CN114917933A - Cadmium sulfide-palladium monatomic nano catalytic material, preparation method and application thereof - Google Patents
Cadmium sulfide-palladium monatomic nano catalytic material, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a cadmium sulfide-palladium monatomic nano catalytic material, a preparation method and application thereof. The preparation method of the cadmium sulfide-palladium monatomic nano catalytic material comprises the following steps: cadmium sulfide nanoparticles are mixed with soluble palladium salt solution, organic alcohol and organic amine, and photocatalytic reaction is carried out in protective atmosphere. The preparation method of the cadmium sulfide-palladium monatomic nano catalytic material has simple preparation process and lower equipment requirement. The cadmium sulfide-palladium monatomic nano catalytic material is prepared by the photocatalytic reaction of cadmium sulfide nanoparticles, soluble palladium salt, organic alcohol and organic amine and the coordination load of palladium monatomic on the cadmium sulfide nanoparticles, and the selective synthesis and hydrogen production process of the organic amine are realized at the same time, so that the material synthesis and the catalytic reaction are organically combined, the experimental steps are reduced, and the production process is simplified.
Description
Technical Field
The invention relates to the technical field of semiconductor nano materials, in particular to a cadmium sulfide-palladium monatomic nano catalytic material and a preparation method and application thereof.
Background
Organic amine generally refers to an organic substance generated by a chemical reaction between an organic substance and ammonia, and is widely applied to the fields of agriculture, medicine, home furnishing, military industry and the like. The synthesis of organic amines is therefore of increasing importance in industrial production. Based on the "hydrogen borrowing mechanism (hydrogen transfer)", carbon-nitrogen coupling of amines with alcohols is considered to be a greener ideal route for the synthesis of organic amines. However, there are some disadvantages in the thermocatalytic synthesis of organic amines: (1) the dehydrogenation speed-determining step of the alcohol requires harsh conditions (the reaction temperature is 160-500 ℃); (2) excessive coupling is easy to occur, so that the product is widely distributed and is not beneficial to separation; (3) the catalyst used in the reaction is a high-load supported noble metal catalyst, and the cost is high. Therefore, there is a challenge to develop efficient, low cost catalysts and catalytic pathways.
The synthesis of organic amine can be realized under normal temperature and pressure by carrying out homogeneous catalytic reaction by adopting some noble metal organic complex molecules, but the catalyst is difficult to separate after the reaction, and is difficult to be applied on a large scale in the actual industrial production.
Disclosure of Invention
Therefore, it is necessary to provide a cadmium sulfide-palladium monatomic nano catalytic material which can be easily separated and has high catalytic efficiency, and a preparation method and application thereof.
One aspect of the invention provides a preparation method of a cadmium sulfide-palladium monatomic nano catalytic material, which comprises the following steps:
cadmium sulfide nano particles are mixed with soluble palladium salt solution, organic alcohol and organic amine, and the mixture undergoes photocatalytic reaction in protective atmosphere to prepare the cadmium sulfide-palladium single-atom nano catalytic material.
In some of these embodiments, the organic alcohol is selected from at least one of benzyl alcohol, 4-methylbenzyl alcohol, 4-chlorobenzyl alcohol, 2-methylbenzyl alcohol, and furfuryl alcohol.
In some of these embodiments, the organic amine is selected from at least one of aniline, 2-methylaniline, 4-chloroaniline, and butylamine.
In some embodiments, the molar ratio of the organic alcohol to the organic amine is (1-100): 1.
In some embodiments, the method further comprises the step of preparing the cadmium sulfide nanoparticles:
dissolving cadmium acetate hydrate and thiourea in water, and carrying out hydrothermal reaction.
In some of these embodiments, the molar ratio of the cadmium acetate hydrate to the thiourea is 1: (1-50).
In some embodiments, the temperature of the hydrothermal reaction is 120 ℃ to 180 ℃; the time of the hydrothermal reaction is 3-10 h.
In some of these embodiments, the soluble palladium salt is selected from at least one of palladium chloride, palladium nitrate, and palladium acetate.
In some embodiments, the mass concentration of palladium in the soluble palladium salt solution is 0.01-0.1%.
In some embodiments, the light source used for the photocatalytic reaction has a wavelength greater than 420 nm; the time of the photocatalytic reaction is 1-16 h.
The invention also provides a cadmium sulfide-palladium monatomic nano catalytic material, which is prepared according to the preparation method of the cadmium sulfide-palladium monatomic nano catalytic material.
The third aspect of the invention also provides the application of the cadmium sulfide-palladium monatomic nano catalytic material in organic amine synthesis.
The preparation method of the cadmium sulfide-palladium monatomic nano catalytic material has simple preparation process and lower equipment requirement. The cadmium sulfide-palladium monatomic nano catalytic material is prepared by the photocatalytic reaction of cadmium sulfide nanoparticles, soluble palladium salt, organic alcohol and organic amine and the coordination load of palladium monatomic on the cadmium sulfide nanoparticles, and the selective synthesis and hydrogen production process of the organic amine are realized at the same time, so that the material synthesis and the catalytic reaction are organically combined, the experimental steps are reduced, and the production process is simplified.
Compared with the traditional nano-particle catalytic material, the cadmium sulfide-palladium single-atom nano catalytic material prepared by the method has the advantages that the single-atom palladium has more abundant catalytic active sites, the loading capacity of the palladium is reduced, the cost is reduced, meanwhile, the cadmium sulfide-palladium single-atom nano catalytic material has more efficient hydrogen transfer performance, the generation of imine is reduced, and the cost for separating the product is reduced.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of cadmium sulfide nanoparticles prepared in example 1;
FIG. 2 is a Transmission Electron Microscope (TEM) picture of the cadmium sulfide nanoparticles prepared in example 1;
FIG. 3 is a graph of the ultraviolet-visible light absorption (UV-Vis) of the cadmium sulfide nanoparticles prepared in example 1;
FIG. 4 is an XRD pattern of the cadmium sulfide-palladium monatomic nanocatalysis material prepared in example 4;
FIG. 5 is a transmission electron microscope image of spherical aberration of the cadmium sulfide-palladium monatomic nano catalytic material prepared in example 4;
FIG. 6 is an X-ray absorption fine structure spectrum (EXAFS) of the cadmium sulfide-palladium monatomic nanocatalysis material prepared in example 4;
FIG. 7 is a graph showing the time-dependent substrate conversion and product selectivity of the cadmium sulfide-palladium monatomic nanocatalysis material prepared in example 4 during the synthesis of photocatalytic organic amine; wherein the line graph represents substrate conversion and the bar graph represents product selectivity;
FIG. 8 shows the substrate conversion and product distribution in the photocatalytic organic amine synthesis process of examples 4 to 7;
FIG. 9 shows hydrogen generation performance during photocatalytic organic amine synthesis of CdS of example 1, CdS-Pd SAs of example 4, and CdS-Pd NPs of comparative example 1, respectively;
FIG. 10 is a Transmission Electron Microscope (TEM) image of CdS-Pd NPs of comparative example 1;
FIG. 11 is a Transmission Electron Microscope (TEM) image of CdS-Pd NPs of comparative example 2;
FIG. 12 is a Transmission Electron Microscope (TEM) image of CdS-Pd NPs of comparative example 3.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the present invention, "first aspect", "second aspect", "third aspect", "fourth aspect" and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity indicating the technical feature indicated. Also, "first," "second," "third," "fourth," etc. are used for non-exhaustive enumeration of description purposes only and should not be construed as a closed limitation to the number.
In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features. The terms "comprising" and "including" as used herein mean open or closed unless otherwise specified. For example, the terms "comprising" and "comprises" may mean that additional components not listed may also be included or included, or that only listed components may be included or included.
In the present invention, the numerical intervals are regarded as continuous, and include the minimum and maximum values of the range and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
The percentage contents referred to in the present invention mean, unless otherwise specified, mass percentages for solid-liquid mixing and solid-solid phase mixing, and volume percentages for liquid-liquid phase mixing.
The percentage concentrations referred to in the present invention are, unless otherwise specified, the final concentrations. The final concentration refers to the ratio of the additive component in the system to which the component is added.
The temperature parameter in the present invention is not particularly limited, and is allowed to be a constant temperature treatment or a treatment within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
An embodiment of the present invention provides a method for preparing a cadmium sulfide-palladium monatomic nano catalytic material, including the following steps S100 and S200.
Step S100: and preparing cadmium sulfide nano particles.
In some of these embodiments, in step S100, the step of preparing cadmium sulfide nanoparticles comprises:
dissolving cadmium acetate hydrate and thiourea in water, and carrying out hydrothermal reaction.
The cadmium sulfide nano-particles prepared by the hydrothermal method have uniform size, stable chemical properties and physical structures, and can be used as a coordination carrier synthesized by palladium single atoms and a photocatalyst with good visible light response.
In some of these embodiments, the molar ratio of cadmium acetate hydrate to thiourea is 1: (1-50).
In some of these embodiments, the temperature of the hydrothermal reaction is 120 ℃ to 180 ℃; the time of the hydrothermal reaction is 3-10 h. Alternatively, the temperature of the hydrothermal reaction is 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃. Alternatively, the hydrothermal reaction time is 3h, 4h, 5h, 6h, 7h, 8h, 9h, or 10 h.
Specifically, cadmium acetate hydrate and thiourea were dissolved in water and stirred to form a clear mixed solution prior to hydrothermal reaction. The stirring speed is 500 rpm-800 rpm; the stirring time is 1-5 h. Alternatively, the rate of agitation is 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, or 800 rpm; the stirring time is 1h, 2h, 3h, 4h or 5 h.
In some embodiments, after the hydrothermal reaction is finished, the hydrothermal reaction system is sequentially subjected to filtering, washing and drying to obtain the cadmium sulfide nanoparticles.
Specifically, the drying treatment is carried out in a vacuum oven, and the drying temperature is 60-100 ℃; the drying time is 2-12 h. Optionally, the drying temperature is 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃; the drying time is 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12 h.
In some of these embodiments, the cadmium sulfide nanoparticles have a particle size of 20nm to 150 nm. Alternatively, the particle size of the cadmium sulfide nanoparticles may be selected from a range consisting of any of the following values: 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm or 150 nm.
Step S200: cadmium sulfide nano particles are mixed with soluble palladium salt solution, organic alcohol and organic amine, and the mixture undergoes photocatalytic reaction in protective atmosphere to prepare the cadmium sulfide-palladium monatomic nano catalytic material.
In some embodiments, step S200 comprises:
step S210: cadmium sulfide nanoparticles are dispersed in an organic solvent to prepare a suspension.
In some of these embodiments, the organic solvent may be selected from at least one of toluene, N-dimethylformamide, acetonitrile, cyclohexane, and tetrahydrofuran.
In some embodiments, in step S210, the cadmium sulfide nanoparticles have a mass of 1mg to 50 mg; the volume of the organic solvent is 1 ml-20 ml. Alternatively, the mass of the cadmium sulfide nanoparticles is 1mg, 5mg, 10mg, 15mg, 20mg, 25mg, 30mg, 35mg, 40mg, 45mg, or 50 mg.
In some of the embodiments, in step S210, the cadmium sulfide nanoparticles are dispersed in the organic solvent by means of ultrasound. Specifically, the time of ultrasonic treatment is 10min to 40 min. Optionally, the time of sonication is 10min, 15min, 20min, 25min, 30min, 35min or 40 min.
Step S220: and mixing the suspension with a soluble palladium salt solution, organic alcohol and organic amine, and carrying out photocatalytic reaction in a protective atmosphere to prepare the cadmium sulfide-palladium monatomic nano catalytic material.
In some of these embodiments, the protective atmosphere may optionally be a nitrogen atmosphere. Further, the pressure of the nitrogen is 1bar to 10 bar. Optionally, the pressure of the nitrogen is 1bar, 2bar, 3bar, 4bar, 5bar, 6bar, 7bar, 8bar, 9bar, or 10 bar.
In some of these embodiments, the organic alcohol is selected from at least one of benzyl alcohol, 4-methylbenzyl alcohol, 4-chlorobenzyl alcohol, 2-methylbenzyl alcohol, and furfuryl alcohol.
In some of these embodiments, the organic amine is selected from at least one of aniline, 2-methylaniline, 4-chloroaniline, and butylamine.
In some of these embodiments, the organic alcohol is benzyl alcohol; the organic amine is aniline.
In some embodiments, the molar ratio of the organic alcohol to the organic amine is (1-100): 1. By controlling the molar ratio of the organic alcohol to the organic amine within the range, the concentration of aldehyde generated in the reaction process can be higher, which is beneficial to the preparation of catalytic materials and the affinity addition of the organic amine; and the concentration of the organic amine is too high, so that the photogenerated holes are quenched. Optionally, the molar ratio of the organic alcohol to the organic amine can be selected from the range consisting of any of the following values: 1: 1. 2: 1. 5: 1. 10: 1. 20: 1. 25: 1. 30: 1. 40: 1. 50: 1. 60: 1. 70: 1. 80: 1. 90: 1 or 100: 1.
in some of these embodiments, the soluble palladium salt is selected from at least one of palladium chloride, palladium nitrate, and palladium acetate. Further, the soluble palladium salt is palladium chloride.
In some embodiments, the mass concentration of palladium in the soluble palladium salt solution is 0.01% to 0.1%. By controlling the mass concentration of palladium in the above range, the coordination load of palladium monoatomic atoms on cadmium sulfide nanoparticles can be realized at a lower concentration. Alternatively, the soluble palladium salt solution has a palladium concentration of 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, or 0.1% by mass.
In some of these embodiments, the photocatalytic reaction employs a light source having a wavelength greater than 420 nm; the time of the photocatalytic reaction is 1-16 h. Specifically, in the embodiment of the invention, the light source of the photocatalytic reaction is a xenon lamp light source, and the wavelength is more than 420 nm. In some of these embodiments, the time for the photocatalytic reaction is 1h, 2h, 4h, 5h, 6h, 8h, 10h, 12h, 14h, 15h, or 16 h.
In some of these embodiments, the suspension is mixed with the soluble palladium salt solution, the organic alcohol, and the organic amine by stirring. Specifically, the stirring rate is 400rpm to 800 rpm. Alternatively, the rate of agitation is 400rpm, 450rpm, 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, or 800 rpm.
The preparation method of the cadmium sulfide-palladium monatomic nano catalytic material has simple preparation process and lower equipment requirement, and is suitable for industrially preparing monatomic catalysts and synthesizing organic amine in mass production. Through the photocatalytic reaction of cadmium sulfide nanoparticles, soluble palladium salt, organic alcohol and organic amine, the organic alcohol can react to generate aldehyde, and photo-generated holes of cadmium sulfide are consumed in the photocatalytic process, so that the separation of carriers is promoted; the organic amine can react with aldehyde generated by the organic alcohol, so that the reaction balance is shifted to the right, and the carrier separation is further promoted; therefore, palladium can be coordinated and loaded on cadmium sulfide nano particles in a monatomic mode to prepare the cadmium sulfide-palladium monatomic nano catalytic material, the selective synthesis of organic amine and the hydrogen production process are realized, the material synthesis and the catalytic reaction are organically combined, the experimental steps are reduced, and the production process is simplified.
Compared with the traditional nano-particle catalytic material, the cadmium sulfide-palladium single-atom nano catalytic material prepared by the method has the advantages that the single-atom palladium has more abundant catalytic active sites, the loading capacity of the palladium is reduced, the cost is reduced, meanwhile, the cadmium sulfide-palladium single-atom nano catalytic material has more efficient hydrogen transfer performance, the generation of imine is reduced, and the cost for separating the product is reduced.
The invention also provides a cadmium sulfide-palladium monatomic nano catalytic material prepared by the preparation method of the cadmium sulfide-palladium monatomic nano catalytic material.
In some embodiments, in the cadmium sulfide-palladium monatomic nano-catalytic material, palladium element is coordinated and supported on cadmium sulfide in a monatomic form.
In some of these embodiments, the cadmium sulfide-palladium monoatomic nanocatalysis material has a particle size of 20nm to 150 nm. Alternatively, the particle size of the cadmium sulfide-palladium monatomic nanocatalysis material may be selected from the range consisting of any of the following values: 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm or 150 nm.
In some embodiments, in the cadmium sulfide-palladium monatomic nano catalytic material, the mass ratio of cadmium sulfide to palladium monatomic is (100-1000): 1. alternatively, the mass ratio of cadmium sulfide to palladium monoatomic is 100:1, 200:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1, 900:1, or 1000: 1.
The invention also provides an application of the cadmium sulfide-palladium monatomic nano catalytic material in organic amine synthesis and hydrogen production.
The cadmium sulfide-palladium monatomic nano catalytic material has high-efficiency hydrogen transfer performance and good catalytic activity and selectivity, can be used for photocatalytic organic amine synthesis and hydrogen production at normal temperature and normal pressure, solves the problem of high energy consumption in production, and can provide a green clean energy source.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Hereinafter, examples of the present invention will be described. The following described embodiments are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers.
Example 1:
the preparation of cadmium sulfide nanoparticles (CdS) of example 1 included the following steps:
(1) 0.3g of cadmium acetate dihydrate and 2.3g of thiourea were dissolved in 30ml of deionized water and stirred at 500rpm for 1h to form a homogeneous clear solution.
(2) And (2) pouring the mixed solution obtained in the step (1) into a 50ml stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, heating to 140 ℃, reacting for 5 hours, and cooling along with a furnace after the reaction is finished.
(3) And after the reaction is cooled, taking out the suspension, washing and filtering the suspension for multiple times by using deionized water and ethanol, and drying the obtained yellow solid in a vacuum oven at the temperature of 80 ℃ for 10 hours to obtain the cadmium sulfide nano-particles.
The product was characterized and analyzed using an X-ray diffractometer (XRD), a Transmission Electron Microscope (TEM) and an ultraviolet-visible absorption spectrometer (UV-Vis).
Referring to fig. 1, an XRD pattern of the cadmium sulfide nanoparticle prepared in example 1 indicates that the cadmium sulfide nanoparticle prepared in example 1 has a hexagonal structure and high crystallinity.
Referring to fig. 2, which is a TEM image of the cadmium sulfide nanoparticles prepared in example 1, it can be seen that the cadmium sulfide nanoparticles prepared in example 1 are spherical particles, have a uniform size distribution, and have an average particle size of 50 nm.
Referring to fig. 3, which is a UV-Vis diagram of the cadmium sulfide nanoparticles prepared in example 1, it can be seen that,
the cadmium sulfide nanoparticles prepared in example 1 have good absorption in the visible light range, and can be used as a good visible light-responsive semiconductor photocatalyst.
Example 2:
the preparation of cadmium sulfide nanoparticles of example 2 included the following steps:
(1) 0.3g of cadmium acetate dihydrate and 1.2g of thiourea were dissolved in 30ml of deionized water and stirred at 500rpm for 1h to form a homogeneous clear solution.
(2) And (2) pouring the mixed solution obtained in the step (1) into a 50ml stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, heating to 140 ℃, reacting for 5 hours, and cooling along with a furnace after the reaction is finished.
(3) And after the reaction is cooled, taking out the suspension, washing and filtering the suspension for multiple times by using deionized water and ethanol, and drying the obtained yellow solid in a vacuum oven at the temperature of 80 ℃ for 10 hours to obtain the cadmium sulfide nano-particles.
Example 3:
the preparation of cadmium sulfide nanoparticles of example 3 included the following steps:
(1) 0.3g of cadmium acetate dihydrate and 2.3g of thiourea were dissolved in 30ml of deionized water and stirred at 500rpm for 1h to form a homogeneous clear solution.
(2) Pouring the mixed solution obtained in the step (1) into a stainless steel high-pressure reaction kettle with a 50ml polytetrafluoroethylene lining, heating to 180 ℃, reacting for 5 hours, and cooling along with the furnace after the reaction is finished.
(3) And after the reaction is cooled, taking out the suspension, washing and filtering the suspension for multiple times by using deionized water and ethanol, and drying the obtained yellow solid in a vacuum oven at the temperature of 80 ℃ for 10 hours to obtain the cadmium sulfide nano-particles.
Example 4:
the preparation of the cadmium sulfide-palladium monatomic nanocatalysis material (CdS-Pd SAs) of example 4 comprises the following steps:
(1) weighing 10mg of the cadmium sulfide nanoparticles prepared in example 1, uniformly dispersing in 10ml of acetonitrile, and performing ultrasonic treatment for 10 min.
(2) 0.01g of a palladium chloride solution (0.1 wt% Pd), 1g of benzyl alcohol and 0.01g of aniline were added dropwise to the suspension obtained in (1), stirred at 500rpm for 30min and then transferred to a photocatalytic reaction vessel.
(3) And purging the photocatalytic reaction kettle by using nitrogen, removing residual air in the kettle, sealing the reaction kettle, and introducing 1bar of nitrogen.
(4) The mixture was illuminated from the top with a xenon lamp (λ >420 nm). The reaction was stirred continuously at 500rpm during the reaction.
(5) After 3.5h of reaction, the reactor was opened, the catalyst was filtered, and the gas and liquid phase products were quantitatively analyzed by gas chromatography.
And (3) performing structural and morphological characterization on the cadmium sulfide-palladium monatomic nano catalytic material prepared after the reaction by adopting an X-ray diffractometer (XRD), a spherical aberration transmission electron microscope and an X-ray absorption fine structure spectrum (EXAFS).
Referring to fig. 4, it is an XRD spectrum of the cadmium sulfide-palladium monatomic nano catalytic material prepared in example 4, and as a result, after the palladium monatomic grows on the surface of the cadmium sulfide in situ, the crystal structure and crystallinity of the cadmium sulfide are not significantly changed, and the cadmium sulfide is still in a hexagonal crystal system, and no significant diffraction peak of elemental palladium appears.
Referring to fig. 5, which is a transmission electron microscope image of the spherical aberration of the cadmium sulfide-palladium monatomic nano catalytic material prepared in example 4, it is apparent from the image that the white bright spot in the cadmium sulfide lattice is monatomic palladium.
Referring to fig. 6, an EXAFS spectrum of the cadmium sulfide-palladium monatomic nanocatalysis material prepared in example 4 is shown. As can be seen from the figure, in the prepared cadmium sulfide-palladium monatomic nano catalytic material, palladium exists in a form which is neither simple substance state nor divalent state, which shows that palladium and cadmium sulfide form coordination and exist in a monatomic form.
Aniline conversion and product selectivity testing:
example 4 also tested the effect of photocatalytic reaction time of the cadmium sulfide-palladium monatomic nanocatalysis material on aniline conversion and product selectivity.
The specific test method is as follows:
(1) weighing 10mg of the cadmium sulfide nanoparticles prepared in example 1, uniformly dispersing in 10ml of acetonitrile, and performing ultrasonic treatment for 10 min.
(2) 0.01g of a palladium chloride solution (0.1 wt% Pd), 1g of benzyl alcohol and 0.01g of aniline were added dropwise to the suspension obtained in (1), and the mixture was stirred at 500rpm for 30min and then transferred to a photocatalytic reaction vessel.
(3) And purging the photocatalytic reaction kettle by using nitrogen, removing residual air in the kettle, sealing the reaction kettle, and introducing 1bar of nitrogen.
(4) The mixture was irradiated from the top with a xenon lamp (λ >420 nm). The stirring was continued at 500rpm during the reaction.
(5) After reacting for 0, 3, 6, 12, 15 and 18 hours respectively, opening the reaction kettle, filtering the catalyst, and quantitatively analyzing gas phase and liquid phase products by using a gas chromatograph.
Referring to fig. 7, the curves of the substrate conversion rate and the product selectivity with time during the synthesis of organic amine by using the cadmium sulfide-palladium monatomic nano catalytic material prepared in example 4 are shown. As can be seen from the figure, the conversion and the selectivity of the product N-benzylaniline continuously increase with time, and the yield of N-benzylaniline reaches 100% after 16 hours.
Example 5:
example 5 is essentially identical to example 4, except that acetonitrile is replaced by cyclohexane.
Example 6:
example 6 is essentially identical to example 4, except that acetonitrile is replaced with N, N-dimethylformamide.
Example 7:
example 7 is essentially identical to example 4, except that acetonitrile is replaced by toluene.
FIG. 8 shows the substrate conversion and product distribution in the photocatalytic organic amine synthesis process of examples 4-7. It can be seen that under the same reaction conditions, the aniline conversion is highest with cyclohexane solvent, while the product selectivity is the best with N, N-dimethylformamide solvent.
Comparative example 1:
the cadmium sulfide-palladium nanoparticles (CdS-Pd NPs) of comparative example 1 were prepared as follows:
weighing 10mg of the cadmium sulfide nanoparticles prepared in example 1, uniformly dispersing in 10ml of acetonitrile, and performing ultrasonic treatment for 10 min. 0.01g of a palladium chloride solution (0.1 wt% Pd) was added dropwise to the suspension obtained in (1), stirred at 500rpm for 30min and then transferred to a photocatalytic reaction vessel. And purging the photocatalytic reaction kettle by using nitrogen, removing residual air in the kettle, sealing the reaction kettle, and introducing 1bar of nitrogen. The mixture was irradiated from the top with a xenon lamp (λ >420 nm). Stirring is continuously carried out in the reaction process.
The organic amine synthesis hydrogen production performance of CdS of example 1, CdS-Pd SAs of example 4 and CdS-Pd NPs of comparative example 1 were respectively tested by the following test methods: after the reaction is finished, 1ul of gas is extracted by using a gas sampling needle, and the hydrogen yield is detected by manually sampling a gas chromatograph.
Referring to FIG. 9, the hydrogen production performance of the CdS of example 1, CdS-Pd SAs of example 4, and CdS-Pd NPs of comparative example 1 during the photocatalytic organic amine synthesis process are shown. As can be seen from the figure, compared with cadmium sulfide (CdS) and palladium nanoparticle modified cadmium sulfide (CdS-Pd NPs), the hydrogen production performance of the cadmium sulfide/palladium monatomic nano catalytic material (CdS-Pd SAs) is obviously higher.
Referring to fig. 10, a Transmission Electron Microscope (TEM) image of cadmium sulfide-palladium nanoparticles (CdS-Pd NPs) prepared in comparative example 1, in which Pd is attached to the surface of the CdS nanoparticles in the form of nanoparticles, is shown.
Comparative example 2:
comparative example 2 differs from example 4 in that no benzyl alcohol was added in step (2). According to the preparation method of comparative example 2, the catalytic material prepared was cadmium sulfide-palladium nanoparticles (CdS-Pd NPs).
Referring to fig. 11, a Transmission Electron Microscope (TEM) image of cadmium sulfide-palladium nanoparticles (CdS-Pd NPs) prepared in comparative example 2, in which Pd is attached to the surface of the CdS nanoparticles in the form of nanoparticles, is shown.
Comparative example 3:
comparative example 3 differs from example 4 in that no aniline was added in step (2). According to the preparation method of comparative example 3, the catalytic material prepared was cadmium sulfide-palladium nanoparticles (CdS-Pd NPs).
Referring to fig. 12, a Transmission Electron Microscope (TEM) image of cadmium sulfide-palladium nanoparticles (CdS-Pd NPs) prepared in comparative example 3, in which Pd is attached to the surface of the CdS nanoparticles in the form of nanoparticles, is shown.
Example 8:
the preparation of the cadmium sulfide-palladium monatomic nanocatalysis material (CdS-Pd SAs) of example 8 comprises the following steps:
(1) weighing 10mg of the cadmium sulfide nanoparticles prepared in example 1, uniformly dispersing in 10ml of acetonitrile, and performing ultrasonic treatment for 10 min.
(2) 0.01g of palladium chloride solution (0.1 wt% Pd), 10mmol of organic alcohol and 0.16mmol of organic amine are respectively dripped into the suspension obtained in the step (1), and the suspension is stirred at the rotating speed of 500rpm for 30min and then transferred into a photocatalytic reaction kettle.
(3) And purging the photocatalytic reaction kettle by using nitrogen, removing residual air in the kettle, sealing the reaction kettle, and introducing 1bar of nitrogen.
(4) The mixture was irradiated from the top with a xenon lamp (λ >420 nm). The stirring was continued at 500rpm during the reaction.
(5) After 3.5h of reaction, the reactor was opened, the catalyst was filtered, and the gas and liquid products were quantitatively analyzed by gas chromatography.
In example 8, the C-N coupling reaction of an organic alcohol and an organic amine is shown by the following formula:
the kinds of organic alcohols and organic amines, and the conversion and yield of the organic amine synthesis in example 8 are reported in table 1.
Table 1 kinds of organic alcohols and organic amines of example 8, and conversion and yield of organic amine synthesis.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, which is convenient for specific and detailed understanding of the technical solutions of the present invention, but the present invention should not be construed as being limited to the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the present patent shall be subject to the content of the appended claims, and the description and drawings can be used to explain the content of the claims.
Claims (10)
1. A preparation method of a cadmium sulfide-palladium monatomic nano catalytic material is characterized by comprising the following steps:
cadmium sulfide nano particles are mixed with soluble palladium salt solution, organic alcohol and organic amine, and the mixture undergoes photocatalytic reaction in protective atmosphere to prepare the cadmium sulfide-palladium single-atom nano catalytic material.
2. The method of claim 1, wherein the organic alcohol is at least one selected from the group consisting of benzyl alcohol, 4-methylbenzyl alcohol, 4-chlorobenzyl alcohol, 2-methylbenzyl alcohol and furfuryl alcohol;
and/or the organic amine is selected from at least one of aniline, 2-methylaniline, 4-chloroaniline and butylamine.
3. The preparation method of the cadmium sulfide-palladium monatomic nanocatalysis material as claimed in claim 1, wherein the molar ratio of the organic alcohol to the organic amine is (1-100): 1.
4. The method of claim 1, further comprising the step of preparing the cadmium sulfide nanoparticles by:
dissolving cadmium acetate hydrate and thiourea in water, and carrying out hydrothermal reaction.
5. The method for preparing the cadmium sulfide-palladium monatomic nanocatalysis material according to claim 4, wherein the molar ratio of the cadmium acetate hydrate to the thiourea is 1: (1-50);
and/or the temperature of the hydrothermal reaction is 120-180 ℃; the time of the hydrothermal reaction is 3-10 h.
6. The method of claim 1, wherein the soluble palladium salt is at least one selected from the group consisting of palladium chloride, palladium nitrate, and palladium acetate.
7. The method of claim 1, wherein the palladium concentration of the soluble palladium salt solution is 0.01-0.1% by mass.
8. The method for preparing cadmium sulfide-palladium monatomic nanocatalysis material according to claim 1, wherein the wavelength of a light source used for the photocatalytic reaction is more than 420 nm; the time of the photocatalytic reaction is 1-16 h.
9. A cadmium sulfide-palladium monatomic nano catalytic material, characterized by being prepared by the method for preparing a cadmium sulfide-palladium monatomic nano catalytic material according to any one of claims 1 to 8.
10. Use of the cadmium sulfide-palladium monatomic nanocatalysis material of claim 9 in organic amine synthesis.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103331174A (en) * | 2013-07-02 | 2013-10-02 | 上海电力学院 | Palladium-loaded cadmium sulfide visible-light-induced photocatalyst and preparation method thereof |
| CN107785576A (en) * | 2017-09-15 | 2018-03-09 | 香港中文大学（深圳） | Carbene Li1‑xNaxFePO4Nano material and its preparation method and application |
| CN113042071A (en) * | 2021-03-26 | 2021-06-29 | 陕西科技大学 | Monoatomic Pd modified CdS nano-catalyst and preparation method thereof |
| CN113546652A (en) * | 2020-04-26 | 2021-10-26 | 中国科学院理化技术研究所 | Catalyst for photocatalytic Suzuki coupling reaction and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103331174A (en) * | 2013-07-02 | 2013-10-02 | 上海电力学院 | Palladium-loaded cadmium sulfide visible-light-induced photocatalyst and preparation method thereof |
| CN107785576A (en) * | 2017-09-15 | 2018-03-09 | 香港中文大学（深圳） | Carbene Li1‑xNaxFePO4Nano material and its preparation method and application |
| CN113546652A (en) * | 2020-04-26 | 2021-10-26 | 中国科学院理化技术研究所 | Catalyst for photocatalytic Suzuki coupling reaction and preparation method and application thereof |
| CN113042071A (en) * | 2021-03-26 | 2021-06-29 | 陕西科技大学 | Monoatomic Pd modified CdS nano-catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| FENG NIU ET.AL: ""Single Pd−Sx Sites In Situ Coordinated on CdS Surface as Efficient Hydrogen Autotransfer Shuttles for Highly Selective Visible-Light-Driven C−N Coupling"", 《ACS CATAL.》, pages 1 * |
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