaction so as to realize efficient optical drive thermal catalysis, and the method has important significance.
Disclosure of Invention
The invention provides a nickel-titanium composite catalyst, which is expressed by a chemical formula of Ni/TiO 2, wherein a catalyst carrier is TiO 2, and Ni element is uniformly dispersed on the catalyst carrier in a small-sized metallic nickel nano particle; the Ni and the TiO 2 have strong interaction, and the surface has rich oxygen defects.
According to an embodiment of the invention, the loading of Ni element on the support is 2-50wt%, preferably 5-30wt%, more preferably 5-20wt%, for example 5wt%, 8wt% or 10wt%.
According to an embodiment of the invention, the catalyst support TiO 2 is prepared by a metal organic framework method.
According to an embodiment of the invention, the specific surface area of the nickel titanium composite catalyst is 50-160m 2/g, preferably 60-150m 2/g, for example 146m 2/g、131m2/g、61m2/g.
According to an embodiment of the invention, the pore volume of the nickel titanium composite catalyst is 0.2-0.5cm 3/g, preferably 0.21-0.36cm 3/g, for example 0.36cm 3/g、0.31cm3/g、0.25cm3/g.
According to an embodiment of the invention, the nickel titanium composite catalyst has an average pore diameter of 5-20nm, preferably 8-18nm, more preferably 9-15nm, for example 9.7nm, 9.3nm or 13.7nm.
According to an embodiment of the invention, the nickel titanium composite catalyst has an average particle diameter of 100 to 2500nm, for example 150 to 800nm, 200 to 500nm.
According to an embodiment of the present invention, the catalyst may be prepared from a raw material selected from the following compositions: nickel salts, organotitanates, and benzoic acid type compounds; wherein the nickel salt may be selected from at least one of nickel nitrate (Ni (NO 3)2·6H2 O), nickel chloride (NiCl 2·6H2 O), nickel acetate (Nickelous acetate), preferably nickel nitrate, the organic titanate may be selected from at least one of tetrabutyl titanate, isopropyl titanate or n-propyl titanate, and the organic titanate is exemplified by isopropyl titanate, and further, the benzoic acid compound may be selected from at least one of benzene dicarboxylic acid type compound, benzene tricarboxylic acid type compound, benzene tetracarboxylic acid type compound or benzene polycarboxylic acid type compound, and exemplified by benzene dicarboxylic acid type compound.
Preferably, the composition may further include an organic solvent, which is not particularly limited in the present invention, and may be selected from at least one of organic solvents known in the art, such as methanol, N-dimethylformamide, ethanol, isopropanol, triethanolamine, etc. Preferably, the organic solvent is selected from methanol and/or N, N-dimethylformamide. Illustratively, the solvent is methanol and N, N-dimethylformamide in a volume ratio of 1 (5-20), preferably 1 (8-10), for example 1:9.
The invention also provides a preparation method of the nickel-titanium composite catalyst, which comprises the following steps: the composition is adopted to prepare a precursor of the nickel salt and the titanium-based metal organic framework, and the precursor is roasted and reduced to obtain the nickel-titanium composite catalyst; the catalyst carrier is prepared by a metal organic framework method.
According to an embodiment of the invention, the preparation method specifically comprises the following steps:
(1) Synthesizing organic titanate, a benzoic acid type compound, methanol and N, N-dimethylformamide by a solvothermal method to prepare a titanium-based metal organic framework;
(2) Uniformly mixing nickel salt and the titanium-based metal organic framework obtained in the step (1), filtering and drying to obtain a catalyst precursor with uniform dispersivity;
(3) And (3) roasting the catalyst precursor in the step (2) through air and reducing and roasting to obtain the nickel-titanium composite catalyst.
According to an embodiment of the present invention, in step (1), the organic titanate is tetrabutyl titanate, isopropyl titanate, or n-propyl titanate, and illustratively, the organic titanate is isopropyl titanate;
According to an embodiment of the present invention, in step (1), the selected benzoic acid type compound is a terephthalic acid type compound, an isophthalic acid type compound, and illustratively terephthalic acid.
According to an embodiment of the invention, in step (1), the synthesis time is 12-24 hours, preferably 15-20 hours.
According to an embodiment of the invention, in step (1), the synthesis temperature is 120-180 ℃, preferably 150-160 ℃.
According to an embodiment of the present invention, the nickel salt in step (2) is selected from at least one of nickel nitrate (Ni (NO 3)2·6H2 O), nickel chloride (NiCl 2·6H2 O), nickel acetate (Nickelous acetate), preferably nickel nitrate.
According to an embodiment of the present invention, in step (2), the amounts of the nickel salt, the organotitanate, the benzoic acid compound and the organotitanate are calculated according to the stoichiometric number required in the nickel titanium composite catalyst.
According to the embodiment of the invention, in the step (2), the filtering and drying can be performed by adopting the technical means known in the technical field.
Preferably, the temperature of the drying is 60-100 ℃, preferably 60-80 ℃; preferably, the drying time is 1 to 24 hours, preferably 4 to 12 hours.
According to an embodiment of the invention, the homogeneous mixing in step (2) may be obtained by means of ultrasound and/or stirring. Preferably, the ultrasound time is 5-30 minutes, preferably 5-10 minutes. Preferably, the stirring time is 2 to 24 hours, preferably 4 to 6 hours.
According to an exemplary scheme of the invention, in the step (2), the uniform mixing comprises dispersing a titanium-based metal organic frame and nickel salt in water to obtain a nickel salt water solution and a titanium-based metal organic frame water solution, adding the nickel salt water solution into the titanium-based metal organic frame water solution, and mixing after ultrasonic treatment and stirring to obtain the catalyst precursor. In the invention, means such as ultrasonic and stirring are beneficial to anchoring Ni ions in the pore canal of the titanium-based metal organic framework, and are beneficial to promoting the uniform dispersion of nickel particles and controlling the size of the nickel particles.
According to an embodiment of the present invention, in the step (3), the air firing means firing by introducing air.
Preferably, the temperature of the air calcination is 250-600 ℃, preferably 400-500 ℃, e.g. 450 ℃.
Preferably, the air calcination is carried out for a period of time ranging from 2 to 10 hours, preferably from 4 to 8 hours, for example 6 hours.
Preferably, the air flow rate is 10-200mL/min, preferably 50-100mL/min, for example 50mL/min, when air calcined.
Preferably, the air calcination is carried out at a temperature increase rate of 1-10deg.C/min, preferably 2-5deg.C/min, for example 3 deg.C/min.
According to an embodiment of the present invention, in the step (3), the reducing roasting means roasting by passing a reducing gas such as hydrogen.
Preferably, the temperature of the reduction roasting is 300-600 ℃, preferably 350-450 ℃, for example 400 ℃.
Preferably, the air calcination is carried out for a period of time ranging from 2 to 10 hours, preferably from 3 to 6 hours, for example 3 hours.
Preferably, the flow rate of the reducing gas is 10-100mL/min, preferably 20-50mL/min.
Preferably, the temperature rise rate of the reduction roasting is 1-10 ℃/min, preferably 2-5 ℃/min, for example 3 ℃/min.
According to an exemplary scheme of the invention, the preparation method of the nickel-titanium composite catalyst comprises the following steps:
(1) Uniformly mixing organic titanate, a benzoic acid compound and methanol, N, N-dimethylformamide, and synthesizing a titanium-based metal organic framework by a solvothermal method;
(2) Dispersing the titanium-based metal organic framework and nickel salt in water to obtain nickel salt water solution and titanium-based metal organic framework water solution;
(3) Uniformly mixing nickel salt aqueous solution and titanium-based metal organic framework aqueous solution, filtering and drying to obtain a catalyst precursor;
(4) And (3) roasting the catalyst precursor obtained in the step (3) in the air atmosphere and in the hydrogen atmosphere sequentially to obtain the nickel-titanium composite catalyst.
The invention also provides application of the nickel-titanium composite catalyst in catalyzing CO 2 methanation reaction. Preferably, the catalysis is photo-thermal catalysis; more preferably, the photo-thermal catalysis is to absorb light energy of at least one of visible light, infrared light and ultraviolet light through the nickel-titanium catalyst as a driving energy source for the reaction, and illustratively, an infrared light source is selected as a driving light source to convert the absorbed light energy into heat energy, so as to catalyze the methanation of CO 2. Further, the incident light intensity used for the photo-thermal catalysis may be 100-2000mW/cm 2, and for example, the incident light intensity may be 630mW/cm 2、930mW/cm2、1230mW/cm2、1530mW/cm2.
The invention also provides a method for photo-thermal catalytic methanation of CO 2, which comprises the following steps: the nickel-titanium catalyst absorbs light energy of at least one of visible light, infrared light and ultraviolet light, preferably, an infrared light source is selected as a driving light source to convert the absorbed light energy into heat energy so as to catalyze the methanation of CO 2.
The invention has the beneficial effects that:
The nickel-titanium composite catalyst provided by the invention is a nickel-loaded TiO 2 -based catalyst, has strong interaction between Ni and Ti, has rich oxygen defects, can absorb and utilize infrared light, fully utilizes the heat energy converted by light energy, efficiently drives CO 2 to reduce and form the nickel-titanium composite catalyst synthesized by the invention, has high light absorption and good light-to-heat energy capability, has high activity, and has good application prospect in high methane selectivity.
The method has the following advantages:
(1) The preparation method provided by the invention prepares the nickel-titanium composite catalyst with high uniform mixing in synthesis, and the preparation method has the advantages of easily available raw materials, simple process and easy industrialization;
(2) According to the preparation method provided by the invention, nickel ions are uniformly adsorbed in the pore canal of the organic framework by utilizing the porous characteristic of the titanium-based organic metal framework in the preparation process, the synthesized titanium-based organic metal framework is uniformly combined with nickel salt, and strong interaction is formed between Ni and Ti in the roasting process; the synthesized uniformly dispersed nickel-loaded TiO 2 -based catalyst still has the characteristics of high dispersion and small size of zero-valent Ni after hydrogen roasting reduction, and abundant surface oxygen defects are formed on the surface of the catalyst due to the hydrogen overflow effect, so that the capability of adsorbing and activating CO 2 of the material is greatly improved, and the conversion from CO 2 to CH 4 can be efficiently realized.
(3) The catalyst can realize photo-thermal conditions without an external heating device, and the nickel-loaded TiO 2 -based catalyst can realize strong light absorption under the full spectrum, particularly can effectively absorb infrared light, and has obviously improved catalytic activity. The catalyst disclosed by the invention converts absorbed light energy into heat energy, and can realize efficient CO 2 illumination methanation without using an external heating device.
(4) The catalyst of the invention still maintains high-efficiency catalytic activity and stability after long-time catalytic experiments.
Drawings
FIG. 1 is an X-ray diffraction pattern of the catalyst.
Fig. 2 is a transmission electron microscopic image of the nickel-titanium composite catalyst (left) of example 1 and the catalyst (right) of comparative example 2.
Fig. 3 is an elemental distribution profile of the nickel titanium composite catalyst of example 1 (left) and an elemental distribution profile of the catalyst of comparative example 1 (right).
FIG. 4 is a graph of a comparison of UV-visible diffuse reflectance spectra of a nickel titanium composite catalyst.
Fig. 5 is a hydrogen temperature programmed reduction map of the nickel titanium composite catalyst of example 1 and the catalysts of comparative examples 1 and 2.
Fig. 6 is an electron paramagnetic resonance spectrum of the nickel-titanium composite catalyst of example 1 and comparative example 1.
FIG. 7 is a graph of the rates of CH 4 and CO produced by the catalysts of examples 1-3 and comparative examples 1-2.
FIG. 8 is a graph showing CH 4 yield and catalyst surface temperature of the nickel titanium composite catalyst of example 1 under different light intensity irradiation.
Fig. 9 is a graph of CH 4 formation rate and CH 4 formation selectivity of the nickel titanium composite catalyst of example 1 in a durability experiment.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
The preparation process of the nickel-titanium composite catalyst in the embodiment comprises the following steps:
The first step: 6mL of methanol and 54mL of N, N-dimethylformamide were taken and stirred for 10min, then 3.53g of terephthalic acid was added, followed by vigorous stirring for 30min, then 2.1mL of isopropyl titanate was added, and after vigorous stirring for 30min, the mixture was transferred to an autoclave and placed in an oven and heated to 150℃for 16h. After the autoclave was cooled, the sample was centrifuged out, then dispersed in methanol and stirred for 12 hours, finally centrifuged and dried under vacuum at 80 ℃ overnight to obtain a titanium-based metal-organic framework.
And a second step of: dispersing 1g of the titanium-based metal organic frame in 100mL of water, and stirring for 10min by ultrasonic; 10mL of 58.4mg/mL Ni (NO) 3·6H2 O is taken and added into the solution, ultrasonic treatment is carried out for 30min, stirring is carried out for 6 hours, then filtration is carried out, and the obtained solution is placed in an oven at 80 ℃ for drying for 12 hours, thus obtaining the precursor of the nickel salt and the titanium-based metal organic framework which are uniformly dispersed.
And a third step of: and (3) placing the dried precursor in a quartz tube, and heating to 450 ℃ at a speed of 3 ℃/min under an air atmosphere of 50mL/min, and keeping for 6 hours to obtain 8NiO/TiO 2.
Fourth step: the sample calcined in the air atmosphere was placed in a quartz tube, and kept at a temperature of 400℃for 3 hours at a rate of 3℃per minute under a hydrogen atmosphere of 30 mL/min.
Fifth step: the reduced sample was taken out and surface adsorbed H 2 was blown off by N 2 to give an 8Ni/TiO 2 catalyst. The actual loading of Ni was found to be 8wt% after ICP testing of the catalyst of this example (i.e., ni: tiO 2 mass ratio was 8 wt%).
Example 2
The preparation process of the nickel-titanium composite catalyst in the embodiment comprises the following steps:
The first step: 6mL of methanol and 54mL of N, N-dimethylformamide were taken and stirred for 10min, then 3.53g of terephthalic acid was added, followed by vigorous stirring for 30min, then 2.1mL of isopropyl titanate was added, and after vigorous stirring for 30min, the mixture was transferred to an autoclave and placed in an oven and heated to 150℃for 16h. After the autoclave was cooled, the sample was centrifuged out, then dispersed in methanol and stirred for 12 hours, finally centrifuged and dried under vacuum at 80 ℃ overnight to obtain a titanium-based metal-organic framework.
And a second step of: dispersing 1g of the titanium-based metal organic frame in 100mL of water, and stirring for 10min by ultrasonic; 5mL of 58.4mg/mL Ni (NO) 3·6H2 O is taken and added into the solution, ultrasonic treatment is carried out for 30min, stirring is carried out for 6 hours, then filtration is carried out, and the obtained solution is placed in an oven at 80 ℃ for drying for 12 hours, thus obtaining the precursor of the nickel salt and the titanium-based metal organic framework which are uniformly dispersed.
And a third step of: and (3) placing the dried precursor in a quartz tube, and heating to 450 ℃ at a speed of 3 ℃/min under an air atmosphere of 50mL/min, and keeping for 6 hours to obtain 5NiO/TiO 2.
Fourth step: the sample calcined in the air atmosphere was placed in a quartz tube, and kept at a temperature of 400℃for 3 hours at a rate of 3℃per minute under a hydrogen atmosphere of 30 mL/min.
Fifth step: the reduced sample was taken out and surface adsorbed H 2 was blown off by N 2 to give a 5Ni/TiO 2 catalyst. The actual loading of Ni was found to be 5.1wt% after ICP testing of the catalyst of this example (i.e., ni: tiO 2 mass% was found to be 5.1 wt%).
Example 3
The preparation process of the nickel-titanium composite catalyst in the embodiment comprises the following steps:
The first step: 6mL of methanol and 54mL of N, N-dimethylformamide were taken and stirred for 10min, then 3.53g of terephthalic acid was added, followed by vigorous stirring for 30min, then 2.1mL of isopropyl titanate was added, and after vigorous stirring for 30min, the mixture was transferred to an autoclave and placed in an oven and heated to 150℃for 16h. After the autoclave was cooled, the sample was centrifuged out, then dispersed in methanol and stirred for 12 hours, finally centrifuged and dried under vacuum at 80 ℃ overnight to obtain a titanium-based metal-organic framework.
And a second step of: dispersing 1g of the titanium-based metal organic frame in 100mL of water, and stirring for 10min by ultrasonic; 15mL of 58.4mg/mL Ni (NO) 3·6H2 O is taken and added into the solution, ultrasonic treatment is carried out for 30min, stirring is carried out for 6 hours, then filtration is carried out, and the obtained solution is placed in an oven at 80 ℃ for drying for 12 hours, thus obtaining the precursor of the nickel salt and the titanium-based metal organic framework which are uniformly dispersed.
And a third step of: and (3) placing the dried precursor in a quartz tube, and heating to 450 ℃ at a speed of 3 ℃/min under an air atmosphere of 50mL/min, and keeping for 6 hours to obtain 10NiO/TiO 2.
Fourth step: the sample calcined in the air atmosphere was placed in a quartz tube, and kept at a temperature of 400℃for 3 hours at a rate of 3℃per minute under a hydrogen atmosphere of 30 mL/min.
Fifth step: the reduced sample was taken out and surface adsorbed H 2 was blown off by N 2 to give a 10Ni/TiO 2 catalyst. The actual loading of Ni was found to be 10.1wt% after ICP testing of the catalyst of this example (i.e., the mass ratio of Ni to TiO 2 was 10.1 wt%).
Comparative example 1
The specific preparation process for synthesizing commercial P25 supported nickel-based catalyst comprises the following steps:
The first step: 1g of commercial P25 was dispersed in 100mL of water and stirred ultrasonically for 10min; adding 6.8mL of 58.4mg/mL Ni (NO) 3·6H2 O into the solution, carrying out ultrasonic treatment for 30min, stirring for 3 hours, heating to 80 ℃ for drying by distillation, and placing in an 80 ℃ oven for drying for 12 hours to obtain a precursor of nickel salt and P25.
And a third step of: and (3) placing the dried precursor in a quartz tube, and heating to 450 ℃ at a speed of 3 ℃/min under an air atmosphere of 50mL/min, and keeping for 6 hours to obtain 8NiO/P25.
Fourth step: the sample calcined in the air atmosphere was placed in a quartz tube, and kept at a temperature of 400℃for 3 hours at a rate of 3℃per minute under a hydrogen atmosphere of 30 mL/min.
Fifth step: the reduced sample was taken out and surface adsorbed H 2 was blown off by N 2 to give an 8Ni/P25 catalyst. The actual loading of Ni was found to be 7.9wt% after ICP testing of the catalyst of this comparative example (i.e., the mass ratio of Ni: P25 was 7.9 wt%).
Comparative example 2
The TiO 2 catalyst is prepared by taking a metal organic framework as a template, and the specific preparation process comprises the following steps:
The first step: 6mL of methanol and 54mL of N, N-dimethylformamide were taken and stirred for 10min, then 3.53g of terephthalic acid was added, followed by vigorous stirring for 30min, then 2.1mL of isopropyl titanate was added, and after vigorous stirring for 30min, the mixture was transferred to an autoclave and placed in an oven and heated to 150℃for 16h. After the autoclave was cooled, the sample was centrifuged out, then dispersed in methanol and stirred for 12 hours, finally centrifuged and dried under vacuum at 80 ℃ overnight to obtain a titanium-based metal-organic framework.
And a third step of: 1g of the titanium-based metal organic frame is taken and placed in a quartz tube, and the temperature is raised to 450 ℃ at a speed of 3 ℃/min under an air atmosphere of 50mL/min, and the quartz tube is kept for 6 hours.
Fourth step: the sample calcined in the air atmosphere was placed in a quartz tube, and kept at a temperature of 400℃for 3 hours at a rate of 3℃per minute under a hydrogen atmosphere of 30 mL/min.
Fifth step: the reduced sample was taken out and the surface adsorbed H 2 was blown off by N 2 to give TiO 2 catalyst.
FIG. 1 is an X-ray diffraction pattern of the catalysts of examples 1-3 and comparative examples 1, 2, showing that Ni was uniformly dispersed on TiO 2 and had strong interactions, and the calculated Ni particle sizes are shown in Table 1.
FIG. 2 is a transmission electron microscope image of the catalyst of example 1 (left) and the catalyst of comparative example 2 (right). It can be seen that the sample prepared in example 1 maintained good morphology and the surface was more porous.
Physical adsorption of the materials prepared in examples 1-3 and comparative examples 1-2 is shown in Table 1. Physical adsorption indicates that: the sample of example 1 has a large specific surface area, which is favorable for the adsorption of the reaction gas, and the smaller average pore diameter can increase the turbulence speed of the reactant in the material, thereby improving the contact between the material and the reactant. Meanwhile, the Ni particle size of example 1 is much smaller than that of comparative example 1, so that more active sites can be provided for reaction, and the catalytic activity is improved.
TABLE 1
FIG. 3 is a surface view of the elemental distribution of catalyst 8Ni/TiO 2 prepared in example 1 (left) and of catalyst 8Ni/P25 prepared in comparative example 1 (right). As can be seen from fig. 3, the catalyst prepared in example 1 has very uniform dispersion of Ni and Ti compared to the catalyst of comparative example 1, indicating that the interaction between the two is enhanced, and the uniform dispersion of Ni also provides more active sites for the reaction, which is one of the reasons that the catalyst of example 1 has higher reactivity.
Fig. 4 is a graph showing the comparison of the uv-visible diffuse reflectance spectra of the catalysts prepared in examples 1-3 and comparative examples 1 and 2, and it can be seen from fig. 4 that the catalysts prepared in examples 1-3 have higher light absorption intensity in the full spectrum range than those of the catalysts prepared in comparative examples 1 and 2, which indicates that the nickel-titanium composite catalyst of the present invention can achieve effective light absorption in the full spectrum range, because Ni is uniformly dispersed in the nickel-titanium composite catalyst prepared in the present invention, there are more surface oxygen defects, and the porous cavity structure has more pores, which can enhance the light absorption effect.
FIG. 5 is a hydrogen temperature programmed reduction plot of the catalysts prepared in example 1, comparative examples 1, 2, and it can be seen from FIG. 5 that catalyst 8Ni/TiO 2 prepared in example 1 exhibits a stronger interaction peak of Ni reduction peaks relative to catalyst 8Ni/P25 of comparative example 1; a lower temperature Ti 4+ reduction peak was exhibited relative to the catalyst of comparative example 2. This shows that Ni and TiO 2 in the nickel-titanium composite catalyst have tighter combination and are easier to generate surface oxygen defects.
FIG. 6 electron paramagnetic resonance spectra of the catalysts prepared in example 1 and comparative example 1, it can be seen from FIG. 6 that the catalyst 8Ni/TiO 2 prepared in example 1 exhibits oxygen vacancies at a lower temperature and characteristic peaks of Ti 3+, and that there are abundant defect sites on the surface of the catalyst 8Ni/TiO 2, relative to the catalyst 8Ni/P25 of comparative example 1.
Example 4
Evaluation of catalyst Activity under static conditions (evaluation of catalyst by testing the rate of CO 2 to CH 4 and CO formation)
The reactor used was a stainless steel static reactor with a volume of 40 mL. Before the experiment, 40mg of each of the catalysts prepared in the examples 1-3 and the comparative examples 1-2 was weighed as a sample, mixed with 10mL of absolute ethyl alcohol, dispersed uniformly by ultrasonic, and uniformly coated on a glass fiber film (phi 50 mm) by a sand core filtration method, and dried at 80 ℃. The dried glass fiber film is placed in a reactor, and mixed gas (volume ratio is 10 percent: 40 percent: 50 percent, volume flow rate is 10mL/min, gas source is Xiamen Linde gas Co., ltd.) of CO 2、H2 and He is introduced into the reactor for 30min, then a lamp is turned on for reaction, and the light source used in the reaction is a Philips infrared lamp with power of 375W. The products CH 4 and CO produced in the reaction process are detected by gas chromatography, wherein the CH 4 generation rate and the CO generation rate are respectively shown by the following formulas (1) and (2):
CH 4 production Rate (mmol/g Ni·h)＝[CH4 ]/(Ni mass. Reaction time) (1)
CO production Rate (mmol/g Ni. H) = [ CO ]/(Ni mass. Reaction time) (2)
Wherein, the molar concentrations of [ CH 4 ] and [ CO ] are all used.
FIG. 7 is a graph of CH 4 and CO rates generated by the catalysts prepared in examples 1-3 and comparative examples 1-2 under the conditions of example 4 (light intensity 1230mW/cm 2) (left). Demonstrating that the materials prepared in examples 1-3 possess a relatively strong CH 4 formation rate and methane selectivity approaching 100%, much higher than comparative example 1. By adjusting the amount of nickel supported in the catalyst of the present invention in an appropriate amount, the reactivity can be further controlled, wherein the catalyst prepared in example 1 exhibits the highest CH 4 production rate.
FIG. 8 is a graph of CH 4 production rate and surface temperature for the catalyst of example 1 under the test conditions of example 4, showing that temperature has a significant effect on the activity of the catalyst.
Fig. 9 is a graph showing the rate and selectivity of CH 4 produced by the catalyst of example 1 after 48 hours of durability test under the test conditions of example 4 (light intensity of 1230mW/cm 2), and it can be shown that the nickel titanium composite catalyst of the present invention has good and stable methane yield and excellent selectivity, and can be put into practical use.
The above description has been given of exemplary embodiments of the present invention. The present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, or the like, which are within the spirit and principles of the present invention, should be made by those skilled in the art, and are intended to be included within the scope of the present invention.
Claims (13)
1. The application of the nickel-titanium composite catalyst in the photo-thermal catalysis of CO 2 methanation reaction is characterized in that the catalyst is expressed by a chemical formula of Ni/TiO 2, wherein a catalyst carrier is TiO 2, and Ni element is uniformly dispersed on the catalyst carrier in a small-size metallic state nickel nano-particles; the Ni and the TiO 2 have strong interaction, and the surface has rich oxygen defects; the loading amount of the Ni element on the carrier is 5-10wt%;
The preparation method of the nickel-titanium composite catalyst comprises the following steps: the preparation raw material composition of the nickel-titanium composite catalyst is as follows: nickel salt, organic titanate and a benzoic acid type compound, and a precursor of the nickel salt and the titanium-based metal-organic framework is prepared, wherein Ni ions are anchored in pore channels of the titanium-based metal-organic framework; roasting and reducing the precursor to obtain the nickel-titanium composite catalyst; the catalyst carrier TiO 2 is prepared by a metal organic framework method.
2. The use according to claim 1, wherein the nickel titanium composite catalyst has a specific surface area of 50-160 m 2/g;
The pore volume of the nickel-titanium composite catalyst is 0.2-0.5 cm 3/g;
the average pore diameter of the nickel-titanium composite catalyst is 5-20nm;
the average particle size of the nickel-titanium composite catalyst is 100-2500 nm.
3. The use according to claim 1, wherein the nickel titanium composite catalyst has a specific surface area of 60-150 m 2/g;
The pore volume of the nickel-titanium composite catalyst is 0.21-0.36cm 3/g;
The average pore diameter of the nickel-titanium composite catalyst is 8-18nm.
4. The use according to claim 1, wherein the nickel salt is selected from at least one of nickel nitrate, nickel chloride, nickel acetate; the organic titanate is at least one selected from tetrabutyl titanate, isopropyl titanate or n-propyl titanate.
5. The use according to claim 4, wherein the benzoic acid type compound is selected from at least one of benzene dicarboxylic acid type compounds, benzene tricarboxylic acid type compounds, benzene tetracarboxylic acid type compounds;
The composition further comprises an organic solvent selected from at least one of methanol, N-dimethylformamide, ethanol, isopropanol and triethanolamine.
6. Use according to claim 5, characterized in that the organic solvent is selected from methanol and/or N, N-dimethylformamide.
7. The use according to claim 1, characterized in that the preparation method comprises in particular the following steps:
(1) Synthesizing organic titanate, a benzoic acid type compound, methanol and N, N-dimethylformamide by a solvothermal method to prepare a titanium-based metal organic framework;
(2) Uniformly mixing nickel salt and the titanium-based metal organic framework obtained in the step (1), filtering and drying to obtain a catalyst precursor with uniform dispersivity;
(3) And (3) roasting the catalyst precursor in the step (2) through air and reducing and roasting to obtain the nickel-titanium composite catalyst.
8. The use according to claim 7, wherein in step (1) the organic titanate is tetrabutyl titanate, isopropyl titanate or n-propyl titanate;
In the step (1), the benzoic acid type compound is a terephthalic acid type compound and an isophthalic acid type compound.
9. The use according to claim 7, wherein in step (1) the synthesis time is 12-24 hours;
In the step (1), the synthesis temperature is 120-180 o C.
10. The use according to claim 7, wherein the nickel salt in step (2) is selected from at least one of nickel nitrate, nickel chloride, nickel acetate;
in the step (2), the dosages of the nickel salt, the benzoic acid compound and the organic titanate are calculated according to the stoichiometric number required in the nickel-titanium composite catalyst;
The temperature of the drying is 60-100 o ℃; the drying time is 1-24 hours;
The uniform mixing in the step (2) is obtained by means of ultrasound and/or stirring; the ultrasonic time is 5-30 minutes; stirring for 2-24 hours;
In the step (2), the uniform mixing comprises dispersing a titanium-based metal organic frame and nickel salt in water to obtain nickel salt water solution and titanium-based metal organic frame water solution, adding the nickel salt water solution into the titanium-based metal organic frame water solution, and mixing after ultrasonic treatment and stirring to obtain the catalyst precursor; the Ni ions are anchored in the pore canal of the titanium-based metal organic framework, which promotes the uniform dispersion of the nickel particles and controls the size of the nickel particles.
11. The use according to claim 7, wherein in step (3), the air firing means firing by introducing air; the temperature of the air roasting is 250-600 o ℃; the air roasting time is 2-10 hours; when the air is roasted, the air flow is 10-200 mL/min; the temperature rising rate of the air roasting is 1-10 o C/min;
In the step (3), the reduction roasting refers to roasting by introducing a reducing gas; the temperature of the reduction roasting is 300-600 o ℃; the reduction roasting time is 2-10 hours; the flow rate of the reducing gas is 10-100 mL/min; the temperature rising rate of the reduction roasting is 1-10 o C/min.
12. The use according to claim 7, wherein the preparation method of the nickel titanium composite catalyst comprises the following steps:
(1) Uniformly mixing organic titanate, a benzoic acid compound and methanol, N, N-dimethylformamide, and synthesizing a titanium-based metal organic framework by a solvothermal method;
(2) Dispersing the titanium-based metal organic framework and nickel salt in water to obtain nickel salt water solution and titanium-based metal organic framework water solution;
(3) Uniformly mixing nickel salt aqueous solution and titanium-based metal organic framework aqueous solution, filtering and drying to obtain a catalyst precursor;
(4) And (3) roasting the catalyst precursor obtained in the step (3) in the air atmosphere and in the hydrogen atmosphere sequentially to obtain the nickel-titanium composite catalyst.
13. The use of claim 1, wherein the photo-thermal catalysis is to absorb light energy of at least one of visible light, infrared light and ultraviolet light as a driving energy source for the reaction by the nickel-titanium composite catalyst, and convert the absorbed light energy into heat energy, thereby catalyzing methanation of CO 2; the light intensity of the incident light used for the photo-thermal catalysis is 100-2000 mW/cm 2.
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