CN115770576A - 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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- CN115770576A CN115770576A CN202111038753.8A CN202111038753A CN115770576A CN 115770576 A CN115770576 A CN 115770576A CN 202111038753 A CN202111038753 A CN 202111038753A CN 115770576 A CN115770576 A CN 115770576A
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Abstract
The invention discloses a nickel-titanium composite catalyst, a preparation method and application thereof. The nickel-titanium composite catalyst of the invention has the chemical formula of Ni/TiO 2 Wherein the catalyst carrier is TiO 2 The Ni element is uniformly dispersed on the catalyst carrier in the form of small-sized metal nickel nano particles; ni and TiO 2 The surface of the material has rich oxygen defects due to strong interaction; the loading amount of the Ni element on the carrier is 2-50wt%. The invention utilizes the porous characteristic of a titanium-based organic metal framework to uniformly adsorb nickel ions in pore channels of the organic framework, and the nickel ions are bakedThe catalyst of the invention is obtained by reduction, has more surface oxygen defects, greatly improves the adsorption of the material and activates CO 2 Of the cell. The catalyst can realize strong light absorption under full spectrum, convert absorbed light energy into heat energy, and realize high-efficiency CO without using an external heating device 2 And (4) methanation.
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 the essential main power element for the economic development of human society at present, and the consumption of a large amount of fossil fuel brings great economic benefits to human beings, improves the living standard of the human beings, but also generates a large amount of CO 2 Leading to greenhouse effect and energy crisis. The international committee on climate change predicted that, by 2100 years, CO in the earth's atmosphere 2 The content will be as high as 590ppm and the global average temperature will rise by 1.9 c, whereby global climate changes will lead to unfortunate catastrophic consequences. In view of atmospheric CO 2 The serious influence of the rising concentration on global climate, and the development of new technology for CO 2 Removal or transformation of (a) is urgently inevitable.
The electrocatalysis technology directly degrades a substrate through electrode reaction under the action of an external electric field, or generates a large amount of free radicals with strong oxidability to react with the substrate by utilizing the catalytic activity of an electrode or a 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, but needs to continuously supplement external energy; the thermal catalysis technology is to inject energy crossing thermodynamic barrier into a catalytic reaction system in the form of heat energy to drive the catalytic reaction, and the technology is usually carried out at high temperature and high pressure, so that the large consumption of energy also becomes the biggest obstacle to the development of the technology; the basic principle of the photocatalytic technology is as follows: when light irradiates a semiconductor photocatalyst, if the energy of a photon is higher than the forbidden bandwidth of the semiconductor, the valence band electron of the semiconductor transits from the valence band to the conduction band, and photo-generated electrons and holes are generated in the conduction band and the valence band, respectively. The holes have strong oxidizing power, while the photo-generated electrons have strong reducing power, so that the electron acceptor on the surface of the semiconductor is reduced. The advantages of this technique are, but are limited by its own band limitations, with the catalysts currently used, such as WO 3 (Journal of Materials Chemistry A,2018,6(15):6265-72.)、TiO 2 (Applied Catalysis BMaterials such as Environmental,2017,210 (131-40.), znO (Journal of Materials Chemistry A,2019,7 (27): 16294-303.) can respond to ultraviolet or ultraviolet light and part of visible light, and the part of light only occupies about 47% of the full spectrum, namely, nearly 50% of sunlight is wasted (Journal of Materials Chemistry A,2019,7 (19): 11985-95). Therefore, the improvement of the utilization rate of sunlight becomes a research hotspot in the field of photocatalysis.
Considering the energy consumption of thermal catalysis and the problems of low sunlight utilization rate and insufficient catalytic reaction power of the traditional photocatalytic system, the method has important significance in realizing efficient optical drive thermal catalysis by driving catalytic reaction by using the heating effect of infrared light in a full-spectrum light source.
Disclosure of Invention
The invention provides a nickel-titanium composite catalyst which is expressed by the chemical formula Ni/TiO 2 Wherein the catalyst carrier is TiO 2 The Ni element is uniformly dispersed on the catalyst carrier in the form of small-sized metal nickel nano particles; ni and TiO 2 Have strong interaction and rich oxygen defects on the surface.
According to an embodiment of the present invention, the supported amount of Ni element on the support is 2 to 50wt%, preferably 5 to 30wt%, more preferably 5 to 20wt%, for example 5wt%, 8wt% or 10wt%.
According to an embodiment of the invention, the catalyst support is TiO 2 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 to 160m 2 A/g, preferably from 60 to 150m 2 A/g, e.g. of 146m 2 /g、131m 2 /g、61m 2 /g。
According to an embodiment of the invention, the nickel titanium composite catalyst has a pore volume of 0.2-0.5cm 3 Per g, preferably 0.21-0.36cm 3 In terms of/g, e.g. 0.36cm 3 /g、0.31cm 3 /g、0.25cm 3 /g。
According to an embodiment of the invention, the average pore size of the nickel titanium composite catalyst is between 5 and 20nm, preferably between 8 and 18nm, more preferably between 9 and 15nm, for example 9.7nm, 9.3nm or 13.7nm.
According to an embodiment of the invention, the average particle size of the nickel titanium composite catalyst is 100-2500nm, such as 150-800nm, 200-500nm.
According to an embodiment of the invention, the starting material for the preparation of the catalyst may be selected from the following compositions: nickel salts, organic titanates and benzoic acid type compounds; wherein the nickel salt may be selected from nickel nitrate (Ni (NO) 3 ) 2 ·6H 2 O), nickel chloride (NiCl) 2 ·6H 2 O), nickel acetate (nickel acetate), preferably nickel nitrate; the organic titanate may be selected from at least one of tetrabutyl titanate, isopropyl titanate, or n-propyl titanate, and is exemplified by isopropyl titanate; further, the benzoic acid compound may be at least one selected from a benzenedicarboxylic acid type compound, a benzenetricarboxylic acid type compound, a benzenetetracarboxylic acid type compound, benzene, or a benzenepolycarboxylic acid type compound, and may be, for example, a benzenedicarboxylic acid type compound. Illustratively, the selected benzenedicarboxylic acid type compound may be selected from the terephthalic acid type compound, the isophthalic acid type compound, and illustratively, terephthalic acid.
Preferably, the composition may further include an organic solvent, which is not particularly limited in the present invention and may be selected from organic solvents known in the art, such as at least one of 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), such as 1.
The invention also provides a preparation method of the nickel-titanium composite catalyst, which comprises the following steps: preparing a precursor of a nickel salt and a titanium-based metal organic framework by adopting the composition, and roasting and reducing the precursor to obtain the nickel-titanium composite catalyst; wherein the catalyst carrier is prepared by a metal organic framework method.
According to an embodiment of the present invention, the preparation method specifically comprises the steps of:
(1) Organic titanate, benzoic acid type compounds, methanol and N, N-dimethylformamide are synthesized 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), and filtering and drying to obtain a catalyst precursor with uniform dispersibility;
(3) And (3) roasting the catalyst precursor obtained in the step (2) in air, 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 exemplary 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 present invention, in step (1), the synthesis time is from 12 to 24 hours, preferably from 15 to 20 hours.
According to an embodiment of the present invention, in step (1), the synthesis temperature is 120 to 180 ℃, preferably 150 to 160 ℃.
According to an embodiment of the present invention, the nickel salt in step (2) is selected from nickel nitrate (Ni (NO) 3 ) 2 ·6H 2 O), nickel chloride (NiCl) 2 ·6H 2 O), nickel acetate (nickel acetate), preferably nickel nitrate.
According to the embodiment of the present invention, in the step (2), the amounts of the nickel salt, the organic titanate, the benzoic acid type compound and the organic titanate are calculated according to the stoichiometric number required in the nickel titanium composite catalyst.
According to the embodiment of the present invention, in the step (2), the filtration and the drying can be performed by using the technical means known in the art.
Preferably, the drying temperature 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 present invention, the uniform mixing in step (2) may be obtained by means of ultrasound and/or stirring. Preferably, the sonication time is between 5 and 30 minutes, preferably between 5 and 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 uniformly mixing comprises dispersing the titanium-based metal organic framework and the nickel salt in water to obtain a nickel salt aqueous solution and a titanium-based metal organic framework aqueous solution, adding the nickel salt aqueous solution into the titanium-based metal organic framework aqueous solution, performing ultrasonic treatment and stirring, and mixing to obtain the catalyst precursor. In the invention, the ultrasonic and stirring means is helpful to anchor Ni ions in the pore canal of the titanium-based metal organic framework, which is 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 calcination refers to calcination by introducing air.
Preferably, the air firing temperature is 250-600 ℃, preferably 400-500 ℃, e.g. 450 ℃.
Preferably, the air calcination is carried out for a period of 2 to 10 hours, preferably 4 to 8 hours, for example 6 hours.
Preferably, the air flow rate during air calcination is 10-200mL/min, preferably 50-100mL/min, e.g., 50mL/min.
Preferably, the air calcination is carried out at a temperature rise rate of 1-10 deg.C/min, preferably 2-5 deg.C/min, for example 3 deg.C/min.
According to an embodiment of the present invention, in the step (3), the reductive calcination refers to calcination by introducing a reducing gas, such as hydrogen.
Preferably, the temperature of the reductive calcination is in the range of 300 to 600 ℃, preferably in the range of 350 to 450 ℃, for example 400 ℃.
Preferably, the air calcination is carried out for a period of 2 to 10 hours, preferably 3 to 6 hours, for example 3 hours.
Preferably, the flow rate of the reducing gas is 10 to 100mL/min, preferably 20 to 50mL/min.
Preferably, the temperature rise rate of the reduction roasting is 1-10 deg.C/min, preferably 2-5 deg.C/min, for example 3 deg.C/min.
According to an exemplary embodiment of the present invention, the preparation method of the nickel titanium composite catalyst comprises the following steps:
(1) Uniformly mixing organic titanate, a benzoic acid type compound, methanol and 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 respectively to obtain a nickel salt aqueous solution and a titanium-based metal organic framework aqueous solution;
(3) Uniformly mixing a nickel salt aqueous solution and a titanium-based metal organic frame aqueous solution, filtering and drying to obtain a catalyst precursor;
(4) And (4) roasting the catalyst precursor obtained in the step (3) in an air atmosphere and a hydrogen atmosphere in sequence to obtain the nickel-titanium composite catalyst.
The invention also provides the application of the nickel-titanium composite catalyst in catalyzing CO 2 Application in methanation reaction. Preferably, the catalysis is photo-thermal catalysis; more preferably, the photothermal 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 exemplarily, an infrared light source is selected as a driving light source to convert the absorbed light energy into heat energy, so as to catalyze CO 2 And (4) methanation. Further, the incident light intensity used for the photothermal catalysis may be 100-2000mW/cm 2 Illustratively, the incident intensity may be 630mW/cm 2 、930mW/cm 2 、1230mW/cm 2 、1530mW/cm 2 。
The invention also provides photo-thermal catalytic CO 2 A process for methanation, said process comprising: 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, the absorbed light energy is converted into heat energy, and then CO is catalyzed 2 And (4) methanation.
The invention has the beneficial effects that:
the nickel-titanium composite catalyst provided by the invention is TiO loaded with nickel 2 Based on the catalyst, ni and Ti have strong interaction, rich surface oxygen defects, can absorb and utilize infrared light, fully utilize the heat energy converted by light energy and efficiently drive CO 2 The nickel-titanium composite catalyst synthesized by the invention has high light absorption, good light-to-heat conversion capability, high activity and high methane selectivity, and has good application prospect.
The method has the following advantages:
(1) The preparation method provided by the invention can be used for preparing the nickel-titanium composite catalyst with high uniform mixing degree in the synthesis process, and the preparation method has the advantages of easily obtained raw materials, simple process and easy industrialization;
(2) According to the preparation method provided by the invention, nickel ions are uniformly adsorbed in pore channels of the organic framework by utilizing the porous characteristic of the titanium-based organic metal framework in the preparation process, the synthesized titanium-based metal organic 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 on the catalyst, the zero-valence Ni still has the characteristics of high dispersion and small size after being roasted and reduced by hydrogen, and rich surface oxygen defects are formed on the surface of the catalyst due to the hydrogen overflow effect, so that the adsorption of the material and the activation of CO are greatly promoted 2 Ability to efficiently realize CO 2 To CH 4 The transformation of (3).
(3) The catalyst can realize photo-thermal condition without an external heating device, and the TiO supported with nickel can realize the photo-thermal condition 2 The base catalyst can realize strong light absorption under full spectrum, especially can effectively absorb infrared light, and the catalytic activity is obviously improved. The catalyst of the invention converts absorbed light energy into heat energy, and can realize high-efficiency CO without using an external heating device 2 And (4) performing methanation by illumination.
(4) After long-time catalytic experiments, the catalyst still maintains high-efficiency catalytic activity and stability.
Drawings
FIG. 1 is an X-ray diffraction pattern of the catalyst.
Fig. 2 is a transmission electron micrograph of the nickel titanium composite catalyst of example 1 (left) and the catalyst of comparative example 2 (right).
Fig. 3 is a schematic diagram showing the element distribution of the nickel titanium composite catalyst of example 1 (left) and the element distribution of the catalyst of comparative example 1 (right).
FIG. 4 is a comparison graph of the 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, 2.
FIG. 6 is an electron paramagnetic resonance spectrum of the nickel titanium composite catalyst of example 1 and comparative example 1.
FIG. 7 shows CH formation in catalysts of examples 1 to 3 and comparative examples 1 to 2 4 CO rate map.
FIG. 8 is a graph of CH of the nickel titanium composite catalyst of example 1 under different light intensity irradiation 4 Yield and catalyst surface temperature profile.
FIG. 9 shows CH generation in durability experiment for the nickel titanium composite catalyst of example 1 4 Rate sum generation CH 4 And (4) a selectivity graph.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
The preparation process of the nickel titanium composite catalyst of the embodiment comprises the following steps:
the first step is as follows: 6mL of methanol and 54mL of N, N-dimethylformamide are taken and stirred for 10min, then 3.53g of terephthalic acid is added and stirred vigorously for 30min, then 2.1mL of isopropyl titanate is added, and after stirring vigorously for 30min, the mixture is transferred into an autoclave and placed in an oven to be heated to 150 ℃ for 16h. After the autoclave was cooled, the sample was centrifuged, then dispersed in methanol and stirred for 12h, finally centrifuged and vacuum dried at 80 ℃ overnight to obtain a titanium-based metal organic framework.
The second step is that: taking 1g of the titanium-based metal organic framework, dispersing the titanium-based metal organic framework in 100mL of water, and ultrasonically stirring for 10min; collecting 10mL 58.4mg/mL Ni (NO) 3 ·6H 2 And adding O into the solution, performing ultrasonic treatment for 30min, stirring for 6 hours, filtering, and drying in an oven at 80 ℃ for 12 hours to obtain a precursor of the uniformly dispersed nickel salt and the titanium-based metal organic framework.
The third step: placing the dried precursor in a quartz tube, heating to 450 ℃ at the speed of 3 ℃/min in the air atmosphere of 50mL/min, and keeping for 6 hours to obtain 8NiO/TiO 2 。
The fourth step: the sample calcined in the air atmosphere was placed in a quartz tube, and heated to 400 ℃ at a rate of 3 ℃/min in a hydrogen atmosphere of 30mL/min for 3 hours.
The fifth step: taking out the reduced sample and passing through N 2 Blowing off surface adsorption H 2 To obtain 8Ni/TiO 2 A catalyst. The actual loading of Ni was 8wt% as determined by ICP testing of the catalyst of this example (i.e., ni: tiO) 2 Mass ratio 8 wt%).
Example 2
The preparation process of the nickel titanium composite catalyst of the embodiment comprises the following steps:
the first step is as follows: 6mL of methanol and 54mL of N, N-dimethylformamide were stirred for 10min, then 3.53g of terephthalic acid was added, stirred vigorously for 30min, then 2.1mL of isopropyl titanate was added, stirred vigorously for 30min and transferred to an autoclave, and heated in an oven to 150 ℃ for 16h. After the autoclave is cooled, centrifuging out a sample, then dispersing the sample in methanol, stirring for 12h, finally centrifuging and vacuum drying at 80 ℃ overnight to obtain the titanium-based metal organic framework.
The second step: dispersing 1g of the titanium-based metal organic framework in 100mL of waterPerforming ultrasonic stirring for 10min; fetching 5mL 58.4mg/mL Ni (NO) 3 ·6H 2 And adding O into the solution, performing ultrasonic treatment for 30min, stirring for 6 hours, filtering, and drying in an oven at 80 ℃ for 12 hours to obtain a precursor of the uniformly dispersed nickel salt and the titanium-based metal organic framework.
The third step: placing the dried precursor in a quartz tube, heating to 450 ℃ at the speed of 3 ℃/min in the air atmosphere of 50mL/min, and keeping for 6 hours to obtain 5NiO/TiO 2 。
The fourth step: the sample calcined in the air atmosphere was placed in a quartz tube, and heated to 400 ℃ at a rate of 3 ℃/min in a hydrogen atmosphere of 30mL/min for 3 hours.
The fifth step: taking out the reduced sample and passing through N 2 Blowing off surface adsorption H 2 To obtain 5Ni/TiO 2 A catalyst. The actual loading of Ni was 5.1wt% as determined by ICP testing of the catalyst of this example (i.e., ni: tiO) 2 Mass ratio 5.1 wt%).
Example 3
The preparation process of the nickel titanium composite catalyst of the embodiment comprises the following steps:
the first step is as follows: 6mL of methanol and 54mL of N, N-dimethylformamide are taken and stirred for 10min, then 3.53g of terephthalic acid is added and stirred vigorously for 30min, then 2.1mL of isopropyl titanate is added, and after stirring vigorously for 30min, the mixture is transferred into an autoclave and placed in an oven to be heated to 150 ℃ for 16h. After the autoclave is cooled, centrifuging out a sample, then dispersing the sample in methanol, stirring for 12h, finally centrifuging and vacuum drying at 80 ℃ overnight to obtain the titanium-based metal organic framework.
The second step: taking 1g of the titanium-based metal organic framework, dispersing the titanium-based metal organic framework in 100mL of water, and ultrasonically stirring for 10min; take 15mL 58.4mg/mL Ni (NO) 3 ·6H 2 And adding O into the solution, performing ultrasonic treatment for 30min, stirring for 6 hours, filtering, and drying in an oven at 80 ℃ for 12 hours to obtain a precursor of the uniformly dispersed nickel salt and the titanium-based metal organic framework.
The third step: placing the dried precursor into a quartz tube, and keeping the temperature of the quartz tube at 3 ℃ in an air atmosphere of 50mL/minThe min speed is increased to 450 ℃, and the temperature is kept for 6 hours to obtain 10NiO/TiO 2 。
The fourth step: the sample calcined in the air atmosphere was placed in a quartz tube, and heated to 400 ℃ at a rate of 3 ℃/min in a hydrogen atmosphere of 30mL/min for 3 hours.
The fifth step: taking out the reduced sample and passing through N 2 Blowing off surface adsorption H 2 To obtain 10Ni/TiO 2 A catalyst. The actual loading of Ni, as determined by ICP testing of the catalyst of this example, was 10.1wt% (i.e., ni: tiO) 2 Mass ratio 10.1 wt%).
Comparative example 1
The preparation process of synthesizing commercial P25 supported nickel-based catalyst includes the following steps:
the first step is as follows: 1g of commercial P25 is taken and dispersed in 100mL of water, and ultrasonic stirring is carried out for 10min; 6.8mL58.4mg/mL Ni (NO) 3 ·6H 2 And O is added into the solution, ultrasonic treatment is carried out for 30min, stirring is carried out for 3 hours, then heating is carried out until the temperature reaches 80 ℃, evaporation is carried out, and the dried product is placed in an oven at 80 ℃ for drying for 12 hours, thus obtaining the precursor of the nickel salt and the P25.
The third step: and (3) placing the dried precursor in a quartz tube, heating to 450 ℃ at the speed of 3 ℃/min in the air atmosphere of 50mL/min, and keeping for 6 hours to obtain 8NiO/P25.
The fourth step: the sample calcined in the air atmosphere was placed in a quartz tube, and heated to 400 ℃ at a rate of 3 ℃/min in a hydrogen atmosphere of 30mL/min for 3 hours.
The fifth step: taking out the reduced sample and passing through N 2 Blowing off surface adsorption H 2 To obtain the 8Ni/P25 catalyst. The actual loading of Ni, as determined by ICP testing of the catalyst of this comparative example, was 7.9wt% (i.e., the mass ratio of Ni to P25 was 7.9 wt%).
Comparative example 2
Preparation of TiO by using metal organic framework as template 2 The preparation process of the catalyst comprises the following steps:
the first step is as follows: 6mL of methanol and 54mL of N, N-dimethylformamide are taken and stirred for 10min, then 3.53g of terephthalic acid is added and stirred vigorously for 30min, then 2.1mL of isopropyl titanate is added, and after stirring vigorously for 30min, the mixture is transferred into an autoclave and placed in an oven to be heated to 150 ℃ for 16h. After the autoclave is cooled, centrifuging out a sample, then dispersing the sample in methanol, stirring for 12h, finally centrifuging and vacuum drying at 80 ℃ overnight to obtain the titanium-based metal organic framework.
The third step: 1g of the titanium-based metal organic framework is placed in a quartz tube, and the temperature is raised to 450 ℃ at the speed of 3 ℃/min under the air atmosphere of 50mL/min and is kept for 6 hours.
The fourth step: the sample calcined in the air atmosphere was placed in a quartz tube, and heated to 400 ℃ at a rate of 3 ℃/min in a hydrogen atmosphere of 30mL/min for 3 hours.
The fifth step: taking out the reduced sample and passing through N 2 Blowing off surface adsorption H 2 To obtain TiO 2 A catalyst.
FIG. 1 is an X-ray diffraction pattern of the catalysts of examples 1 to 3 and comparative examples 1 and 2, and it can be seen that Ni is present in TiO 2 Uniformly dispersed and having strong interaction, the calculated Ni particle size is listed in table 1.
Fig. 2 is a transmission electron micrograph 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 was more porous and loose on the surface.
The physical adsorption of the materials prepared in examples 1-3 and comparative examples 1-2 is shown in Table 1. Physical adsorption shows that: the sample of example 1 has a large specific surface area, which is favorable for the adsorption of the reactant gas, and a smaller average pore size can increase the turbulent velocity of the reactant inside the material, so that the contact between the material and the reactant is improved. Meanwhile, the Ni particle size of the embodiment 1 is far smaller than that of the comparative example 1, so that more active sites can be provided for the reaction, and the catalytic activity is improved.
TABLE 1
FIG. 3 shows catalyst 8N prepared in example 1i/TiO 2 The element distribution profile of (a) and the element distribution profile of the catalyst 8Ni/P25 prepared in comparative example 1 (a) are shown (left). As can be seen from fig. 3, in the catalyst prepared in example 1, ni and Ti are uniformly dispersed, indicating that the interaction between them is enhanced, and the uniform dispersion of Ni also provides more active sites for the reaction, which is one of the reasons why the catalyst of example 1 has higher reactivity, compared to the catalyst of comparative example 1.
Fig. 4 is a comparison graph of uv-visible diffuse reflectance spectra of the catalysts prepared in examples 1 to 3 and comparative examples 1 and 2, and it can be seen from fig. 4 that the catalysts prepared in examples 1 to 3 have higher absorption intensity in the full spectrum range than the catalysts of comparative examples 1 and 2, indicating that the nickel-titanium composite catalyst of the present invention can achieve effective absorption of light 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, which can enhance the light absorption effect.
FIG. 5 is a hydrogen temperature-programmed reduction map of the catalysts prepared in example 1 and comparative examples 1 and 2, and it can be seen from FIG. 5 that the catalyst 8Ni/TiO prepared in example 1 2 The reduction peak of Ni exhibited a stronger interacting peak relative to catalyst 8Ni/P25 of comparative example 1; exhibiting lower temperature Ti relative to the catalyst of comparative example 2 4+ Reduction of the peak. This shows that in the nickel-titanium composite catalyst of the invention, ni and TiO 2 The bonding is tighter, and surface oxygen defects are easier to generate.
FIG. 6 Electron Paramagnetic Resonance (EPR) spectra of catalysts prepared in example 1 and comparative example 1. As can be seen from FIG. 6, catalyst 8Ni/TiO prepared in example 1 2 Lower temperature oxygen vacancies and Ti were exhibited relative to catalyst 8Ni/P25 of comparative example 1 3+ Characteristic peak of (1), surface catalyst 8Ni/TiO 2 The surface is rich in defect sites.
Example 4
Evaluation of catalyst Activity under static conditions (by testing for CO) 2 To CH 4 And evaluation of CO production Rate catalyst)
The reactor used was a stainless steel static reactor having 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 is weighed as a sample, and is respectively mixed with 10mL of absolute ethyl alcohol, the mixture is uniformly dispersed by ultrasonic waves, and is uniformly coated on a glass fiber membrane (phi 50 mm) by adopting a sand core filtering method, and the glass fiber membrane is dried at 80 ℃. Placing the dried glass fiber membrane in a reactor, and introducing CO into the reactor 2 、H 2 And He gas mixture (volume ratio 10%:40%:50%, volume flow rate 10mL/min, gas source manamond gas Co., ltd.) 30min later, the lamp reaction was started, and the light source used in the reaction was a Philips infrared lamp with power of 375W. Product CH produced during the reaction 4 And CO by gas chromatography, wherein CH 4 The generation rate and the CO generation rate are respectively shown by the following equations (1) and (2):
CH 4 production Rate (mmol/g) Ni ·h)＝[CH 4 ]V (Ni Mass reaction time) (1)
CO production Rate (mmol/g) Ni ·h)＝[CO]V (Ni Mass reaction time) (2)
Wherein, [ CH ] is used 4 ]、[CO]Are all molar concentrations.
FIG. 7 shows the results of catalysts prepared in examples 1-3 and comparative examples 1-2 under the conditions of example 4 (illumination intensity of 1230 mW/cm) 2 ) Generating CH 4 CO rate plot (left). Illustrating that the materials prepared in examples 1-3 possess stronger CH 4 The rate of formation and methane selectivity, which is close to 100%, are much higher than in comparative example 1. While the reaction activity can be further controlled by adjusting the amount of supported nickel in the catalyst of the present invention in a proper amount, wherein the catalyst prepared in example 1 exhibited the highest CH 4 A rate is generated.
FIG. 8 is the CH for the catalyst of example 1 after varying the light intensity under the test conditions of example 4 4 A plot of rate and surface temperature was generated, which can indicate that temperature has a significant effect on the activity of the catalyst.
FIG. 9 shows the catalyst of example 1 under the test conditions of example 4 (illumination intensity of 1230 mW/cm) 2 ) Resistance to 48hCH formation after long-term test 4 The velocity and selectivity diagram can show that the nickel-titanium composite catalyst has good and stable methane yield and excellent selectivity, and can be put into practical application.
The exemplary embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement and the like made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (10)
1. The nickel-titanium composite catalyst is characterized in that the catalyst is represented by the chemical formula Ni/TiO 2 Wherein the catalyst carrier is TiO 2 Ni element is uniformly dispersed on the catalyst carrier in small-sized metal state nickel nano particles; ni and TiO 2 The surface of the material has rich oxygen defects due to strong interaction; the loading amount of the Ni element on the carrier is 2-50wt%.
2. The nickel titanium composite catalyst of claim 1, wherein the catalyst support is TiO 2 Prepared by a metal organic framework method.
Preferably, the specific surface area of the nickel-titanium composite catalyst is 50-160m 2 A ratio of/g, preferably 60 to 150m 2 /g。
Preferably, the pore volume of the nickel-titanium composite catalyst is 0.2-0.5cm 3 A/g, preferably of 0.21 to 0.36cm 3 /g。
Preferably, the average pore diameter of the nickel titanium composite catalyst is 5-20nm, preferably 8-18nm.
Preferably, the average particle size of the nickel titanium composite catalyst is 100-2500nm.
Preferably, the amount of the Ni element supported on the carrier is 5 to 30wt%, more preferably 5 to 20wt%.
3. The nickel titanium composite catalyst of claim 1 or 2, wherein the catalyst is selected from the group consisting ofThe preparation raw material of the agent can be selected from the following compositions: nickel salts, organic titanates and benzoic acid type compounds; wherein the nickel salt may be selected from nickel nitrate (Ni (NO) 3 ) 2 ·6H 2 O), nickel chloride (NiCl) 2 ·6H 2 O), nickel acetate (nickel acetate); the organic titanate is selected from at least one of tetrabutyl titanate, isopropyl titanate or n-propyl titanate; preferably, the benzoic acid compound is at least one selected from benzene dicarboxylic acid type compounds, benzene tricarboxylic acid type compounds, benzene tetracarboxylic acid type compounds and benzene polycarboxylic acid type compounds.
Preferably, the composition may further include an organic solvent, preferably, the organic solvent is at least one selected from methanol, N-dimethylformamide, ethanol, isopropanol, triethanolamine, and the like. Preferably, the organic solvent is selected from methanol and/or N, N-dimethylformamide.
4. A method of preparing the nickel titanium composite catalyst of any one of claims 1 to 3, wherein the method of preparation comprises: preparing a precursor of a nickel salt and a titanium-based metal organic framework by adopting the composition, and roasting and reducing the precursor to obtain the nickel-titanium composite catalyst; the catalyst carrier is prepared by a metal organic framework method.
Preferably, the preparation method specifically comprises the following steps:
(1) Organic titanate, benzoic acid type compound, methanol and N, N-dimethylformamide are synthesized 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), and filtering and drying to obtain a catalyst precursor with uniform dispersibility;
(3) And (3) roasting the catalyst precursor obtained in the step (2) in air, and carrying out reduction roasting to obtain the nickel-titanium composite catalyst.
5. The method according to claim 4, wherein in step (1), the organic titanate is tetrabutyl titanate, isopropyl titanate, or n-propyl titanate, and the organic titanate is isopropyl titanate;
preferably, in step (1), the selected benzoic acid type compound is a terephthalic acid type compound, an isophthalic acid type compound, and illustratively, terephthalic acid.
Preferably, in step (1), the synthesis time is 12 to 24 hours, preferably 15 to 20 hours.
Preferably, in step (1), the synthesis temperature is from 120 to 180 ℃, preferably from 150 to 160 ℃.
6. The method according to claim 4 or 5, wherein the nickel salt in the step (2) is selected from nickel nitrate (Ni (NO) 3 ) 2 ·6H 2 O), nickel chloride (NiCl) 2 ·6H 2 O), nickel acetate (nickel acetate), preferably nickel nitrate.
Preferably, in the step (2), the amounts of the nickel salt, the organic titanate, the benzoic acid type compound and the organic titanate are calculated according to the stoichiometric number required in the nickel-titanium composite catalyst.
Preferably, in the step (2), the filtration and the drying can be performed by adopting the technical means known in the technical field.
Preferably, the drying temperature is 60-100 ℃, preferably 60-80 ℃; preferably, the drying time is 1 to 24 hours, preferably 4 to 12 hours.
Preferably, the uniform mixing in step (2) can be obtained by means of ultrasound and/or stirring. Preferably, the sonication time is between 5 and 30 minutes, preferably between 5 and 10 minutes. Preferably, the stirring time is from 2 to 24 hours, preferably from 4 to 6 hours.
Preferably, in the step (2), the uniformly mixing includes dispersing the titanium-based metal organic framework and the nickel salt in water to obtain a nickel salt aqueous solution and a titanium-based metal organic framework aqueous solution, adding the nickel salt aqueous solution into the titanium-based metal organic framework aqueous solution, performing ultrasonic treatment and stirring, and mixing to obtain the catalyst precursor. In the invention, the ultrasonic and stirring means is helpful to anchor Ni ions in the pore canal of the titanium-based metal organic framework, which is beneficial to promoting the uniform dispersion of nickel particles and controlling the size of the nickel particles.
7. The method according to any one of claims 4 to 6, wherein in the step (3), the air calcination means calcination by introducing air.
Preferably, the air firing temperature is 250-600 ℃, preferably 400-500 ℃.
Preferably, the air calcination time is 2 to 10 hours, preferably 4 to 8 hours.
Preferably, the air flow rate during air calcination is 10-200mL/min, preferably 50-100mL/min.
Preferably, the heating rate of the air calcination is 1-10 deg.C/min, preferably 2-5 deg.C/min.
Preferably, in the step (3), the reductive roasting refers to roasting by introducing a reducing gas.
Preferably, the temperature of the reduction roasting is 300-600 ℃, preferably 350-450 ℃.
Preferably, the air calcination time is 2 to 10 hours, preferably 3 to 6 hours.
Preferably, the flow rate of the reducing gas is 10 to 100mL/min, preferably 20 to 50mL/min.
Preferably, the heating rate of the reduction roasting is 1-10 ℃/min, preferably 2-5 ℃/min.
8. The method for preparing the nickel-titanium composite catalyst according to any one of claims 4 to 7, wherein the method for preparing the nickel-titanium composite catalyst comprises the following steps:
(1) Uniformly mixing organic titanate, a benzoic acid type compound, methanol and 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 respectively to obtain a nickel salt aqueous solution and a titanium-based metal organic framework aqueous solution;
(3) Uniformly mixing a nickel salt aqueous solution and a titanium-based metal organic frame aqueous solution, filtering and drying to obtain a catalyst precursor;
(4) And (4) roasting the catalyst precursor obtained in the step (3) in an air atmosphere and a hydrogen atmosphere in sequence to obtain the nickel-titanium composite catalyst.
9. The use of the nickel titanium composite catalyst of any one of claims 1 to 3 in catalyzing CO 2 Application in methanation reaction. Preferably, the catalysis is photo-thermal catalysis. More preferably, the photothermolysis is to absorb light energy of at least one of visible light, infrared light and ultraviolet light through the nickel titanium catalyst to serve as a driving energy source for the reaction, and exemplarily, an infrared light source is selected as a driving light source to convert the absorbed light energy into heat energy, so as to catalyze CO 2 And (4) methanation. Preferably, the intensity of incident light used for the photothermal catalysis may be 100-2000mW/cm 2 。
10. Photo-thermal catalysis CO 2 A process for methanation, characterized in that the process comprises: the nickel titanium catalyst of any of claims 1-3 that absorbs light energy from at least one of visible light, infrared light and ultraviolet light, preferably using an infrared light source as the driving light source, and converting the absorbed light energy into heat energy to catalyze CO 2 And (4) methanation.
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