CN115430450A - Preparation method and application of Rh nanoparticle modified III-group nitrogen oxide Si catalyst - Google Patents

Preparation method and application of Rh nanoparticle modified III-group nitrogen oxide Si catalyst Download PDF

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CN115430450A
CN115430450A CN202211045142.0A CN202211045142A CN115430450A CN 115430450 A CN115430450 A CN 115430450A CN 202211045142 A CN202211045142 A CN 202211045142A CN 115430450 A CN115430450 A CN 115430450A
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CN115430450B (en
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周宝文
王新强
李景林
盛博文
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Peking University
Shanghai Jiaotong University
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J37/08—Heat treatment
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Abstract

The invention relates to the technical field of thermal catalysts, in particular to a preparation method and application of a Rh nanoparticle modified III-group nitrogen oxide Si catalyst. The preparation method has the advantages of simple operation, high controllability and low manufacturing cost. Application of the prepared thermal catalyst to CO 2 In the reaction of thermocatalytic hydrogenation to CO, severe experimental conditions such as high temperature and high pressure are avoided, and CO is greatly improved 2 The rate of CO production by hydrogenation. Rh NPs have a heightThe dispersity ensures high-efficiency and long-acting catalysis of CO 2 Hydrogenation reactions occur. CO compared to existing commercial catalytic systems 2 The hydrogenation activity is higher than 4 orders of magnitude, and the method has great application prospect.

Description

Preparation method and application of Rh nanoparticle modified III-group nitrogen oxide Si catalyst
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of thermal catalysts, in particular to a preparation method and application of a Rh nanoparticle modified III-group nitrogen oxide Si catalyst.
[ background of the invention ]
CO 2 Is one of the serious problems facing human beings at present. CO 2 2 The fixation and the refining of the (C) and the conversion of the (C) into other high value-added chemicals and high-energy-density synthetic fuels have very important significance for solving the current greenhouse effect and relieving the problem of energy shortage. As CO 2 One of the hydrogenated products, CO, is the main raw material for Fischer-Tropsch synthesis, and plays a significant role in the process of producing chemicals and fuels through chemical refining. At the same time, with respect to CO 2 The conversion of CO to other hydrogenation products is relatively easy both kinetically and thermodynamically. Thus, CO is converted 2 The conversion to CO by hydrogenation is a good choice. Compared with other conversion technologies (biocatalysis and electrocatalysis), the thermocatalysis technology is used for CO 2 The processing capacity is high, and the device has high compatibility with the existing industrial facilities, so that the use and popularization cost is reduced to a certain extent. But CO 2 The bond energy is high, and the high activity and high selectivity of CO production at lower temperature is a great challenge. From the current research situation, most of the thermocatalytic refining means still need the severe conditions of high temperature and high pressure, which has extremely high requirements on refining equipment, and in addition, the yield of CO is low, the catalytic stability is poor, and the CO is further increased 2 The application cost of hydrogenation technology makes it still not very different from industrialization.
In previous studies, rh was considered to be a highly effective catalytic CO 2 A hydrogenated metal. However, when supported on a conventional carrier (alumina, ceria, etc.), conditions of high temperature and high pressure are still required, and the yield of CO is low. This is largely due to the limitations of conventional supports that make it difficult to exert excellent synergy with Rh. Therefore, the temperature of the molten steel is controlled,the development of a new carrier for enhancing the synergistic capability with Rh can greatly promote CO 2 Hydrogenation reactions occur.
[ summary of the invention ]
The invention aims to provide a preparation method and application of Rh nanoparticle modified III-group nitrogen oxide Si catalyst, wherein a molecular beam epitaxy Method (MBE) is combined with high-temperature annealing to prepare a III-group nitrogen oxide NWs/Si carrier, rh NPs (nitrogen phosphide)/NPs (nitrogen phosphide) is anchored on the surface of the carrier by a photo-deposition method, and the prepared thermal catalyst is applied to CO 2 In the reaction from thermocatalytic hydrogenation to CO, the reaction conditions of high temperature and high pressure are avoided, and the reaction rate is improved.
Growing a III-group nitride NWs/Si epitaxial wafer by a Molecular Beam Epitaxy (MBE) method, partially oxidizing the surface of the III-group nitride NWs/Si epitaxial wafer by high-temperature annealing to prepare a III-group oxynitride NWs/Si carrier, and finally preparing the Rh/III-group oxynitride NWs/Si thermal catalyst by a photo-deposition method.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of Rh nanoparticle modified III-group nitrogen oxide Si catalyst is characterized by comprising the following steps: the method comprises the specific steps of,
step 1, cleaning a silicon wafer by using a cleaning agent, taking the silicon wafer as a substrate, and growing by using a molecular beam epitaxy method to prepare a III-group nitride NWs/Si carrier;
step 2, carrying out high-temperature annealing on the III-group nitride NWs/Si in an air atmosphere to obtain a III-group nitrogen oxide NWs/Si carrier;
and 3, loading Rh on the III-group nitrogen oxide NWs/Si by a photo-deposition method to prepare the Rh/III-group nitrogen oxide NWs/Si thermal catalyst.
As a further improvement of the invention, the cleaning agent comprises any one or two of an organic solvent and an acidic solvent.
As a further improvement of the invention, the growth conditions of the molecular beam epitaxy method comprise 5 × 10 -8 Torr Ga-Beam Equivalent Pressure (BEP), 350W forward plasma power.
As a further refinement of the present invention, the bottom group III nitride layer is first grown in situ to serve as a template for group III nitride NWs.
As a further improvement of the invention, the growth conditions further comprise that the substrate temperature is 680-720 ℃, and the growth time is 45-75 min.
As a further improvement of the invention, the temperature of the high-temperature annealing is 150-250 ℃, and the heat preservation time is 1-2 hours.
As a further improvement of the invention, the photo-deposition method comprises the steps of putting the III-group nitrogen oxide NWs/Si into a reactor, and respectively adding a mixed solution of an organic alcohol solvent and water and an Rh precursor H 2 RhCl 6 And in a vacuum state of an argon atmosphere, a xenon lamp is used as a light deposition light source for illumination, and then the Rh/III group nitrogen oxide NWs/Si thermal catalyst is prepared.
As a further development of the invention, the illumination time is 0.5 hours.
The application of Rh nanoparticle modified group III nitrogen oxide Si catalyst is characterized in that: use of the catalyst prepared by the process of claim 1 for the thermocatalytic CO 2 In the reaction for preparing CO.
As a further development of the invention, the thermocatalytic CO 2 The reaction for preparing CO can be controlled at the minimum 170 ℃.
Compared with the prior art, the invention has the advantages that:
1. the invention develops a brand new III-group nitride carrier, which is different from the traditional catalytic carriers such as alumina, cerium oxide and the like, and the III-group nitride has good one-dimensional morphology and higher specific surface area, thereby being beneficial to the high dispersion of a cocatalyst; to linear CO 2 The molecules have excellent adsorption and activation effects; modifications can be made at the atomic layer level.
2. MBE is combined with air atmosphere annealing to prepare a III-group nitrogen oxide NWs/Si carrier, and Rh NPs are anchored on the surface of the carrier in a photo-deposition mode. The speed-dependent step is changed by reducing the activation energy of the key element reaction, so that lower reaction starting temperature is obtained and high-efficiency and long-acting CO is realized 2 Hydrogenation and refining.
3. The preparation method has the advantages of simple operation and low manufacturing cost.
4. The Rh-loaded III-group nitrogen oxide thermal catalyst prepared by the invention is applied to thermal catalysis of CO 2 In the reaction for preparing CO, severe experimental conditions such as high temperature and high pressure are avoided, and CO is greatly improved 2 The rate of CO production by hydrogenation. Rh NPs have high dispersity and ensure high-efficiency and long-acting catalysis of CO 2 Hydrogenation reactions occur. CO compared to existing commercial catalytic systems 2 The hydrogenation activity is higher than 4 orders of magnitude, and the method has a great application prospect.
[ description of the drawings ]
FIG. 1 is a graph of the CO of Rh/group III nitrides NWs/Si and Rh/group III oxynitrides NWs/Si at different reaction temperatures 2 Hydrogenation activity.
FIG. 2 is a graph of the CO of Rh/group III nitroxides NWs/Si at different reaction temperatures 2 Hydroconversion frequency (TOF).
FIG. 3 is a CO of Rh/group III oxynitride NWs/Si-250 and Rh/group III nitride TP/Sapphire at 260 deg.C 2 Hydrogenation activity.
FIG. 4 shows Rh/group III oxynitride/NWs/Si-250 and Rh/Al 2 O 3 CO at 260 deg.C 2 Hydrogenation activity.
FIG. 5 is a graph of Rh/group III nitroxide NWs/Si-250 catalyzing CO at 260 deg.C 2 Stability of hydrogenation.
[ detailed description ] embodiments
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of the present invention.
Example 1
Preparation of group III nitride support
Epitaxial growth of III Using a Veeco Gen II MBE System equipped with a radio frequency plasma assisted Nitrogen SourceGroup nitrogen oxides NWs. A 4 inch silicon (111) wafer was used as the substrate. Prior to loading into the MBE chamber, the silicon wafer was cleaned with acetone and methanol to remove organic contaminants, and then rinsed with 10% hydrofluoric acid to remove silicon oxide. The growth conditions for these nanowires include 5 × 10 -8 Ga Beam Equivalent Pressure (BEP) of Torr and forward plasma power of 350W. The nitrogen flow rate was set at 1.0 standard cubic centimeters per minute (sccm) to ensure that the nitrogen rich atmosphere facilitated the formation of the N-side surface (m-plane) of the nanowires. Furthermore, the use of a Ga seed layer to facilitate the formation of a Ga-polar basal plane is terminated for N. The substrate temperature for growth was about 700 ℃. Typically, the bottom group III oxynitride layer is first grown in situ to serve as a template for the group III oxynitride NWs. After the growth time is 1 hour, the carrier of the III-group nitrogen oxide NWs/Si is prepared.
Example 2
Preparation of Rh/III group nitride NWs/Si thermal catalyst
The group III nitride NWs/Si (geometric surface area about 0.2 cm) 2 ) The pretreatment was rinsed with deionized water and then placed in a 0.4L glass reactor equipped with a top quartz window. 60mL of a methanol/water mixed solution (volume ratio 1/5) was poured into the reactor, and 70. Mu.L of Rh precursor (0.2 mol/L of H) was added 2 RhCl 6 ). After evacuating the reactor chamber for about 2min, the chamber was evacuated 5 times with argon to remove residual air in the system. A300W xenon lamp (AuLight, CEL-HLF 300-T3) was used as the light source for the light deposition, with an illumination time of 0.5 hours. The Rh/group III nitride NWs/Si thermal catalyst was prepared by thoroughly rinsing with deionized water to remove carbon residue.
Examples 3 to 5
Preparation of Rh/III group nitrogen oxide NWs/Si catalyst
Putting the III group nitride NWs/Si into a thermal reaction kettle, keeping the contact with air and keeping the interior of the kettle at normal pressure, then gradually increasing the temperature to the annealing temperature and keeping the temperature for one hour, and cooling to room temperature after the heat preservation is finished to prepare the III group nitrogen oxide NWs/Si carrier.
The group III nitrogen oxide NWs/Si (geometric surface area-0.2 cm) 2 ) Rinsing with deionized water to obtain a pre-treated solution, and placing into a containerTop quartz window in a 0.4L glass reactor. 60mL of a methanol/water mixed solution (volume ratio: 1/5) was poured into the reactor, and 70. Mu.L of Rh precursor (0.2 mol/L of H) was added 2 RhCl 6 ). After evacuating the reactor chamber for about 2min, the chamber was evacuated 5 times with argon to remove residual air in the system. A300W xenon lamp (AuLight, CEL-HLF 300-T3) was used as the light source for the light deposition, with an illumination time of 0.5 hours. The Rh/III-family nitrogen oxide NWs/Si thermal catalyst is prepared by thoroughly washing with deionized water to remove carbon residues, and the specific experimental conditions and product names are shown in the following table 1.
TABLE 1 Experimental conditions and products of examples 3-5
Examples Annealing temperature Group III nitrogen oxides Product of
3 150℃ Group III oxynitride NWs/Si/Si-150 Rh/group III oxynitride NWs/Si-150
4 200℃ Group III oxynitride NWs/Si-200 Rh/III-group nitrogen oxide NWs/Si-200
5 250℃ Group III oxynitride NWs/Si-250 Rh/group III oxynitride NWs/Si-250
Example 6
Preparation of Rh/group III nitride TP/Sapphire catalyst
A commercially available group III nitride thin film (designated as group III nitride TP/Sapphire, with a geometric surface area of 0.2 cm) 2 ) The pretreatment was rinsed with deionized water and then placed in a 0.4L glass reactor equipped with a top quartz window. 60mL of a methanol/water mixed solution (volume ratio: 1/5) was poured into the reactor, and 70. Mu.L of Rh precursor (0.2 mol/L of H) was added 2 RhCl 6 ). After evacuating the reactor chamber for about 2min, the chamber was evacuated 5 times with argon to remove residual air in the system. A300W xenon lamp (AuLight, CEL-HLF 300-T3) was used as the light source for the light deposition, and the illumination time was 0.5 hour. Thoroughly rinsing with deionized water to remove carbon residue to obtain Rh/III nitride TP/Sapphire thermal catalyst,
example 7
Application experiment of thermal catalyst
The thermal catalysts prepared in examples 2-6 and Rh/Al were separately added 2 O 3 (Shanxi Kaida chemical industry, ltd.) for CO production 2 Experiment for preparing CO by catalytic hydrogenation. The method comprises the following specific steps: catalyst (commercial catalyst Rh/Al) was added to a sealed 0.25L stainless steel reactor 2 O 3 1 g), sealing the kettle body, completely pumping to vacuum, and introducing CO into the kettle 2 And H 2 Mixed gas (CO) of (2) 2 ：H 2 =10: 1) To normal pressure. The temperature was gradually raised and kept at different reaction temperatures (170 ℃, 200 ℃, 230 ℃, 260 ℃ and 290 ℃) for one hour. After cooling to room temperature, 50mL of gas was taken out by a syringe and injected into a gas chromatograph equipped with a FID detector, and the CO yield was measured.
As can be seen from FIGS. 1 and 2, the Rh/group III nitrides NWs/Si and RH/group III nitrogen oxides NWs/Si to CO 2 The hydrogenation catalytic activity is positively correlated with the reaction temperature: the higher the reaction temperature, the higher the CO 2 The faster the hydrogenation rate. After partial oxidation of the surface of the group III nitride, the minimum temperature at which the reaction starts is lowered to 170 ℃, and the reactivity gradually increases as the degree of oxidation increases (the oxidation temperature increases). When the oxidation temperature reached 250 ℃ (Rh/III oxynitride NWs/Si-250), 127 mmol g was obtained at 290 ℃ reaction temperature -1 ·h -1 High CO yield of Rh/group III nitride NWs/Si (85.9 mmol. Multidot.g) -1 ·h -1 ) The improvement is 47.8 percent. At the same time, the conversion frequency (TOF) of the Rh/group III nitroxide NWs/Si-250 reached 270.2 mol CO per mole Rh.
As can be seen from FIGS. 3 and 4, 106.4 mmol.g was obtained for the Rh/group III oxynitride NWs/Si-250 at a reaction temperature of 260 deg.C -1 ·h -1 The CO generation rate of (2.7 mmol. Multidot.g) to Rh/group-III nitride TP/Sapphire (2.7 mmol. Multidot.g) based on the commercial group-III nitride TP/Sapphire at the same temperature -1 ·h -1 ) 39 times higher than commercial catalyst Rh/Al 2 O 3 （0.017 mmol·g -1 ·h -1 ) Has a 6259-fold higher CO production rate. This demonstrates that the group III nitride NWs catalytic system we developed has a higher CO generation rate than the commercial catalytic system at the same temperature.
As can be seen from FIG. 5, the Rh/group III oxynitride NWs/Si-250 gave a total CO yield of 1.22 mol and an intrinsic activity (TON) of 2616 mol CO per mol Rh after 9 cycles of stability tests for a total of 45 hours, and the catalytic activity did not decay significantly.

Claims (10)

1. A preparation method of Rh nanoparticle modified III-group nitrogen oxide Si catalyst is characterized by comprising the following steps: the method comprises the following specific steps of,
step 1, cleaning a silicon wafer by using a cleaning agent, taking the silicon wafer as a substrate, and growing by using a molecular beam epitaxy method to prepare a III-group nitride NWs/Si carrier;
step 2, carrying out high-temperature annealing on the III-group nitride NWs/Si in an air atmosphere to obtain a III-group nitrogen oxide NWs/Si carrier;
and 3, loading Rh on the III-group nitrogen oxide NWs/Si by a photo-deposition method to prepare the Rh/III-group nitrogen oxide NWs/Si thermal catalyst.
2. The preparation method of the Rh nanoparticle modified group III oxynitride Si catalyst as claimed in claim 1, wherein: the cleaning agent comprises any one or two of an organic solvent and an acidic solvent.
3. The preparation method of the Rh nanoparticle modified group III oxynitride Si catalyst as claimed in claim 1, wherein the preparation method comprises the following steps: the growth conditions of the molecular beam epitaxy method comprise 5 multiplied by 10 -8 Torr Ga Beam Equivalent Pressure (BEP), 350W forward plasma power.
4. The preparation method of the Rh nanoparticle modified group III oxynitride Si catalyst as claimed in claim 1, wherein the preparation method comprises the following steps: the bottom group III nitride layer is first grown in situ to serve as a template for group III nitride NWs.
5. The preparation method of the Rh nanoparticle modified group III oxynitride Si catalyst as claimed in claim 1, wherein: the growth conditions also comprise that the substrate temperature is 680-720 ℃, and the growth time is 45-75 min.
6. The preparation method of the Rh nanoparticle modified group III oxynitride Si catalyst as claimed in claim 1, wherein the preparation method comprises the following steps: the temperature of the high-temperature annealing is 150-250 ℃, and the heat is preserved for 1-2 hours.
7. The preparation method of the Rh nanoparticle modified group III oxynitride Si catalyst as claimed in claim 1, wherein the preparation method comprises the following steps: the photo-deposition method comprises the steps of putting III-group nitrogen oxide NWs/Si into a reactor, and respectively adding a mixed solution of an organic alcohol solvent and water and an Rh precursor H 2 RhCl 6 And in a vacuum state of an argon atmosphere, a xenon lamp is used as a light deposition light source for illumination, and then the Rh/III group nitrogen oxide NWs/Si thermal catalyst is prepared.
8. The preparation method of the Rh nanoparticle modified group III oxynitride Si catalyst as claimed in claim 1, wherein: the illumination time was 0.5 hours.
9. The application of Rh nanoparticle modified III-group nitrogen oxide Si catalyst is characterized in that: use of the thermal catalyst prepared by the process of claim 1 for the thermal catalysis of CO 2 In the reaction for preparing CO.
10. The use of the Rh nanoparticle modified group III oxynitride Si catalyst as claimed in claim 9, wherein: the thermocatalytic CO 2 The reaction for preparing CO can be controlled at a minimum of 170 ℃.
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