CN114471613A - Pt/Co-Al for high-efficiency photo-thermal catalysis carbon dioxide methane dry reforming2O3Catalyst and preparation method thereof - Google Patents

Pt/Co-Al for high-efficiency photo-thermal catalysis carbon dioxide methane dry reforming2O3Catalyst and preparation method thereof Download PDF

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CN114471613A
CN114471613A CN202210124550.9A CN202210124550A CN114471613A CN 114471613 A CN114471613 A CN 114471613A CN 202210124550 A CN202210124550 A CN 202210124550A CN 114471613 A CN114471613 A CN 114471613A
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李远志
谢正海
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Wuhan University of Technology WUT
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Abstract

The invention discloses a high-efficiency carbon dioxide methane dry reforming photo-thermal catalyst, which is cobalt-doped alumina (Co-Al)2O3) Pt/Co-Al formed by taking platinum nano particles as main active components as carrier2O3A nanocomposite catalyst; by Co-Al2O3Active lattice oxygen participates in the dry reforming reaction of carbon dioxide and methane, and carbon deposition side reaction is effectively inhibited; by Co-Al simultaneously2O3Strong absorption in the full solar spectrum improves the photo-thermal conversion efficiency; by using Pt and Co-Al2O3The synergistic effect between the two obviously promotes the improvement of the photo-thermal catalytic performance. The catalyst has the advantages of high photo-thermal catalytic activity, high conversion efficiency from solar energy to chemical energy, good photo-thermal catalytic stability and the like; the related preparation method is simple, easy to control and low in cost;the method is applied to dry reforming of carbon dioxide and methane, and can provide an efficient solution for carbon dioxide emission reduction and solar energy storage.

Description

Pt/Co-Al for high-efficiency photo-thermal catalysis carbon dioxide methane dry reforming2O3Catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of functional materials and synthesis thereof, and particularly relates to Pt/Co-Al for high-efficiency photo-thermal catalysis carbon dioxide methane dry reforming2O3A nano composite photocatalyst and a preparation method thereof.
Background
Since fossil fuels are burned in various industrial processes, a large amount of greenhouse gases are emitted, thereby causing serious environmental problems (e.g., global warming, extreme weather) and energy shortage. Many countries have enacted schedules for carbon dioxide peak emissions and carbon neutralization. In order to achieve the goal of action planning, development of effective carbon dioxide abatement technology is urgently required. Over the past decades, one strategy for photocatalytic carbon dioxide reduction has attracted considerable attention as carbon dioxide energy has been converted to solar fuels and solar energy storage. For the strategy of photocatalytic carbon dioxide, two major challenges need to be addressed, namely low fuel generation rate and light to fuel conversion efficiency. To address these challenges, there is a continuing effort to produce a large number of highly efficient photocatalysts that can be excited by ultraviolet, visible, and even infrared light.
In recent years, photo-thermal catalytic carbon dioxide reduction of H2O and methane attract the interest of researchers, the scheme can perfectly combine the high catalytic efficiency of the thermocatalytic carbon dioxide reduction and the photocatalytic carbon dioxide reduction, and can effectively utilize solar energy including ultraviolet rays, visible light and infrared light; the level of fuel yield is significantly improved compared to the photocatalytic carbon dioxide reduction strategy. Patent CN 112973704A discloses a Cu/ZnO catalyst with light enhancement effect, which simulates sunlight (300 mW cm)-2) The CO yield for photo-thermal catalytic carbon dioxide reduction under irradiation was 358.87 μmol g-1h-1(5.98×10-3 mmol min-1g-1) (ii) a Patent CN 113117675A discloses that Rh NPs and Er NPs are loaded on Al2O3The preparation method of the composite metal photo-thermal catalyst on the surface of the carrier is 2.0mW cm-2Introducing CH with the mass ratio of 1:1 under the irradiation of all-optical-segment light of a xenon lamp under normal pressure4/CO2Gas, highest H is obtained2And CO yields of 17.1 and 51.2mmol g, respectively-1h-1(0.285 and 0.853mmol min-1g-1) (ii) a Patent CN 113441160A discloses a nickel hydroxide/titanium carbide photo-thermal catalytic material, a preparation method and application thereof, Ni (OH) prepared by the invention2/Ti3C2The material is used for photo-thermal carbon dioxide hydrogenation to improve Ti3C2Tests show that the conversion rate of the photo-thermal carbon dioxide based on the catalytic material reaches 0.9mmol g-1h-1(0.015mmol min-1g-1). Among these strategies, photo-thermal catalytic methane dry reforming (CRM, CO)2+CH4＝2H2+2CO，ΔH298＝247kJ mol-1) The method has wide application prospect because two greenhouse gases (carbon dioxide and methane) are converted into solar energy fuel.
Further improvement of fuel yield (r) for photo-thermal catalytic CRM strategiesfuel) And conversion efficiency (η), improved catalytic durability and anti-coking, are significant challenges to solve. In principle, the first key issue can be solved by increasing the thermocatalytic activity. Solving the second critical problem is particularly difficult because of the carbon deposit side reaction CH4Complete dissociation (CH)4＝2H2+C，ΔH298＝75kJ mol-1) And CO disproportionation (2CO ═ CO)2+C，ΔH298＝-171kJ mol-1) Leading to catalyst deactivation and dangerous reaction plugging, which is unavoidable at CRM thermodynamics.
Disclosure of Invention
The main object of the present invention is to provide a cobalt-doped alumina (Co-Al) for solving the problems and deficiencies of the prior art2O3) High-efficiency photo-thermal catalytic carbon dioxide and methane dry reforming nano composite catalyst (Pt/Co-Al) with platinum nano particles as main active component as carrier2O3) By Co-Al2O3The active lattice oxygen participates in the dry reforming reaction of carbon dioxide and methane, and the carbon deposition side reaction is inhibited; by Co-Al simultaneously2O3Strong absorption in the full solar spectrum and Pt and Co-Al2O3The synergistic effect between the two components, thereby obviously improving the photo-thermal catalytic activity (r)H2＝75.60mmol min-1g-1，rCO＝89.41mmol min- 1g-1) The conversion efficiency from solar energy to chemical energy (27.2%) and the photo-thermal catalytic stability; the related preparation process is simple, the preparation process is easy to operate and control, and the cost is low; is suitable for popularization and application.
In order to achieve the purpose, the invention adopts the technical scheme that:
Pt/Co-Al for high-efficiency photo-thermal catalysis carbon dioxide methane dry reforming2O3The nano composite catalyst comprises cobalt-doped alumina and platinum nanoparticles loaded on the surface of the cobalt-doped aluminaRice grain, alumina doped with cobalt (Co-Al)2O3) As a carrier, platinum nano-particles are distributed on the surface of the cobalt-doped alumina as a main active component.
In the scheme, the loading amount of the platinum nanoparticles relative to cobalt-doped alumina is 0.25-2 wt%.
In the scheme, the doping amount of the cobalt nanoparticles is 2-5 wt%.
In the scheme, the particle size of the platinum nanoparticles is 0.75-3.25 nm.
Co-Al as described above2O3The preparation method of the nano composite catalyst comprises the following steps:
1) taking aluminum salt, cobalt salt and urea as main raw materials to carry out hydrothermal reaction and calcining to obtain Co-Al2O3A carrier;
2) mixing Co-Al2O3Dispersing the carrier and the platinum salt in water, and then heating, grinding and drying;
3) carrying out heat treatment on the solid product obtained in the step 2) in a reducing atmosphere to obtain the Pt/Co-Al2O3A nanocomposite catalyst.
In the scheme, the aluminum salt can be selected from aluminum nitrate, aluminum chloride, aluminum sulfate and the like; the cobalt salt can be selected from cobalt nitrate or cobalt chloride; the platinum salt is soluble platinum salt, and specifically platinum nitrate and the like can be selected.
In the scheme, the mass ratio of the aluminum salt to the cobalt salt to the urea is 7.5 (0.1-0.5) to 1.8-2.2.
In the scheme, the hydrothermal reaction product obtained in the step 1) is washed, dried, ground and calcined to obtain the Co-Al2O3And (3) a carrier.
In the scheme, the drying temperature is 100-120 ℃, and the drying time is 10-12 h.
In the scheme, the hydrothermal reaction temperature is 120-180 ℃, and the time is 6-24 hours.
In the scheme, the calcining temperature is 400-500 ℃, and the time is 8-12 h.
In the scheme, the platinum element introduced by the platinum salt in the step 2) accounts for Co-Al2O30.25-2.0 wt% of the carrier
In the scheme, Co-Al is adopted in the step 2)2O3The dosage ratio of the carrier to the water is (0.2-0.5) g, (5-10) mL.
In the scheme, the heating and grinding temperature is 150-180 ℃.
In the above scheme, the heat treatment process comprises: carrying out heat preservation treatment for 0.5-2 h under the conditions of reducing gas/inert gas atmosphere and temperature of 700-800 ℃; wherein the volume percentage of the reducing gas is 5-40%.
In the above scheme, the reducing gas used in the reducing atmosphere (reducing gas/inert gas) may be hydrogen gas or the like; the inert gas can be argon gas and the like.
Co-Al prepared according to the above scheme2O3The nano composite material can realize the Pt/Co-Al by only utilizing focused ultraviolet-visible-infrared illumination2O3The efficient photo-thermal catalysis CRM. With Pt/Al2O3In contrast, rCO、rH2And eta can be increased by 5.4, 6.0 and 6.2 times respectively; at the same time, the catalyst can show good catalytic durability (coke deposition side reaction is obviously hindered, Pt/Al2O3Rapid deactivation due to its higher coke deposition rate, specific to Pt/Co-Al2O315.3 times higher), and Pt and Co-Al2O3The synergistic effect between the two can obviously promote the improvement of the photo-thermal catalytic performance. The obtained Pt/Co-Al2O3The above photothermocatalytic CRM follows a photo-driven thermocatalytic mechanism, which is greatly facilitated by a new photo-activation, completely different from traditional semiconductor photocatalysts. According to various evidences, the origin of the synergistic effect and light activation is revealed.
The principle of the invention is as follows:
the photocatalytic methane and carbon dioxide reforming reaction is a strong endothermic process, the reaction can be carried out only when high temperature is reached under the illumination condition, and the whole process is accompanied with the generation of carbon deposition side reaction; the high temperature reaction causes three problems: in the process CH occurs4The cracking reaction and the CO disproportionation reaction form carbon deposition, so that the catalyst is inactivated; photo-thermal conversion effectThe low rate causes the surface temperature of the catalyst to be too low, resulting in low or no activity of the catalyst; the high temperature causes the sintering of the active component and the carrier of the catalyst, so that the active component particles of the catalyst are enlarged, the surface area is greatly reduced, and the catalyst is inactivated; therefore, the improvement of the light absorption intensity and the carbon deposit resistance of the catalyst are key problems in the field.
The Pt/Co-Al of the invention2O3In the nano composite catalyst, Al is added2O3Cobalt doping is carried out, so that the cobalt nanoparticles modify the alumina carrier to change the surface electronic state of the alumina carrier and generate active lattice oxygen, the provided active lattice oxygen participates in the reaction to effectively inhibit the elementary reaction related to carbon deposition, the strong absorption effect of cobalt on light is utilized to improve the photo-thermal conversion efficiency of the obtained catalyst, and the reaction can be carried out at a higher temperature and cannot be inactivated due to carbon deposition; at the same time, Pt and Co-Al2O3There is a synergistic effect with Pt/Al2O3In contrast, Pt/Co-Al2O3The formation of the interface significantly promotes CH4The dissociation of carbon species can further promote the improvement of photo-thermal catalytic performance; the catalyst is applied to the dry reforming reaction of the photocatalytic carbon dioxide and methane, and can provide an efficient solution for carbon dioxide emission reduction and solar energy storage.
Compared with the prior art, the invention has the beneficial effects that:
1) the low-content metal platinum and cobalt have wide sources, so that the production cost is greatly reduced; the preparation method of the related catalyst has the advantages of simple process, easy operation of the preparation process, mild reaction conditions and obvious energy consumption effect;
2) the obtained catalyst has high light absorption strength and anti-carbon deposition capability;
3) the prepared catalyst has higher H under the irradiation of focused light2Yield (r)H2＝75.60mmol min-1g-1) CO yield (r)CO＝89.41mmol min-1g-1) Solar to chemical energy conversion efficiency (27.2%) and stability performance.
Drawings
FIG. 1 is a TEM image and a Pt nanoparticle size distribution diagram of the product obtained in example 1;
FIG. 2 shows CH obtained under different spectral irradiation conditions for the product obtained in example 14、CO2、H2And the photocatalytic reaction rate of CO and the average of 40 minutes before the production rate;
FIG. 3 shows CH obtained under the condition of full gloss spectrum of the product obtained in example 14、CO2、H2And the photocatalytic reaction rate of CO and the average of 40 minutes before the production rate;
FIG. 4 shows CH as the product obtained in example 14And CO2Reaction rate of (3), H2And the rate of CO production over time;
FIG. 5 is an average value of the solar to chemical energy conversion efficiencies obtained by the catalysts obtained in example 1, comparative example 2 and comparative example 3, for 40 minutes before;
FIG. 6 shows CH obtained under the condition of full gloss spectrum of the product obtained in example 24、CO2、H2And the photocatalytic reaction rate of CO and the average 40 minutes before the production rate;
FIG. 7 shows CH obtained under the condition of full gloss spectrum of the product obtained in example 34、CO2、H2And the photocatalytic reaction rate of CO and the average of 40 minutes before the production rate;
FIG. 8 shows CH obtained under the condition of full gloss spectrum of the product obtained in example 44、CO2、H2And the photocatalytic reaction rate of CO and the average of 40 minutes before the production rate;
FIG. 9 shows CH obtained under the condition of full gloss spectrum of the product obtained in example 54、CO2、H2And the photocatalytic reaction rate of CO and the average of 40 minutes before the production rate;
FIG. 10 shows CH obtained under the condition of full gloss spectrum of the product obtained in comparative example 14、CO2、H2And the photocatalytic reaction rate of CO and the average of 40 minutes before the production rate;
FIG. 11 shows CH obtained under the condition of full gloss spectrum of the product obtained in comparative example 24、CO2、H2Photocatalytic reaction with COAverage of the response rate and production rate over the first 40 minutes;
FIG. 12 shows CH obtained under the condition of full gloss spectrum of the product obtained in comparative example 34、CO2、H2And the photocatalytic reaction rate of CO and the average of 40 minutes before the production rate;
FIG. 13 shows CH as a product obtained in comparative example 34And CO2Reaction rate of (3), H2And the rate of CO production over time.
Detailed Description
In order to better understand the present invention, the following embodiments are further illustrated, but the present invention is not limited to the following embodiments.
Example 1
Pt/Co-Al2O3The preparation method of the nano composite catalyst comprises the following steps:
1) 7.5000g of aluminum nitrate nonahydrate (Al (NO)3)3·9H2O), 0.3055g of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O) and 2.1100g Urea (CO (NH)2)2) Dissolving in 50ml deionized water for 30min by magnetic stirring;
2) pouring the obtained solution into a 70ml polytetrafluoroethylene hydrothermal kettle, carrying out hydrothermal reaction at 150 ℃ for 24h, naturally cooling to room temperature, carrying out suction filtration and washing, drying the obtained precipitate at 120 ℃ for 12h, calcining in a muffle furnace at 500 ℃ for 8h, and cooling to room temperature to obtain 3% Co-Al2O3A carrier;
3) 0.0055g of platinum nitrate solution (Pt (NO) was collected3)3Pt 18.02 wt%) and 0.2000g of 3% Co-Al2O3(mass% Pt/carrier 0.5%) were mixed together in 5ml of deionized water, and ground and dried at 180 ℃;
4) taking 0.0500g of the product obtained, placing the product in a fluid bed and introducing 5 vol% H2Heating the mixed gas to 800 ℃ at the speed of 10 ℃/min, preserving heat, reducing for 1h, and cooling to room temperature to obtain the Pt/Co-Al2O3Nano composite catalyst (0.5% Pt/3% Co-Al)2O3)。
The products obtained in this example were characterized by ICP and TEM: ICP analysis shows that the obtained Pt/Co-Al2O3The content of Pt in the alloy is 0.297 wt%, and the content of Co is 3.860 wt%; TEM analysis shows that Pt nanoparticles are uniformly dispersed in Co-Al2O3The carrier has a surface and the particle size is concentrated in the range of 0.75 to 3.25nm (see FIG. 1).
The product obtained in the example is subjected to photocatalytic activity and stability tests, and the method specifically comprises the following steps:
full spectrum conditional testing
1) 0.010g of the obtained Pt/Co-Al is weighed2O3The nano composite catalyst is evenly placed in a vent hole with the diameter of 0.80cm in a self-made stainless steel reaction cavity, and methane and carbon dioxide mixed gas (28.5/28.7/42.8 vol% CH) is introduced4/CO2/Ar)；
2) The gas flow rate is adjusted by a mass flow meter (MT-52) to be kept stable at 89.8mL min-1After stabilization, the reaction is carried out for 50h under the irradiation of focused light of a 500WXe lamp;
testing of different spectral conditions
1) Repeating the steps 1) and 2), wherein the difference is that: after the first step is completed, filters with lambda of more than 420nm, lambda of more than 560nm and lambda of more than 690nm are respectively replaced, and then the Xe lamp light source is turned on to react under the condition;
2) the tail gas was passed through a gas chromatograph (GC-9560) to perform gas composition analysis every 10 min.
H obtained under different spectral irradiation conditions under the action of the catalyst obtained in the example2And the photocatalytic yield of CO averaged over the first 40 minutes as shown in figure 2; h obtained under the condition of full light spectrum2And the average value of the photocatalytic yields of CO before 40 minutes (as shown in FIG. 3) was 75.60mmol min-1g-1And 89.41mmol min-1g-1；H2And the yield of CO as a function of time is shown in fig. 4; the average value obtained 40 minutes before the solar to chemical conversion efficiency (see fig. 5) was 27.2%. The above results show that: under the condition of high-temperature illumination, the catalyst obtained in the embodiment can show excellent photocatalytic performance under different spectral illumination conditions, and can catalyze within 50hThe activity is high and is not obviously reduced, side reactions such as carbon deposition and the like can be effectively inhibited, and the conversion efficiency from solar energy to chemical energy is high.
Example 2
Pt/Co-Al2O3The preparation method of the nano composite catalyst comprises the following steps:
1) 7.5000g of aluminum nitrate nonahydrate (Al (NO)3)3·9H2O), 0.2328g of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O) and 2.1100g Urea (CO (NH)2)2) Dissolving in 50ml deionized water for 30min by magnetic stirring;
2) pouring the obtained solution into a 70ml polytetrafluoroethylene hydrothermal kettle, carrying out hydrothermal reaction at 150 ℃ for 24h, naturally cooling to room temperature, carrying out suction filtration and washing, drying the obtained precipitate at 120 ℃ for 12h, calcining in a muffle furnace at 500 ℃ for 8h, and cooling to room temperature to obtain a sample of 2% Co-Al2O3A carrier;
3) 0.0055g of platinum nitrate solution (Pt 18.02 wt%) and 0.2000g of 2% Co-Al2O3(mass% Pt/carrier 0.5%) were mixed together in 5ml of deionized water, and ground and dried at 180 ℃;
4) 0.0500g of the product obtained is taken in a fluidized bed and 5% H is passed2Heating the mixed gas to 700 ℃ at the speed of 10 ℃/min, preserving heat, reducing for 1h, and cooling to room temperature to obtain the Pt/Co-Al2O3Nano composite catalyst (0.5% Pt/2% Co-Al)2O3)。
The product obtained in this example was tested for activity over the full spectrum with reference to the procedure described in example 1. The results show that: under the action of the catalyst obtained in this example, H was obtained2And the average value of the photocatalytic yields of CO before 40 minutes (as shown in FIG. 6) was 41.45mmol min-1g-1And 45.21mmol min-1g-1Under the condition of reducing the content of Co doping, higher catalytic activity can be also shown.
Example 3
Pt/Co-Al2O3The preparation method of the nano composite catalyst comprisesThe method comprises the following steps:
1) 7.5000g of aluminum nitrate nonahydrate (Al (NO)3)3·9H2O), 0.3055g of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O) and 2.1100g Urea (CO (NH)2)2) Dissolving in 50ml deionized water for 30min by magnetic stirring;
2) pouring the obtained solution into a 70ml polytetrafluoroethylene hydrothermal kettle, carrying out hydrothermal reaction at 150 ℃ for 24h, naturally cooling to room temperature, carrying out suction filtration and washing, drying the obtained precipitate at 120 ℃ for 12h, calcining in a muffle furnace at 500 ℃ for 8h, and cooling to room temperature to obtain a sample of 3% Co-Al2O3A carrier;
3) 0.0110g of platinum nitrate solution (Pt (NO)3)3Pt 18.02 wt%) and 0.2000g of 3% Co-Al2O3(mass% Pt/carrier 1%) were mixed together in 5ml of deionized water, and ground and dried at 180 ℃;
4) 0.0500g of the product obtained is taken in a fluidized bed and 5 vol% H is introduced2Heating the mixed gas to 700 ℃ at the speed of 10 ℃/min, preserving heat, reducing for 1h, and cooling to room temperature to obtain the Pt/Co-Al2O3Nano composite catalyst (1% Pt/3% Co-Al)2O3)。
The product obtained in this example was tested for activity over the full spectrum with reference to the procedure described in example 1. The results show that: under the action of the catalyst obtained in this example, H was obtained2And the average values of the photocatalytic yields of CO before 40 minutes (see FIG. 7) were 59.41mmol min-1g-1And 69.81mmol min-1g-1The results show that increasing the platinum metal loading (1 wt% Pt) also gives higher catalytic activity, but not optimal loading, as measured by the photocatalytic activity test.
Example 4
Pt/Co-Al2O3The preparation method of the nano composite catalyst comprises the following steps:
1) 7.5000g of aluminum nitrate nonahydrate (Al (NO)3)3·9H2O), 0.3055g of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O) and 2.1100g Urea (CO (NH)2)2) Dissolving in 50ml deionized water for 30min by magnetic stirring;
2) pouring the obtained solution into a 70ml polytetrafluoroethylene hydrothermal kettle, carrying out hydrothermal reaction at 120 ℃ for 24h, naturally cooling to room temperature, carrying out suction filtration and washing, drying the obtained precipitate at 120 ℃ for 12h, calcining in a muffle furnace at 500 ℃ for 8h, and cooling to room temperature to obtain 3% Co-Al2O3A carrier;
3) 0.0055g of platinum nitrate solution Pt (NO) was again collected3)3Pt 18.02 wt%) and 0.2000g of 3% Co-Al2O3(mass% Pt/carrier 0.5%) were mixed together in 5ml of deionized water, and ground and dried at 180 ℃;
4) taking 0.0500g of the product obtained, placing the product in a fluid bed and introducing 5 vol% H2Heating the/Ar mixed gas to 700 ℃ at the speed of 10 ℃/min, preserving heat, reducing for 1h, and cooling to room temperature to obtain the Pt/Co-Al2O3Nano composite catalyst (0.5% Pt/3% Co-Al)2O3)。
The product obtained in this example was tested for activity over the full spectrum with reference to the procedure described in example 1. The results show that: under the action of the catalyst obtained in this example, H was obtained2And the average value of the photocatalytic yields of CO (see FIG. 8) at the first 40 minutes was 61.60mmol min-1g-1And 70.38mmol min-1g-1The results show that the carrier (Co-Al) is changed2O3) The hydrothermal temperature is 120 ℃, the reduction temperature is changed to 700 ℃, and the photocatalytic activity test also shows higher catalytic activity.
Example 5
Pt/Co-Al2O3The preparation method of the nano composite catalyst comprises the following steps:
1) 7.5000g of aluminum nitrate nonahydrate (Al (NO)3)3·9H2O), 0.3055g of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O) and 2.1100g Urea (CO (NH)2)2) Dissolving in 50ml deionized water for 30min by magnetic stirring;
2) the resulting solution was poured into 70ml of TeflonCarrying out hydrothermal reaction at 180 ℃ for 24h in a hydrothermal kettle, naturally cooling to room temperature, carrying out suction filtration and washing, drying the obtained precipitate at 120 ℃ for 12h, calcining at 500 ℃ in a muffle furnace for 8h, and cooling to room temperature to obtain a sample of 3% Co-Al2O3A carrier;
3) 0.0055g of platinum nitrate solution (Pt (NO) was collected3)3Pt 18.02 wt%) and 0.2000g of 3% Co-Al2O3(mass% Pt/carrier 0.5%) were mixed together in 5ml of deionized water, and ground and dried at 180 ℃;
4) 0.0500g of the product obtained is taken in a fluidized bed and 5 vol% H is introduced2Heating the mixed gas to 700 ℃ at the speed of 10 ℃/min, preserving heat, reducing for 1h, and cooling to room temperature to obtain the Pt/Co-Al2O3Nano composite catalyst (0.5% Pt/3% Co-Al)2O3)。
The product obtained in this example was tested for activity over the full spectrum with reference to the procedure described in example 1. The results show that: under the action of the catalyst obtained in this example, H was obtained2And the photocatalytic yield of CO was 64.06mmol min in the first 40 minutes average value (FIG. 9)-1g-1And 74.15mmol min-1g-1The results show that the carrier (Co-Al) is changed2O3) The hydrothermal temperature is 180 ℃, the reduction temperature is changed to 700 ℃, and the photocatalytic activity test also shows higher catalytic activity.
Comparative example 1
Al (aluminum)2O3The preparation method of the nano composite catalyst comprises the following steps:
1) 7.5000g of aluminum nitrate nonahydrate (Al (NO)3)3·9H2O) and 2.1100g Urea (CO (NH)2)2) Dissolving in 50ml deionized water for 30min by magnetic stirring;
2) pouring the solution into a 70ml polytetrafluoroethylene hydrothermal kettle, carrying out hydrothermal reaction at 150 ℃ for 24h, naturally cooling to room temperature, carrying out suction filtration and washing, drying the obtained precipitate at 120 ℃ for 12h, calcining in a muffle furnace at 500 ℃ for 8h, and cooling to room temperature;
3) 0.0500g of the product obtained is taken in a fluidized bed and 5% H is passed2Heating the mixed gas to 800 ℃ at the speed of 10 ℃/min, preserving heat, reducing for 1h, cooling to room temperature to obtain a sample Al2O3。
The product obtained in this comparative example was tested for activity over the full spectrum with reference to the procedure described in example 1. The results show that: the average value (as shown in figure 5) of the obtained solar energy to chemical energy conversion efficiency in the first 40 minutes is 0.14 percent; obtained H2And the photocatalytic yields of CO were averaged before 40 minutes (see FIG. 10) to be 2.16mmol min-1g-1And 0.66mmol min-1g-1(ii) a The results show that the photocatalytic activity of the catalyst is very low or inactive.
Comparative example 2
Co-Al2O3The preparation method of the nano composite catalyst comprises the following steps:
1) 7.5000g of aluminum nitrate nonahydrate (Al (NO)3)3·9H2O), 0.3055g of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O) and 2.1100g Urea (CO (NH)2)2) Dissolving in 50ml deionized water for 30min by magnetic stirring;
2) pouring the obtained solution into a 70ml polytetrafluoroethylene hydrothermal kettle, carrying out hydrothermal reaction at 150 ℃ for 24h, naturally cooling to room temperature, carrying out suction filtration and washing, drying the obtained precipitate at 120 ℃ for 12h, calcining in a muffle furnace at 500 ℃ for 8h, and cooling to room temperature;
3) 0.0500g of the product obtained is taken in a fluidized bed and 5 vol% H is introduced2The mixed gas of/Ar is then reduced for 1h at the temperature of 800 ℃ at the speed of 10 ℃/min, and the mixture is cooled to the room temperature to obtain a sample of 3 percent Co-Al2O3。
The product obtained in this comparative example was tested for activity over the full spectrum with reference to the procedure described in example 1. The results show that: the average value (as shown in figure 5) of the obtained solar energy to chemical energy conversion efficiency in the first 40 minutes is 0.61%; obtained H2And the photocatalytic yield of CO was averaged before 40 minutes (see FIG. 11) to be 2.40mmol min-1g-1And 6.08mmol min-1g-1(ii) a The results show that the catalyst support (Co-Al)2O3) Photocatalytic activityThe performance is very low, but the photocatalytic activity is improved to some extent compared with that obtained in comparative example 1, because the doping of Co causes the alumina to generate lattice oxygen and oxygen vacancies to participate in the methane carbon dioxide photocatalytic reaction.
Comparative example 3
Pt/Al2O3The preparation method of the nano composite catalyst comprises the following steps:
1) 7.5000g of aluminum nitrate nonahydrate (Al (NO)3)3·9H2O) and 2.1100g Urea (CO (NH)2)2) Dissolving in 50ml deionized water for 30min by magnetic stirring;
2) pouring the solution into a 70ml polytetrafluoroethylene hydrothermal kettle, carrying out hydrothermal reaction at 150 ℃ for 24h, naturally cooling to room temperature, carrying out suction filtration and washing, drying the obtained precipitate at 120 ℃ for 12h, calcining in a muffle furnace at 500 ℃ for 8h, and cooling to room temperature to obtain a sample Al2O3；
3) 0.0055g of platinum nitrate solution (Pt (NO) was collected3)3Pt 18.02 wt%) and 0.2000g Al2O3(mass percent Pt/carrier is 0.5%) are mixed in 5ml deionized water, and are grinded and dried at 180 ℃;
4) 0.0500g of the product obtained is taken in a fluidized bed and 5 vol% H is introduced2Heating the mixed gas to 800 ℃ at the speed of 10 ℃/min, preserving heat, reducing for 1h, cooling to room temperature to obtain a sample of 0.5% Pt/Al2O3。
The product obtained in this comparative example was tested for activity under full spectrum conditions, with reference to the procedure described in example 1. The results show that: the average value (as shown in figure 5) of the obtained solar energy to chemical energy conversion efficiency in the first 40 minutes is 3.8%; obtained H2And the photocatalytic yield of CO was averaged over the first 40 minutes (see FIG. 12) to be 10.49mmol min-1g-1And 14.31mmol min-1g-1(ii) a The results show that the photocatalytic activity of the catalyst is relatively low.
The product obtained in the comparative example is subjected to a stability test, and the specific experimental procedure is the same as that of the photocatalytic stability test in example 1. Obtained H2And CO yield over time (see fig. 13); the results show that the time is 5hThe internal catalytic activity is obviously reduced.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (10)

1. Pt/Co-Al for dry reforming of carbon dioxide and methane by efficient photo-thermal catalysis2O3A catalyst comprising cobalt-doped alumina and platinum nanoparticles supported on the surface thereof.
2. Pt/Co-Al according to claim 12O3The catalyst is characterized in that the loading amount of the platinum nanoparticles is 0.25-2 wt%.
3. Pt/Co-Al according to claim 12O3The catalyst is characterized in that the doping amount of the cobalt ions is 2-5 wt%.
4. Pt/Co-Al according to claim 12O3The catalyst is characterized in that the particle size of the platinum nanoparticles is 0.75-3.25 nm.
5. The Pt/Co-Al composition according to claim 1 to 42O3The preparation method of the catalyst is characterized by comprising the following steps:
1) taking aluminum salt, cobalt salt and urea as main raw materials to carry out hydrothermal reaction and calcining to obtain Co-Al2O3A carrier;
2) mixing Co-Al2O3Dispersing the carrier and the platinum salt in water, and then heating, grinding and drying;
3) carrying out heat treatment on the solid product obtained in the step 2) in a reducing atmosphere to obtain the Pt/Co-Al2O3A catalyst.
6. The production method according to claim 5, wherein the aluminum salt is aluminum nitrate, aluminum chloride, or aluminum sulfate; the cobalt salt is cobalt nitrate or cobalt chloride; the platinum salt is soluble platinum salt.
7. The preparation method according to claim 5, wherein the mass ratio of the aluminum salt, the cobalt salt and the urea is 7.5 (0.1-0.5) to (1.8-2.2); the platinum element introduced by the platinum salt in the step 2) accounts for Co-Al2O30.25 to 2.0 wt% of the carrier.
8. The preparation method according to claim 5, wherein the hydrothermal reaction temperature is 120-180 ℃ and the time is 6-24 h; the calcination temperature is 400-500 ℃, and the calcination time is 8-12 h.
9. The method according to claim 5, wherein the heat-grinding temperature is 150 to 180 ℃.
10. The method of claim 5, wherein the heat treatment process comprises: carrying out heat preservation treatment for 0.5-2 h under the conditions of reducing gas/inert gas atmosphere and temperature of 700-800 ℃; wherein the volume percentage of the reducing gas is 5-40%.
CN202210124550.9A 2022-02-10 2022-02-10 Pt/Co-Al for high-efficiency photo-thermal catalysis carbon dioxide methane dry reforming2O3Catalyst and preparation method thereof Pending CN114471613A (en)

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