CN112264008A - Pd/TiO2- {100} composite catalyst, preparation method and application thereof - Google Patents

Pd/TiO2- {100} composite catalyst, preparation method and application thereof Download PDF

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CN112264008A
CN112264008A CN202011324482.8A CN202011324482A CN112264008A CN 112264008 A CN112264008 A CN 112264008A CN 202011324482 A CN202011324482 A CN 202011324482A CN 112264008 A CN112264008 A CN 112264008A
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formic acid
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CN112264008B (en
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张振华
张静
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Zhejiang Normal University CJNU
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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Abstract

The invention relates to the technical field of chemical catalyst application, in particular to Pd/TiO2New application of 100 composite catalyst in heterogeneous catalysis field. The invention provides Pd/TiO2- {100} composite catalyst in CO2Application of the reaction of hydrogenation to prepare formic acid in Pd/TiO2- {100} composite catalyst, Pd was metallic Pd nanoparticles supported on anatase TiO preferentially exposing {100} crystal face2On nanocrystals of CO2The catalytic performance in the reaction of preparing formic acid by hydrogenation is superior to that of the reaction of preparing TiO by preferential exposure of Pd nano-particles loaded on2- {101} and TiO2Pd/TiO of- {001} crystal face2- {101} and Pd/TiO2- {001} composite catalyst, while far superior to commercial TiO2(P25) Pd/TiO of catalyst supported Pd nano-particle2(P25) A catalyst. Compared with the existing catalytic process, the catalyst has the advantages of simple preparation process, mild catalytic reaction conditions and high formic acid yield, and is suitable for popularization and application.

Description

Pd/TiO2- {100} composite catalyst, preparation method and application thereof
Technical Field
The invention relates to the technical field of chemical catalyst application, in particular to Pd/based catalystTiO2- {100} composite catalyst, preparation method and application thereof. More particularly, it relates to a Pd/TiO2- {100} composite catalyst, its preparation method and its application in heterogeneous catalysis field.
Background
CO2One of the most important gases in the "greenhouse effect" is the global temperature and climate, which are statistically significant changes in atmospheric CO2Has increased from 280ppm before the industrial revolution to 390ppm in 2010, and is predicted to reach 570ppm at the end of this century, thereby effectively reducing CO in the atmosphere2The content of (A) is an imminent task.
By CO2The reaction for preparing the formic acid by hydrogenation not only can utilize greenhouse effect gas CO which is harmful to the environment2And meanwhile, the formic acid can be converted into valuable chemical formic acid, which is one of basic organic chemical raw materials, is widely used in the industries of pesticides, leather, dyes, medicines, rubber and the like, can be directly used for textile processing, tanning, textile printing and dyeing and storage of green feeds, and can also be used as a metal surface treating agent, a rubber auxiliary agent and an industrial solvent. The method is used for synthesizing various formate, acridine dyes and formamide series medical intermediates in organic synthesis, thereby having extremely high research value.
In addition, CO is catalyzed using heterogeneous catalysts2The hydrogenation of formic acid has been studied for over 100 years and the development of heterogeneous catalysts has mainly focused on supported metal catalysts, including Ru-based, Au-based and Pd-based catalysts, with Pd-based catalysts being the most interesting. There have also been many studies on the carrier of Pd-based catalysts, including C, γ -Al2O3，CeO2And ZnO, wherein the metal oxide has better performance of producing formic acid, and the metal oxide has the biggest characteristics of good stability, and rich redox property and surface acid-base performance, so that the metal oxide can be subjected to variable regulation and control.
And, TiO2Because of its low cost and good stability, it is attracting much attention in the field of catalysis, and it can be used as a good catalyst or catalyst carrier and widely used in the field of catalystsVarious catalytic reactions including CO catalytic oxidation, organic synthesis catalysis, photocatalysis, biological oxidation resistance and the like. In recent years, researchers have found TiO very well2In CO2The hydrogenation reaction for preparing formic acid also has excellent catalytic application, and CO is used at present2Research work on the hydrogenation of formic acid is mainly carried out in a plurality of international high-level journals. However, for TiO of specific crystal plane2In CO2The application of the reaction for preparing the formic acid by hydrogenation is only reported so far, so that the method has extremely high research value.
Disclosure of Invention
In view of the above, the present invention provides a Pd/TiO material in order to solve the problems in the prior art2- {100} composite catalyst in CO2Compared with the existing catalytic process, the catalyst has the advantages of simple preparation process, mild catalytic reaction conditions, high formic acid yield and suitability for popularization.
In order to achieve the purpose, the technical scheme of the invention is as follows:
Pd/TiO2Preparation method of-100 composite catalyst, Pd/TiO2The-100 composite catalyst is the metal Pd composite 001-TiO2The nano-catalyst and the method specifically comprise the following steps:
1) to synthesize TiO2Dispersing the-100 nano crystal in deionized water, heating and stirring, adding a chloropalladate solution, and mixing to obtain a reaction solution;
2) with Na2CO3Regulating the pH value of the reaction solution by using a buffer solution, heating, stirring, centrifugally washing, drying and grinding to obtain brown yellow solid powder;
3) calcining the brown yellow solid powder prepared in the step 2), and then carrying out H2TPR reduction to obtain black Pd/TiO2- {100} composite catalyst.
Preferably, in the step 1), TiO2The addition mass ratio of the-100 nano crystal to the palladium chloride acid is (31.9-255.2): 1, the reaction temperature is 45-55 ℃, and the reaction time is 30-60 min.
Preferably, in the step 2), Na is added2CO3Adjusting the pH value of the reaction solution to 9.5-10 by using a buffer solution, heating the reaction solution to 45-55 ℃, and reacting for 3-5 h; the drying temperature is 60-80 ℃, and the drying time is 10-12 h.
Preferably, the calcining temperature in the step 3) is 300-400 ℃, and the calcining time is 2-3 h; and said H2The TPR reduction process is: at 5% H2/N2Reducing for 1-2 h at 200-250 ℃ in the atmosphere.
Another object of the present invention is to provide a Pd/TiO compound prepared by the above method2- {100} composite catalyst.
The Pd/TiO2The Pd in the-100 composite catalyst is metal Pd particles and can promote CO2H in hydrogenation2The supported amount of the dissociation is 0.5 to 4 wt.%, and the average size is 1.5 to 5.5 nm;
and, the Pd/TiO2- {100} TiO in composite catalyst2Anatase TiO with preferential exposure of {100} crystal face2The nanocrystalline has higher concentration of surface alkaline sites, and is beneficial to CO2The {100} crystal face of the activation process is in TiO2The proportion of the nano-crystal is 80-90 percent, and TiO2The grain size of the-100 nano crystal is 15-30 nm, and the specific surface area is 95-105m2/g。
Meanwhile, it is to be noted that CO is catalyzed by traditional homogeneous catalysis2Compared with hydrogenation to formic acid, heterogeneous catalysis has the advantages of easy separation, environmental friendliness and the like, but CO is catalyzed by adopting a heterogeneous catalysis mode at present2The biggest defect of hydrogenation for preparing formic acid is that the yield is too low, which limits further development and application of the formic acid. Therefore, the development of a heterogeneous catalyst with high efficiency is of great importance.
In continuous research, it is found that the supported Pd-based catalyst shows the best catalytic performance and the best application prospect. It is believed that, in the case of the supported Pd-based catalyst, the mutual interface between Pd and the carrier is the active center of the reaction, and Pd can play a role in cracking H2And the carrier is used for activating CO2The two cooperate toThe purpose of generating formic acid is achieved.
It is well known that Pd in the metallic state has a good H splitting effect2Function, therefore for this reaction, selection of a suitable support activates CO2Is crucial for the improvement of the catalytic performance of the reaction. The application patent finds anatase TiO2- {100} support having very good CO-activation2The Pd/TiO is synthesized by a precipitation deposition method to obtain Pd/TiO, and the Pd/TiO has strong interaction with Pd2- {100} composite catalyst, which not only can stabilize Pd structure, but also has good catalytic activity and stability; the preparation process is simple, the formic acid can be efficiently generated under mild reaction conditions, and the yield of the formic acid is superior to that of Pd/TiO2- {101} and Pd/TiO2- {001} composite catalyst, while being far superior to commercial Pd/TiO2(P25) A catalyst.
It is yet another object of the present invention to provide Pd/TiO2-100 } use of a composite catalyst in the field of heterogeneous catalysis.
In some application scenarios, the method comprises the following steps: the Pd/TiO2- {100} composite catalyst in CO2The application of the hydrogenation reaction for preparing formic acid comprises the following specific steps:
the Pd/TiO is added2- {100} composite catalyst dispersed in NaHCO3In the water solution, placing the mixture into a high-pressure reaction kettle after ultrasonic homogenization; introducing CO2And H2Mixing the gas, adjusting the pressure of the reaction kettle through a steel bottle pressurizing valve, and then heating for constant temperature reaction; and after the reaction is finished, filtering, and analyzing the obtained filtrate by adopting ion chromatography to finally obtain the yield of the formic acid.
Wherein, said NaHCO3The mass ratio of the catalyst to the composite catalyst is (16.8-33.6): 1, and CO in the reaction gas component2And H2The mixing volume ratio of (0.5-1.5): 1.
further, H2The pressure change of the catalyst is 0.5-1.5MPa, and the temperature of the catalytic reaction is 25-45 ℃.
As can be seen from the technical scheme, compared with the prior art, the Pd/TiO composite material provided by the invention2- {100} composite catalyst andthe preparation method and the application thereof have the following excellent effects:
the invention provides Pd/TiO2- {100} composite catalyst in CO2Application of the reaction of hydrogenation to prepare formic acid in Pd/TiO2- {100} composite catalyst, Pd was metallic Pd nanoparticles supported on anatase TiO preferentially exposing {100} crystal face2On nanocrystals of CO2The catalytic performance in the reaction of preparing formic acid by hydrogenation is superior to that of the reaction of preparing TiO by preferential exposure of Pd nano-particles loaded on2- {101} and TiO2Pd/TiO of- {001} crystal face2- {101} and Pd/TiO2- {001} composite catalyst, while far superior to commercial TiO2(P25) Pd/TiO of catalyst supported Pd nano-particle2(P25) A catalyst. Compared with the existing catalytic process, the catalyst has the advantages of simple preparation process, mild catalytic reaction conditions and high formic acid yield, and is suitable for popularization and application.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is TiO2TEM (left) and HETEM (right) images of the- {100} nanocrystals.
FIG. 2 shows 2% Pd/TiO2TEM (left) and HRTEM (right) images of the-100 } composite catalyst.
FIG. 3 is TiO2- {100} and a load of 0.5 to 4% Pd/TiO2XRD spectrum of the catalyst- {100 }.
FIG. 4 is TiO2- {100} and 0.5% -4% Pd/TiO2XPS spectra of Ti 2p (left) and Pd 3d (right) for the-100 catalyst.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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 protection scope of the present invention.
The embodiment of the invention discloses a catalyst capable of reacting on CO2Pd/TiO applied in reaction for preparing formic acid by hydrogenation2- {100} composite catalyst.
The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention is not to be construed as being limited thereto, and certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing disclosure are intended to be included within the scope of the invention.
The technical solution of the present invention will be further described with reference to the following specific examples.
Example 1
This example is TiO2Method for synthesizing-100 nanocrystalline, TiO with uniform size is obtained by accurately controlling synthesis conditions2- {100} nanocrystals, the specific synthesis method is as follows:
6.6mL of TiCl were added at 0 deg.C4Dropwise added to 20mL of 0.43M aqueous HCl solution, stirred for 0.5 hour, and then the solution was dropwise added to 50mL of 5.5 wt% NH under stirring at room temperature3In an aqueous solution; then, an appropriate amount of 4 wt% NH was used3Adjusting pH of the solution to 6-7 with water solution, stirring at room temperature for 2 hr, filtering to obtain precipitate, washing with ultrapure water repeatedly until no residual Cl can be detected-Until then, it was dried at 70 ℃ for 12 hours to obtain Ti (OH)4(ii) a 2.0g of Ti (OH) was added under stirring at room temperature4And 0.5g (NH4)2SO4Dispersing in a mixed solution of 15mL of ultrapure water and 15mL of isopropanol, transferring the mixed solution into a 50mL stainless steel high-pressure reaction kettle, keeping the reaction kettle at 180 ℃ for 24 hours, collecting obtained white precipitate, and repeatedly washing with ultrapure water to obtain the TiO2- {100} nanocrystals.
The morphology was examined and is shown in FIG. 1. From the figure canTo obtain, the synthesized TiO2The catalyst has uniform size and regular appearance, and preferentially exposes the crystal face of the {100 }.
Example 2
This example is Pd/TiO2The synthesis method of the- {100} composite catalyst obtains Pd/TiO with different Pd loading amounts (0.5-4 wt.%) by accurately controlling the synthesis conditions2The specific synthesis method of the catalyst is as follows:
300mg of freshly synthesized TiO2Dispersing the-100 nano crystal in 100mL of deionized water, placing the mixture in an oil bath kettle at 50 ℃, heating and stirring for half an hour, adding a chloropalladate solution with a certain content (the specific gravity of Pd and the carrier is calculated to be 0.5-4% by weight), and stirring for half an hour to uniformly mix the solution; then using 1mol/L Na2CO3Adjusting the pH value of the solution by using a buffer solution, adjusting the pH value to 10, continuously stirring for 3 hours in an oil bath kettle at the temperature of 50 ℃ to obtain a brown yellow solid, centrifugally washing, and drying for 12 hours in an air drying oven at the temperature of 80 ℃ to obtain brown yellow solid powder; the powder obtained was then calcined in a muffle furnace at 350 ℃ for 2H and the calcined sample was brought to 5% H2/N2Reducing for 1h at 200 ℃ in the atmosphere to obtain Pd/TiO with black loading of 0.5-4%2- {100} composite catalyst.
The morphology was examined and is shown in FIG. 2. As can be derived from the figure, the support TiO2The morphology of (a) is maintained while Pd is supported on the surface of the support in the metallic state.
Example 3
Pd/TiO with different Pd loading amounts prepared in the above way2Application of-100 composite catalyst to CO2In the catalytic reaction of hydrogenation for preparing formic acid, the method for testing the catalytic performance is as follows:
5mg of freshly synthesized 0.5% -4% Pd/TiO2- {100} catalyst was dispersed in 168mg of NaHCO3Ultrasonic treating the water solution (100mL), placing the water solution in a high-pressure reaction kettle, adjusting the pressure of the reaction kettle through a steel bottle pressure valve, and keeping CO: H 21, total pressure of 2MPa, constant temperature catalytic reaction for 1h by heating the reaction kettle in an oil bath at 40 deg.C, and filteringThe catalyst solids dispersed in the solution were filtered off by a filter, and the resulting filtrate was analyzed for formic acid content by ion chromatography.
The formic acid yields obtained were calculated and the results are given in Table 1 by the numbers (1-3) giving Pd/TiO at different Pd loadings2- {100} catalyst for catalyzing CO2The catalytic performance of hydrogenation to prepare formic acid. And as can be seen from the data in table 1, the formic acid yield was highest when the Pd loading was 2% wt, indicating that the metallic Pd nanoparticles had better H at this loading2Dissociation capability, thereby accelerating the catalytic reaction.
TABLE 1 different Pd/TiO2- {100} catalysts catalyze CO under various reaction conditions2Catalytic performance table of catalytic reaction for preparing formic acid by hydrogenation
Figure BDA0002793896570000061
Figure BDA0002793896570000071
Furthermore, TiO2- {100} and a load of 0.5 to 4% Pd/TiO2XRD spectrum of the-100 catalyst is shown in FIG. 3, and from FIG. 3, TiO2- {100} and Pd/TiO at different loadings2- {100} catalyst exhibits anatase TiO2No diffraction peak of Pd appears, indicating that the particle size of Pd is relatively small.
And, TiO2- {100} and 0.5% -4% Pd/TiO2The XPS spectra of Ti 2p (left) and Pd 3d (right) of the-100 catalyst are shown in FIG. 4, and it can be seen from FIG. 4 that the loading of Pd does not affect the TiO2The surface structure of (1), Pd being present mainly in the metallic state with accompanying Pd2+Mainly due to Pd and TiO2Strong interaction of (2) to transfer electrons from Pd to TiO2Surface, resulting in Pd showing positive valence.
Example 4
2% Pd/TiO prepared as described above2Application of the- {100} composite catalyst to different conditions(reaction temperature Change) CO2In the catalytic reaction of hydrogenation for preparing formic acid, the method for testing the catalytic performance is as follows:
5mg of freshly synthesized 2% Pd/TiO2- {100} catalyst was dispersed in 168mg of NaHCO3Ultrasonic treating the water solution (100mL), placing the water solution in a high-pressure reaction kettle, adjusting the pressure of the reaction kettle through a steel bottle pressure valve, and keeping CO: H2The total pressure is 2MPa, the temperature of a reaction kettle is controlled to be 25-45 ℃ through heating of an oil bath kettle, the constant-temperature catalytic reaction is carried out for 1h, catalyst solids dispersed in the solution are filtered out through a filter, and the content of formic acid in the obtained filtrate is analyzed through ion chromatography.
The formic acid yields obtained were calculated and the results are given in Table 1 under numbers (2, 4, 5) giving 2% Pd/TiO at different reaction temperatures2- {100} catalyst for catalyzing CO2The catalytic performance of hydrogenation to prepare formic acid. And as can be seen from the data in table 1, the yield of formic acid increases with the increase of the reaction temperature, which increases the reactivity of the reaction mainly because the increase of the temperature increases the probability of collision between the reactant molecules.
Example 5
2% Pd/TiO prepared as described above2Application of the- {100} composite catalyst to different conditions (varying NaHCO)3Mass) of CO2In the catalytic reaction of hydrogenation for preparing formic acid, the method for testing the catalytic performance is as follows:
5mg of fresh 2% Pd/TiO2- {100} catalyst dispersed in 16.8-168mg of NaHCO3Ultrasonic treating the water solution (100mL), placing the water solution in a high-pressure reaction kettle, adjusting the pressure of the reaction kettle through a steel bottle pressure valve, and keeping CO: H2The total pressure is 2MPa, the temperature of a reaction kettle is controlled to be 40 ℃ through heating of an oil bath kettle, the constant-temperature catalytic reaction is carried out for 1h, then, catalyst solid dispersed in the solution is filtered out by a filter, and the content of formic acid in the obtained filtrate is analyzed by ion chromatography.
The formic acid yields obtained were calculated and the results are given in Table 1 under numbers (2, 6) giving the different NaHCO values 32% by mass of Pd/TiO2- {100} catalyst for catalyzing CO2The catalytic performance of hydrogenation to prepare formic acid. And as can be seen from the data in Table 1, itFormic acid yield was determined by NaHCO3Mass increase due to mainly NaHCO3The function of reactants is realized, and according to the chemical equilibrium principle, the reaction is accelerated by increasing the concentration of the reactants.
Example 6
2% Pd/TiO prepared as described above2Application of the- {100} composite catalyst to different conditions (Change of H)2:CO2Ratio) of CO2In the catalytic reaction of hydrogenation for preparing formic acid, the method for testing the catalytic performance is as follows:
5mg of freshly synthesized 2% Pd/TiO2- {100} catalyst was dispersed in 168mg of NaHCO3Ultrasonic homogenizing in water solution (100mL), placing in high pressure reactor, regulating pressure of the reactor with steel cylinder pressure valve to change CO: H2The proportion is that the total pressure is kept at 2MPa, the temperature of the reaction kettle is controlled at 40 ℃ by heating the oil bath kettle, the constant temperature reaction is carried out, after the catalytic reaction is carried out for 1h, a filter is used for filtering out catalyst solids dispersed in the solution, and the content of formic acid in the obtained filtrate is analyzed by adopting ion chromatography.
The formic acid yields obtained were calculated and the results are given in Table 1 under numbers (2, 7, 8) giving the different H2:CO 22% Pd/TiO2- {100} catalyst for catalyzing CO2The catalytic performance of hydrogenation to prepare formic acid. And as can be seen from the data in Table 1, the formic acid yield is shown as H2:CO2Increase in the ratio, which is mainly due to H2As one of the important reactants of the reaction, the increase of the relative ratio thereof accelerates the reaction to increase the yield of formic acid.
Example 7
According to Pd/TiO2The 2 percent Pd/TiO is synthesized by the same synthetic method of the catalyst of the- (100) }2-{101}、2％Pd/TiO2- {001} and 2% Pd/TiO2(P25) Catalyst and its application to CO2In the catalytic reaction of hydrogenation for preparing formic acid, the method for testing the catalytic performance is as follows:
5mg of freshly synthesized 2% Pd/TiO2-{101}、2％Pd/TiO2- {001} or 2% Pd/TiO2(P25) Catalyst was dispersed in 168mgNaHCO3Ultrasonic treating the water solution (100mL), placing the water solution in a high-pressure reaction kettle, adjusting the pressure of the reaction kettle through a steel bottle pressure valve, and keeping CO: H2The total pressure is 2MPa, the temperature of a reaction kettle is controlled to be 40 ℃ through heating of an oil bath kettle, the constant-temperature catalytic reaction is carried out for 1h, then, catalyst solid dispersed in the solution is filtered out by a filter, and the content of formic acid in the obtained filtrate is analyzed by ion chromatography.
The formic acid yields obtained were calculated and the results are given in Table 2, giving the different Pd/TiO2Catalyst for catalyzing CO2The catalytic performance of hydrogenation to prepare formic acid. And as can be seen from the data in Table 2, under the same synthesis method, different Pd/TiO2Catalyst for catalyzing CO2The yield of formic acid by hydrogenation depends on TiO2Morphology of support, 2% Pd/TiO2(P25) The activity of the catalyst is lowest, 2% Pd/TiO mentioned in this patent2The highest formic acid yields of the catalyst-100-indicate that the application has good applicability.
TABLE 2.2% Pd/TiO2-{101}、2％Pd/TiO2- {001} and 2% Pd/TiO2(P25) Catalyst for catalyzing CO2Catalytic performance table of catalytic reaction for preparing formic acid by hydrogenation
Figure BDA0002793896570000091
The experimental result shows that 2 percent of Pd/TiO2- {100} composite catalyst showed the best CO2The yield of formic acid at 40 ℃ is 321.6molFormic acidmolPd -1h-1The 2% Pd/TiO2- {100} composite catalyst, Pd as metallic nanoparticles, TiO2Anatase TiO with preferential exposure of {100} crystal face2And (4) nanocrystals. Compared with the existing catalytic process, the preparation process of the catalyst is simple, the catalytic reaction conditions are mild, and the yield of formic acid is high.
In addition, the detection of the invention takes place in the following reaction processes:
CO2+H2→HCOOH
and, the chemicals used in the above examples 1 to 7 were purchased from the national drug group, while the gases (hydrogen and carbon dioxide) used in examples 3 to 7 were ordered from the Nanjing Shangyuan company.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. Pd/TiO2-100 composite catalyst, characterized in that the Pd/TiO is added in a solvent2The-100 composite catalyst is the metal Pd composite 001-TiO2The nano-catalyst and the method specifically comprise the following steps:
1) to synthesize TiO2Dispersing the-100 nano crystal in deionized water, heating and stirring, adding a chloropalladate solution, and mixing to obtain a reaction solution;
2) with Na2CO3Regulating the pH value of the reaction solution by using a buffer solution, heating, stirring, centrifugally washing, drying and grinding to obtain brown yellow solid powder;
3) calcining the brown yellow solid powder prepared in the step 2), and then carrying out H2TPR reduction to obtain black Pd/TiO2- {100} composite catalyst.
2. Pd/TiO according to claim 12The preparation method of the- {100} composite catalyst is characterized in that, in the step 1), TiO2The addition mass ratio of the-100 nano crystal to the palladium chloride acid is (31.9-255.2): 1, the reaction temperature is 45-55 ℃, and the reaction time is 30-60 min.
3. Root of herbaceous plantThe Pd/TiO of claim 12The preparation method of the- {100} composite catalyst is characterized in that in the step 2), Na is added2CO3Adjusting the pH value of the reaction solution to 9.5-10 by using a buffer solution, heating the reaction solution to 45-55 ℃, and reacting for 3-5 h; the drying temperature is 60-80 ℃, and the drying time is 10-12 h.
4. Pd/TiO according to claim 12The preparation method of the < - {100} composite catalyst is characterized in that the calcination temperature in the step 3) is 300-400 ℃, and the calcination time is 2-3 h; and said H2The TPR reduction process is: at 5% H2/N2Reducing for 1-2 h at 200-250 ℃ in the atmosphere.
5. Pd/TiO prepared by the method of any one of claims 1 to 42- {100} composite catalyst, characterized in that the Pd/TiO is2The Pd in the-100 composite catalyst is metal Pd particles, the loading amount of the Pd particles is 0.5-4 wt%, and the average size of the Pd particles is 1.5-5.5 nm;
and, the Pd/TiO2- {100} TiO in composite catalyst2Anatase TiO with preferential exposure of {100} crystal face2Nanocrystals with {100} crystal plane in TiO2The proportion of the nano-crystal is 80-90 percent, and TiO2The grain size of the-100 nano crystal is 15-30 nm, and the specific surface area is 95-105m2/g。
6. Pd/TiO prepared by the method of any one of claims 1 to 42- {100} composite catalyst or Pd/TiO according to claim 52-100 } use of a composite catalyst in the field of heterogeneous catalysis.
7. The use according to claim 6, comprising: the Pd/TiO2- {100} composite catalyst in CO2The application of the hydrogenation reaction for preparing formic acid comprises the following specific steps:
p prepared by the process of any one of claims 1 to 4d/TiO2- {100} composite catalyst dispersed in NaHCO3In the water solution, placing the mixture into a high-pressure reaction kettle after ultrasonic homogenization; introducing CO2And H2Mixing the gas, adjusting the pressure of the reaction kettle through a steel bottle pressurizing valve, and then heating for constant temperature reaction; and after the reaction is finished, filtering, and analyzing the obtained filtrate by adopting ion chromatography to finally obtain the yield of the formic acid.
8. Use according to claim 7, wherein said NaHCO is present3The mass ratio of the catalyst to the composite catalyst is (16.8-33.6): 1, and CO in the reaction gas component2And H2The mixing volume ratio of (0.5-1.5): 1.
9. use according to claim 7, wherein H is2The pressure change of the catalyst is 0.5-1.5MPa, and the temperature of the catalytic reaction is 25-45 ℃.
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