CN113262802B - IrCu/TiO 2 Nanosheet catalyst and preparation method and application thereof - Google Patents
IrCu/TiO 2 Nanosheet catalyst and preparation method and application thereof Download PDFInfo
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- 238000001704 evaporation Methods 0.000 abstract 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses IrCu/TiO 2 A nanosheet catalyst, a preparation method and application thereof, belonging to CO 2 The technical field of photocatalytic reduction. The method comprises the steps of dissolving iridium chloride and copper nitrate into ethylene glycol, and preparing IrCu alloy by a microwave-assisted method; dissolving the IrCu alloy in ethanol, and dripping TiO into the solution in a dipping way 2 Evaporating the nanosheet ethanol solution in a water bath to dryness, drying and grinding to obtain IrCu/TiO 2 A nanosheet catalyst. The catalyst is in CO 2 Shows extremely excellent activity and CH in the photocatalytic reduction reaction 4 And (4) selectivity.
Description
Technical Field
The invention belongs to CO 2 The technical field of photocatalytic reduction, in particular to IrCu/TiO 2 A nanosheet catalyst, a preparation method and application thereof.
Background
With the industrialization and the combustion of fossil fuels, the concentration of carbon dioxide in the atmosphere gets higher and higher, reaching 417ppm in 5 months in 2019, which leads to the urgent desire for renewable clean energy and carbon emission control. It is well known that carbon dioxide is a common greenhouse gas, and its concentration in the atmosphere is closely related to long-term climate change such as glacier ablation, sea level rise, ocean acidification, and south-pole continental shelf collapse. Therefore, to expand the renewable energy solar energyUtilization and reduction of greenhouse gas CO 2 Emission targeting, development of efficient CO for conversion of solar energy to chemical energy 2 The photocatalyst has very important significance.
With the traditional nano TiO 2 In contrast, two-dimensional anatase type TiO 2 The nano-sheet (NS) has the advantages of low cost, large specific surface area, many oxygen vacancies, rapid transfer of a photocatalytic carrier and the like, and draws wide attention in the field of photocatalysis. However, there are some limitations due to their large number of applications, such as rapid recombination of photogenerated electrons and holes, less visible light absorption, low quantum efficiency, etc. Therefore, highly effective TiO 2 Much effort has been devoted to the study of NS-based photocatalysts. To raise TiO 2 The photocatalytic performance of NS has taken various strategies, including non-metallic N, S element hybridization, organic modification, and metal doping. Generally, tiO is doped with a metal such as Cu, ag, au, or the like 2 NS can promote the migration of photon-generated carriers and raise photoelectron transferring efficiency under illumination owing to its surface plasma effect, so as to enhance CO transferring effect of the catalyst 2 Activity of photoreduction. However, pure metal doping is due to total yield and CH 4 The selectivity is lower and limited. The alloy provides different local atomic arrangements on the surface of the cocatalyst and provides paired reaction sites to guide CO 2 Converted into a target product and inhibited from side reactions. In addition, the electronic structure and the geometric configuration of the alloy can be modulated according to different metal ratios.
Most of the previous literature research focuses on alloys such as AuCu, pdCu, auPd, etc., but the total yield and CH 4 The selectivity is not too high.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide IrCu/TiO 2 A preparation method of a nanosheet catalyst. The invention also aims to provide IrCu/TiO 2 A nanosheet catalyst. The invention also provides an IrCu/TiO 2 Photocatalytic CO (carbon monoxide) by nanosheet catalyst 2 Application in reduction catalysis.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
IrCu/TiO 2 The preparation method of the nanosheet catalyst comprises the steps of preparing IrCu alloy nanoparticles by ethylene glycol reduction, dissolving IrCu alloy in ethanol to prepare IrCu alloy ethanol solution, and dripping the IrCu alloy ethanol solution into TiO in a dipping mode 2 Drying the nanosheet and ethanol mixed solution in a water bath to dryness, drying and grinding to obtain IrCu/TiO 2 A nanosheet catalyst.
The IrCu/TiO 2 The preparation method of the nanosheet catalyst comprises the following steps of 1.
The IrCu/TiO 2 The preparation method of the nanosheet catalyst comprises the step of drying for 5-7 hours at the temperature of 65-75 ℃.
The IrCu/TiO 2 The preparation method of the nanosheet catalyst for preparing the IrCu alloy nanoparticles by ethylene glycol reduction comprises the following steps of:
(1) Adding ethylene glycol into a reaction container, heating to 120-130 ℃ under the microwave-assisted condition, and keeping for 25-35 min; then adding NaOH and IrCl 3 And CuCl 2 Rapidly cooling after keeping the temperature for 25-35 min;
(2) Adding acetone into the reaction solution, centrifuging for 10-20 min at the rotating speed of 8000-12000 rpm, removing supernatant, dispersing the residual solid into ethanol, adding n-hexane, centrifuging for 10-20 min at the rotating speed of 8000-12000 rpm, removing supernatant, and completely dissolving the residual solid into the ethanol to obtain the IrCu alloy nanoparticles.
The IrCu/TiO 2 The volume ratio of the reaction liquid to acetone is 1.
IrCu/TiO prepared by the method 2 A nanosheet catalyst.
The catalyst is used for photocatalysis of CO 2 Use in reductive catalysis.
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) The catalyst is prepared by the following steps that Ir is added when the atomic ratio of Ir to Cu is 3 75 Cu 25 Material capable of exhibiting excellent CO 2 Photocatalytic reduction Activity and CH 4 And (4) selectivity.
(2) Precursor salts of Ir and Cu are reduced by ethylene glycol to form an IrCu alloy structure; irCu supported on TiO 2 The nano-sheets are uniformly dispersed and have uniform particle size. The reason for improving the activity of the catalyst after the IrCu alloy is loaded is as follows: the light absorption of the catalyst is improved; the separation efficiency of the photo-generated electrons and the holes is improved. IrCu alloy supported post catalyst CH 4 Reasons for the selectivity improvement: providing paired reaction sites to direct CO 2 Converting into a target product; inhibiting the occurrence of side reactions.
(3) The series IrCu/TiO in the invention 2 The total yield of the (NS) photocatalyst is 2-5 times of that of (20-40 umol/g/h) in the prior art, the total reaction rate in 8 hours reaches 101.3umol/g/h, and the total reaction rate of CH 4 The selectivity was 98.7%.
(4) The catalyst can effectively reduce CO under illumination 2 Is CH 4 The carrier of the catalyst prepared by dipping after the reduction of the ethylene glycol is TiO 2 The nano-sheet is a carrier with better photocatalytic activity. TiO before and after dipping and loading after IrCu alloy is prepared by reducing ethylene glycol 2 The nanosheet has remarkable enhancement on photoproduction electron-hole separation, and shows higher photocatalysis yield.
Drawings
FIG. 1 is a synthesis route diagram of an IrCu alloy as an active component in a catalyst;
FIG. 2 shows the photocatalytic CO of the catalyst used 2 Reduced activity and CH 4 A graph of selectivity results;
FIG. 3 is an XRD pattern of the catalyst;
fig. 4 is a graph of photocurrent and impedance characterization results for the catalyst.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
Example 1
IrCu/TiO 2 Preparation of nanosheet catalystThe preparation method comprises the following steps:
(1)TiO 2 preparation of nanosheet catalyst
Accurately weighing 20ml of tetrabutyl titanate, putting the tetrabutyl titanate into a polytetrafluoroethylene lining, starting stirring, and then dropwise adding 2.4ml of hydrofluoric acid solution with the mass fraction of 5% into the polytetrafluoroethylene lining in the stirring process. Stirring was continued for 1h. Packaging with a high-pressure reaction kettle, placing into a constant-temperature electrothermal blowing dry oven, reacting at 200 deg.C for 24 hr, and collecting the generated blue-white precipitate TiO 2 And (3) alternately washing NS with ethanol and distilled water until the precipitate is pure white, drying the NS at 110 ℃ for 24 hours, and roasting the NS in a muffle furnace at 400 ℃ for 2 hours to obtain a sample which is marked as TiO 2 NS。
(2) The preparation of IrCu alloy nanoparticles, FIG. 1 is a schematic diagram of a reaction device for preparing IrCu alloy particles:
placing 15ml of ethylene glycol into a three-neck flask with a magnetic stirring rotor, adjusting the temperature of a microwave reactor to 125 ℃ and keeping the temperature for 30 minutes; then 1mL NaOH solution (0.25M concentration) and IrCl at different Ir to Cu mass ratios 3 Ethylene glycol solution (concentration of 0.02M), cuCl 2 Adding ethylene glycol solution (with the concentration of 0.02M) into a three-neck flask; adding NaOH solution for maintaining alkaline environment to obtain smaller alloy particles, then maintaining the mixture at 125 ℃ for 30 minutes, and immediately soaking the mixture in ice bath for 10 minutes;
then, about 20ml of the liquid was put into 4 centrifuge tubes, acetone was added thereto for centrifugation in an important proportion, an excess amount of acetone was maintained so that the nanoparticles could settle, 5ml of the prepared liquid and 30ml of acetone were added to each centrifuge tube to centrifuge and wash the mixture at 10000rpm for 15 minutes, then the supernatant liquid was poured off, the remaining solid was redispersed in 5ml of ethanol, 25ml of n-hexane was added thereto to centrifuge and wash the mixture at 10000rpm for 15 minutes, and then the supernatant liquid was removed and completely dissolved in ethanol. The sample obtained is denoted Ir x Cu 100-x /(EG). The samples prepared had Cu in common 100 、Ir 100 、Ir 88 Cu 12 、Ir 75 Cu 25 、Ir 68 Cu 32 、 Ir 50 Cu 50 。
(3)IrCu/TiO 2 (NS) production
The prepared IrCu alloy nano particle colloid with 0.1mmol is dispersed in ethanol to obtain IrCu alloy ethanol solution, and then the IrCu alloy ethanol solution is dripped into 300mg TiO 2 NS in a mixture with ethanol. The mixture was dried at 70 ℃ for 6 h and the sample obtained was designated IrCu/TiO 2 (NS)。
FIG. 3 is an XRD pattern of materials of different IrCu ratios for characterizing the formation of alloy particles; FIG. 4 is a resistance characterization of materials with different IrCu ratios, illustrating Ir 75 Cu 25 The material has the best photocatalysis effect because the transfer resistance of photoproduction electrons is smaller, which is beneficial to CO 2 Reduction of (2).
Example 2
IrCu/TiO 2 Photocatalytic CO of (NS) 2 Determination of reductive catalysis Performance
IrCu/TiO to be prepared 2 (NS) catalyst for photocatalytic CO 2 The method comprises the following steps of (1) carrying out reduction catalytic reaction, and specifically evaluating the activity:
(1) Mixing a 20mg catalyst sample and 5ml deionized water, placing the mixture in a polytetrafluoroethylene reactor, adding a stirrer, and carrying out ultrasonic treatment for 20min to ensure that the sample is uniformly dispersed;
(2) Sealing the reactor by using a flange plate, opening a stirrer in the base and carrying out digital display temperature control;
(3) Pure CO is separated by a pressure dividing valve 2 Introducing into a reactor, totally 0.1Mpa, and aerating and deflating for 5 times to ensure that the reactor is pure CO 2 An atmosphere;
(4) Meanwhile, opening nitrogen and air cylinders, opening a hydrogen generator, and opening corresponding software on a chromatographic instrument and a computer; regulating N 2 The partial pressure is 0.4Mpa, and the air partial pressure is adjusted to be 0.2Mpa; carrying out temperature control, ignition and baseline balance processes;
(5) After the inflation and deflation are finished, timing a lamp (300W Xe lamp), and taking a point every 2 h; gas in the reactor is subjected to online detection by using gas chromatography; carrying out qualitative and quantitative analysis on the gas in the reactor through standard gas; CO 2 2 Reduced photocatalytic activitySex and CH 4 The selectivity is calculated by the following formula:
wherein A is CO Is the area of CO peak, A CH4 Is CH 4 Peak area, A 0 Is the CO standard gas peak area, A 1 Is CH 4 Area of standard gas peak, c s Is the concentration of standard CO gas, P is the pressure in the reactor, vr is the reactor volume, T is the reactor temperature, m cat Taking R as a molar gas constant and taking 8.314J mol as the mass of the catalyst -1 K -1 。
FIG. 2 shows the photocatalytic CO of the catalyst used 2 Reduced activity and CH 4 Selectivity results plot illustrating materials of different IrCu ratios for photocatalytic CO 2 Reduced activity and CH 4 And (4) selectivity.
Claims (5)
1. IrCu/TiO 2 The preparation method of the nanosheet catalyst is characterized in that IrCu alloy nanoparticles are prepared by adopting ethylene glycol reduction, the IrCu alloy is dissolved in ethanol to prepare an IrCu alloy ethanol solution, and the IrCu alloy ethanol solution is dripped into TiO in a dipping mode 2 Drying the nanosheet and ethanol solution in a water bath to dryness, drying and grinding to obtain IrCu/TiO 2 A nanosheet catalyst; wherein, in the IrCu alloy, the mass ratio of Ir and Cu metal is 1.
2. IrCu/TiO according to claim 1 2 The preparation method of the nano-sheet catalyst is characterized in that the nano-sheet catalyst is prepared at the temperature of 65-75 DEG CDrying for 5-7 h.
3. IrCu/TiO according to claim 1 2 The preparation method of the nanosheet catalyst is characterized in that the IrCu alloy nanoparticles are prepared by reducing ethylene glycol, and the preparation method comprises the following steps:
(1) Adding ethylene glycol into a reaction container, heating to 120-130 ℃ under the microwave-assisted condition, and keeping for 25-35 min; then NaOH and IrCl 3 And CuCl 2 Rapidly cooling after keeping the temperature for 25-35 min;
(2) Adding acetone into the reaction liquid, centrifuging at the rotating speed of 8000-12000 rpm for 10-20 min, removing supernatant, dispersing the residual solid in ethanol, adding n-hexane, centrifuging at the rotating speed of 8000-12000 rpm for 10-20 min, removing supernatant, and completely dissolving the residual solid in the ethanol to obtain IrCu alloy nanoparticles;
wherein the volume ratio of the reaction liquid to acetone is 1.
4. IrCu/TiO obtainable by a process according to any one of claims 1 to 3 2 A nanosheet catalyst.
5. Use of the catalyst of claim 4 in the photocatalysis of CO 2 Application in reduction catalysis.
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