CN109999837B - Preparation method of metal sulfide catalyst with surface defect state modification - Google Patents

Preparation method of metal sulfide catalyst with surface defect state modification Download PDF

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CN109999837B
CN109999837B CN201910359800.5A CN201910359800A CN109999837B CN 109999837 B CN109999837 B CN 109999837B CN 201910359800 A CN201910359800 A CN 201910359800A CN 109999837 B CN109999837 B CN 109999837B
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nitrate
cysteine
metal sulfide
sulfide catalyst
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CN109999837A (en
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孟苏刚
郑秀珍
吴惠惠
付先亮
陈士夫
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Huaibei Normal 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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J35/39—
    • 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
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom

Abstract

The invention discloses a preparation method of a metal sulfide catalyst with a surface defect state modification, which comprises the following steps: (1) respectively weighing three raw materials of nitrate, indium nitrate hydrate or lanthanum nitrate or zinc nitrate and cysteine, placing the raw materials into a beaker filled with deionized water, and stirring and dissolving to obtain a mixed solution; (2) and (2) respectively transferring the mixed solution obtained in the step (1) into a polytetrafluoroethylene lining, sealing, washing by using deionized water after hydrothermal treatment, and drying in vacuum to obtain the surface defect state modified metal sulfide catalyst. Catalyst of the invention increases N2Molecular reaction activity, and the progress of nitrogen fixation reaction is promoted. The synthetic route is simple and easy to implement and has universality.

Description

Preparation method of metal sulfide catalyst with surface defect state modification
Technical Field
The invention relates to a preparation method of a catalyst, in particular to a preparation method of a metal sulfide catalyst with a modified surface defect state.
Background
Semiconductor photocatalytic nitrogen fixation due to its high efficiency cleaningHas attracted great attention worldwide. Similar to biological nitrogen fixation enzyme, N can be converted under mild conditions by the photocatalysis process by using sunlight to excite a photocatalyst2Reduction to NH3To a cleaner and more sustainable NH3The production provides a non-carbonized road. The photocatalysis technology can directly convert solar energy into chemical energy, and provides a method with great prospect for reducing the energy consumption of ammonia synthesis. However, the ultra-high bonds of the nitrogen-nitrogen triple bonds enable the nitrogen molecules to exhibit stable chemical properties, thereby making it difficult for conventional photocatalytic materials to activate the nitrogen molecules. Therefore, the development of efficient nitrogen fixation ammonia synthesis photocatalyst still faces huge challenges.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a preparation method of a metal sulfide catalyst with surface defect state modification, which improves N2Molecular reaction activity, and the progress of nitrogen fixation reaction is promoted.
The technical scheme is as follows: the invention provides a preparation method of a metal sulfide catalyst with a modified surface defect state, which comprises the following steps:
(1) respectively weighing nitrate, indium nitrate hydrate and cysteine, placing the weighed materials into a beaker filled with deionized water, and stirring and dissolving the materials to obtain a mixed solution;
(2) and (2) respectively transferring the mixed solution obtained in the step (1) into a polytetrafluoroethylene lining, sealing, washing by using deionized water after hydrothermal treatment, and drying in vacuum to obtain the catalysts modified by different surface defect states.
Further, the temperature of the hydrothermal treatment in the step (1) is 200 ℃. The nitrate in the step (1) is zinc nitrate.
Further, the molar amounts of the zinc nitrate, the indium nitrate hydrate and the cysteine in the step (1) are 1.5mmol, 1mmol and 3mmol respectively, and the product in the step (2) is Zn-defect Zn3In2S6. The molar weight of the zinc nitrate, the indium nitrate hydrate and the cysteine in the step (1) are respectively 2mmol, 1mmol and 3.5mmol, and the product in the step (2) is Zn-defect Zn4In2S7. The zinc nitrate, the indium nitrate hydrate and the semi-product of the step (1)The molar weight of cystine is respectively 2.5mmol, 1mmol and 4mmol, and the product in step (2) is Zn-defect Zn5In2S8。
Further, in the step (1), the nitrate is cadmium nitrate.
Further, the molar weight of the cadmium nitrate, the indium nitrate hydrate and the cysteine in the step (1) are respectively 0.5mmol, 1mmol and 2mmol, and the product in the step (2) is Cd defect-CdIn2S4. The molar weights of the cadmium nitrate, the lanthanum nitrate and the cysteine in the step (1) are respectively 0.5mmol, 1mmol and 2mmol, and the product in the step (2) is Cd defect-CdLa2S4. The molar weights of the cadmium nitrate, the lanthanum nitrate and the cysteine in the step (1) are respectively 0.5mmol, 1mmol and 2mmol, and the product in the step (2) is Cd defect-CdLa2S4. The molar weight of the cadmium nitrate, the zinc nitrate and the cysteine in the step (1) are respectively 0.75mmol, 0.25mmol and 2mmol, and the product in the step (2) is Zn defect-Cd0.75Zn0.25S。
In the technical scheme, the surface defect site of the catalyst can be used as an active site for nitrogen molecule chemical adsorption, and electrons in the local defect site can be transferred to enter a reverse bond pi orbit for adsorbing nitrogen molecules, so that the weakening effect on nitrogen-nitrogen triple bonds and the separation of photo-generated electrons and holes are realized. Promoting photocatalytic N2And the reduction reaction efficiency is improved.
Has the advantages that: the construction of the surface defect state of the catalyst of the invention is beneficial to N2Adsorption and activation of molecules and separation of photo-generated electrons and holes improve nitrogen fixation efficiency. The synthesis route is simple and easy to implement, has universality, and can be popularized and applied to synthesis of other various transition metal sulfide semiconductors.
Drawings
FIG. 1 shows Zn deficiency-Zn prepared in examples 1 and 23In2S6And Zn3In2S6X-ray powder diffractogram of the catalyst;
FIG. 2 is a diagram illustrating the preparation of Zn defect-Zn in example 13In2S6The (a) TEM and (b) HRTEM images of (a);
FIG. 3 is a schematic view ofEXAMPLE 2 preparation of Zn3In2S6HRTEM image of (A);
FIG. 4 Zn Defect-Zn prepared in examples 1 and 23In2S6And Zn3In2S6An EPR spectrum of the catalyst;
FIG. 5 shows Zn deficiency-Zn prepared in examples 1 and 23In2S6And Zn3In2S6Coupling a biomass alcohol selective conversion bifunctional system to selectively oxidize benzyl alcohol to benzaldehyde and fix nitrogen in a photocatalytic manner;
FIG. 6 shows Zn defect-Zn prepared in example 13In2S6A pure water system photocatalysis nitrogen fixation activity diagram;
FIG. 7 shows Zn defect-Zn prepared in example 13In2S6A sacrificial agent system photocatalysis nitrogen fixation activity diagram;
FIG. 8 shows Zn defect-Zn prepared in example 13In2S6A nitrogen fixation activity diagram of the 5-hydroxymethylfurfural prepared by photocatalytic biomass glucose selective conversion by a dual-functional system;
FIG. 9 shows Zn prepared in example 6, example 1, example 6, example 11, example 10, example 13 and example 123In2S6Zn defect-Zn3In2S6、Cd0.75Zn0.25S, Zn Defect-Cd0.75Zn0.25S、CdIn2S4Cd defect-CdIn2S4、CdLa2S4Cd defect-CdLa2S4X-ray powder diffractogram of the catalyst;
FIG. 10 shows Zn prepared in example 6, example 1, example 6, example 11, example 10, example 13 and example 123In2S6Zn defect-Zn3In2S6、Cd0.75Zn0.25S, Zn Defect-Cd0.75Zn0.25S、CdIn2S4Cd defect-CdIn2S4、CdLa2S4Cd defect-CdLa2S4An EPR spectrum of the catalyst;
FIG. 11 shows Zn prepared in example 6, example 1, example 6, example 11, example 10, example 13 and example 123In2S6Zn defect-Zn3In2S6、Cd0.75Zn0.25S, Zn Defect-Cd0.75Zn0.25S、CdIn2S4Cd defect-CdIn2S4、CdLa2S4Cd defect-CdLa2S4A pure water system photocatalysis nitrogen fixation activity diagram of the catalyst;
FIG. 12 shows Cd prepared in example 60.75Zn0.25S and Zn Defect-Cd0.75Zn0.25S coupling a biomass alcohol selective conversion dual-function system to selectively oxidize the benzyl alcohol to benzaldehyde and fix nitrogen in a photocatalytic manner;
FIG. 13 shows Zn deficiency-Cd prepared in example 60.75Zn0.25An S dual-function system is used for preparing a nitrogen fixation activity diagram of 5-hydroxymethylfurfural through selective conversion of photocatalytic biomass glucose;
FIG. 14 is a schematic diagram of the mechanism of the photocatalytic nitrogen fixation reaction activity of the present invention.
Detailed Description
The transition metal sulfide may be abbreviated as TMDs, and the transition metal sulfide containing defects may be abbreviated as defect-TMDs.
Example 1
This example prepares Zn-deficient Zn as follows3In2S6(when x is 3) catalyst:
step 1, weighing 1.5mmol of zinc nitrate, 1mmol of indium nitrate hydrate and 3mmol of cysteine respectively, and stirring to dissolve in a beaker filled with 60mL of deionized water;
step 2, transferring the mixed solution obtained in the step 1 into 100ml of polytetrafluoroethylene lining, sealing, carrying out hydrothermal treatment at 200 ℃ for 20 hours, washing by deionized water, and carrying out vacuum drying to obtain Zn defect-Zn3In2S6A catalyst.
Other catalysts for surface defect modification: (Transition metal sulfide (TMDS)) Zn defect-Zn with modified surface defectsxIn2S3+x(x ═ 1 to 5) and the like can be prepared by the above-mentioned production method by changing the raw materials and the process conditions. Wherein, the metal element raw materials are all nitrates thereof, the raw material proportion adopts the atomic composition ratio of TMDS, and other conditions are unchanged.
Example 2
This example prepares a Zn-deficient ZnIn by the following procedure2S4(when x is 1) catalyst:
zn-deficient ZnIn2S4The synthesis of (2): 0.5mmol zinc nitrate, 1mmol indium nitrate hydrate and 2mmol cysteine; other conditions were unchanged.
And Zn defect-Zn in example 13In2S6The synthesis method of the catalyst is the same, and the input amount ratio of raw materials is changed.
Example 3
This example prepares Zn-deficient Zn as follows2In2S5(when x is 2) catalyst:
zn-deficient ZnIn2S5The synthesis of (2): 1mmol zinc nitrate, 1mmol indium nitrate hydrate and 2.5mmol cysteine; other conditions were unchanged.
And Zn defect-Zn in example 13In2S6The synthesis method of the catalyst is the same, and the input amount ratio of raw materials is changed.
Example 4
This example prepares Zn-deficient Zn as follows4In2S7(when x is 4) catalyst:
zn-deficient ZnIn2S7The synthesis of (2): 2mmol zinc nitrate, 1mmol indium nitrate hydrate and 3.5mmol cysteine; other conditions were unchanged.
And Zn defect-Zn in example 13In2S6The synthesis method of the catalyst is the same, and the input amount ratio of raw materials is changed.
Example 5
This example prepares Zn-deficient Zn as follows5In2S8(when x is 5) catalyst:
zn-deficient ZnIn2S8The synthesis of (2): 2.5mmol zinc nitrate, 1mmol indium nitrate hydrate and 4mmol cysteine; other conditions were unchanged.
And Zn defect-Zn in example 13In2S6The synthesis method of the catalyst is the same, and the input amount ratio of raw materials is changed.
Example 6
This example is identical to example 1, except that Zn was prepared in step 2 at a hydrothermal temperature of 180 ℃3In2S6A catalyst.
For Zn defect-Zn prepared in inventive example 13In2S6And Zn prepared in example 63In2S6The catalyst was characterized and the results are shown in fig. 1, fig. 2, fig. 3 and fig. 4. Wherein FIG. 1 is an X-ray diffraction (XRD) pattern, Zn defect-Zn3In2S6And Zn3In2S6All diffraction peaks in the diffraction diagram correspond well to hexagonal phase Zn3In2S6. As can be derived from the figures, the drawing,
Figure BDA0002044826500000041
α ═ β ═ 90 °, γ ═ 120 °. Illustrating pure phase Zn3In2S6Without the formation of new material phases due to Zn-defects.
FIG. 2 shows Zn defect-Zn3In2S6The images of the Transmission Electron Microscope (TEM) and the high-resolution transmission electron microscope (HRTEM) show that the sample is an ultrathin two-dimensional sheet structure (figure (a)), Zn defect-Zn3In2S6In which lattice fringes containing defect states are clearly visible (indicated by arrows, (b) figure). And Zn3In2S6Clear and complete lattice fringes (FIG. 3), and Zn defect-Zn3In2S6In sharp contrast with the HRTEM images of (g).
To further confirm the presence of defect states, Electron Paramagnetic Resonance (EPR) is an advantageous tool for characterizing material defects, as can be seen in fig. 3, Zn3In2S6No obvious EPR peak, and Zn defect-Zn3In2S6The EPR peak of (A) is sharp and the g-factor is 2.003, indicating that Zn was prepared in example 13In2S6The catalyst surface is rich in Zn defects, while Zn prepared in example 63In2S6The catalyst has no Zn defect (in the optimization of experimental conditions, we find that the Zn in a defect state can not be synthesized below 200 DEG C3In2S6). From the above analysis, it is understood that the two-dimensional TMDs containing defects can be easily prepared by the present method by changing the reaction temperature.
To examine the universality of the experimental method, a series of surface defect modified Transition Metal Sulfides (TMDs) (catalysts) were synthesized by changing the reactant raw materials: cd defect-CdIn2S4Cd defect-CdLa2S4Zn defect-CdxZn1-xS (x ═ 0-1) and Zn defect-ZnxIn3S3+x(x-1-5). Wherein, the metal element raw materials are all nitrates thereof, the raw material proportion adopts the atomic composition ratio of TMDS, and other conditions are unchanged.
For example: zn defect-Cd0.5Zn0.5S synthesis: 0.5mmol cadmium nitrate, 0.5mmol zinc nitrate and 2mmol cysteine; other conditions were the same as in example 1.
For example: zn defect-Cd0.75Zn0.25S synthesis: 0.75mmol cadmium nitrate, 0.25mmol zinc nitrate and 2mmol cysteine; other conditions were the same as in example 1.
When the hydrothermal temperature in the step 2 of the above conditions is changed to 180 ℃, other conditions of the raw materials are unchanged, and the Cd is prepared0.75Zn0.25S。
Example 7
This example is the construction of a bifunctional reaction system (the mixed solution of biomass containing alcoholic hydroxyl group and water adopts benzyl alcohol), and the detailed steps are as follows:
step 1, 0.03g of Zn-deficient Zn3In2S6Adding a catalyst and 50mL of benzyl alcohol into a 100mL three-port polytetrafluoroethylene reaction kettle;
step 2, introducing N into the reaction kettle2After the air in the reaction kettle is exhausted, the reaction kettle is kept at N2The pressure is about 0.2 Mpa;
and 3, stirring for about 0.5 hour in a dark state, after adsorption and desorption balance, turning on a visible light source, extracting 5mL of reaction liquid every 1 hour, performing centrifugal separation, and analyzing and detecting liquid-phase products such as ammonia, aldehyde and the like in the reaction liquid.
Example 8
This example is pure water N2Reduction, this example is the same as example 7 except that 50mL of deionized water was added in step 1.
Example 9
This example is a sacrificial agent system N2The reduction procedure was the same as in example 8 except that 50mL of aqueous methanol (20% by volume) was added in step 1.
The results of example 7, example 8 and example 9 are shown in fig. 5, fig. 6 and fig. 7, respectively. As can be seen from FIG. 5, pure Zn3In2S6Only shows selective oxidation activity, namely, can selectively oxidize benzyl alcohol into benzaldehyde, but can not reduce N2. This indicates Zn3In2S6Has proper valence band position (hole oxidizing ability) and can selectively oxidize benzyl alcohol to benzaldehyde, and the conduction band position is relatively negative but can not reduce N2This also states N2The molecules are extremely stable and difficult to activate. And Zn defect-Zn3In2S6Example 3 not only can selectively oxidize benzyl alcohol to benzaldehyde, but also can efficiently oxidize N2Reduction to NH3The yield reaches 0.95 mmol/g/h. This is because on the one hand benzyl alcohol is dehydrogenated to N2The hydrogenation coupling reaction system can obviously improve the N of a pure water system2Thermodynamics of reduction (greatly reduced Gibbs free energy Δ G °), on the other hand Zn-defects can activate N2Molecules and enriched photogenerated electrons enhance reaction kinetics. To illustrate the advantages of this bifunctional coupling reaction system, we performed two sets of control experiments: one is pure water system N2Reduction (FIG. 6) and sacrificial agent System N2Reduction (fig. 7). Zn defect-Zn3In2S6Although N can be reduced in a pure water system2Preparation of NH3But the yield was extremely low. The addition of the hole sacrificial agent can obviously improve the photocatalytic activity of the material, but can release environmentally-unfriendly substances such as CO, CO2 and HCHO. As can be seen from the analysis of the above results, the patent proposes a preparation scheme of TMDs modified in surface defect state and a novel N designed2A reductive bifunctional photocatalytic coupling reaction system is feasible.
In order to further expand the universality of the preparation scheme of the surface defect state modified TMDs, which is provided by the patent, the Cd defect-CdIn is successfully prepared by changing reaction raw materials2S4Cd defect-CdLa2S4Zn defect-CdxZn1-xS (x ═ 0-1) and Zn defect-ZnxIn2S3+xAnd (x-1-5) and the like. And in N2Shows better selective oxidation and N in a reduction bifunctional photocatalytic reaction system2Reduction performance.
In order to further investigate the practical operability of the scheme, biomass glucose which is more widely and easily available is taken as a raw material, and Zn defect-Zn is investigated3In2S6Photocatalytic selective conversion of glucose and N2Reducing the performance of the bifunctional reaction system. As shown in FIG. 8, initially the glucose is slowly converted to the high value-added chemical 5-hydroxymethylfurfural without NH3And (4) generating. Because in the bifunctional coupling reaction system, the light-excited semiconductor generates electron-hole pairs, and the photogenerated holes selectively oxidize hydroxyl and dehydrogenate to generate carbonyl compounds and release hydrogen; then released hydrogen and N2Is reduced by photo-generated electrons to generate NH3(fig. 9), therefore a hysteresis effect is reacted. 5-hydroxymethylfurfural and NH with prolonged reaction time3The yield of the double-function coupling reaction system is steadily increased, and the potential value of the double-function coupling reaction system is proved again.
From the above results, it can be seen that N constructed by the present invention2The reduction bifunctional photocatalytic reaction system has simple and convenient process flow, and can effectively realize N2Resource utilization and can prepare the hydrocarbon CxHyOzThe catalyst of the invention to this N2The reduction bifunctional photocatalytic reaction has very good activity. The method provides more abundant catalyst selection and development space for the industrial application of the dual-function photocatalytic reaction system, such as the selection of different catalysts according to different reaction substrates and different target products or the construction of band transfer and Z-type composite photocatalyst materials.
Example 10
This example prepares Cd defect-CdIn as follows2S4Catalyst:
cd defect-CdIn2S4The synthesis of (2): 0.5mmol cadmium nitrate, 1mmol indium nitrate hydrate and 2mmol cysteine; other conditions were the same as in example 1.
Example 11
This example prepares CdIn as follows2S4Catalyst:
this example is the same as example 10, except that the hydrothermal temperature in step 2 was 180 ℃ to prepare CdIn2S4A catalyst.
Example 12
This example prepares Cd defect-CdLa as follows2S4Catalyst:
cd defect-CdIn2S4The synthesis of (2): 0.5mmol cadmium nitrate, 1mmol lanthanum nitrate and 2mmol cysteine; other conditions were the same as in example 1.
Example 13
This example prepares CdLa as follows2S4Catalyst:
this example is the same as example 12 except that the hydrothermal temperature in step 2 was 180 ℃ to prepare CdLa2S4A catalyst.
Example 14
Zn prepared in example 6, example 1, example 6, example 11, example 10, example 13 and example 123In2S6Zn defect-Zn3In2S6、Cd0.75Zn0.25S, Zn Defect-Cd0.75Zn0.25S、CdIn2S4Cd defect-CdIn2S4、CdLa2S4Cd defect-CdLa2S4X-ray powder diffraction analysis of the catalyst resulted in the preparation of transition metal sulfides (TMDS) Zn3In2S6、Cd0.75Zn0.25S、CdIn2S4And Cdla2S4The XRD spectrum of the compound shows that the prepared transition metal sulfide is pure hexagonal phase. And containing defective transition metal sulfides (V-TMDS) Zn defect-Zn3In2S6Zn defect-Cd0.75Zn0.25S, Cd defect-CdIn2S4And Cd defect-CdLa2S4The XRD spectrum of the catalyst is basically the same as that of the defect-free transition metal sulfide, and no obvious change is generated, which indicates that the crystal phase structure of the defect-containing transition metal sulfide is not changed.
Example 15
The Zn prepared in example 6, example 1, example 6, example 11, example 10, example 13 and example 12 are respectively used3In2S6Zn defect-Zn3In2S6、Cd0.75Zn0.25S, Zn Defect-Cd0.75Zn0.25S、CdIn2S4Cd defect-CdIn2S4、CdLa2S4Cd defect-CdLa2S4The EPR spectrogram analysis is carried out on the catalyst, in order to confirm the existence of a defect state, Electron Paramagnetic Resonance (EPR) is a favorable tool for characterizing material defects, and as seen from figure 10, TMDS has no obvious EPR peak, while the EPR peak of V-TMDS is sharp, which indicates that the TMDS catalyst prepared at the temperature of 200 ℃ contains abundant Zn or Cd defects on the surface, while the TMDS catalyst prepared at the temperature of 180 ℃ has no defects (in the optimization of experimental conditions, we find that the TMDS in the defect state can not be synthesized at the temperature lower than 200 ℃). From the above analysis, it is understood that the two-dimensional TMDs containing defects can be easily prepared by the present method by changing the reaction temperature.
Example 16
Zn prepared in the above examples3In2S6Zn defect-Zn3In2S6、Cd0.75Zn0.25S, Zn Defect-Cd0.75Zn0.25S、CdIn2S4Cd defect-CdIn2S4、CdLa2S4Cd defect-CdLa2S4Carrying out photocatalytic nitrogen fixation activity analysis on the catalyst; in order to examine the superiority of V-TMDs in photocatalytic nitrogen fixation, the performances of the V-TMDs were tested in a pure water system, and as shown in FIG. 11, under the same conditions, the defect-free TMDs showed no activity on photocatalytic nitrogen fixation, while the defect-containing V-TMDs showed significant photocatalytic nitrogen fixation activity, wherein Zn defect-Cd defect0.75Zn0.25S has the best activity.
Example 17
Cd prepared for the above example0.75Zn0.25S and Zn Defect-Cd0.75Zn0.25S coupling the photocatalytic selective oxidation of the benzyl alcohol to benzaldehyde by the biomass alcohol selective conversion dual-function system and analyzing the activity of nitrogen fixation; from FIG. 12, pure Cd can be seen0.75Zn0.25S only shows selective oxidation activity, namely, the benzyl alcohol can be selectively oxidized into benzaldehyde, but N cannot be reduced2. This indicates Cd0.75Zn0.25S has a proper valence band position (hole oxidation capacity) and can selectively oxidize benzyl alcohol into benzaldehyde, and N cannot be reduced although the conduction band position is negative2This also states N2The molecules are extremely stable and difficult to activate. And Zn defect-Cd0.75Zn0.25S not only can selectively oxidize benzyl alcohol into benzaldehyde, but also can efficiently oxidize N2Reduction to NH3The yield reaches 1030 mu mol/g/h. This is because on the one hand benzyl alcohol is dehydrogenated to N2The hydrogenation coupling reaction system can obviously improve the N of a pure water system2Thermodynamics of reduction (Gibbs free energy is greatly reduced delta G DEG, the Gibbs free energy of pure water photocatalysis nitrogen fixation is about 681.1KJ/mol, and the Gibbs free energy of benzyl alcohol coupling photocatalysis nitrogen fixation is about 51.1KJ/mol), on the other hand, Zn-defect can activate N2Molecular and enrichment photogenerationAnd enhances the reaction kinetics.
Example 18
For Zn-deficient-Cd prepared in example 60.75Zn0.25And (3) carrying out nitrogen fixation activity analysis while preparing 5-hydroxymethylfurfural by photocatalytic biomass glucose selective conversion through the S dual-function system.
In order to further investigate the actual operability of the scheme, biomass glucose which is more widely and easily obtained is used as a raw material, and the Zn defect-Cd is investigated0.75Zn0.25S photocatalytic selective conversion of glucose and N2Reducing the performance of the bifunctional reaction system. As shown in FIG. 13, initially the glucose is slowly converted to the high value-added chemical 5-hydroxymethylfurfural without NH3And (4) generating. Because in the bifunctional coupling reaction system, the light-excited semiconductor generates electron-hole pairs, and the photogenerated holes selectively oxidize hydroxyl and dehydrogenate to generate carbonyl compounds and release hydrogen; then released hydrogen and N2Is reduced by photo-generated electrons to generate NH3(fig. 14), therefore a hysteresis effect is reflected. 5-hydroxymethylfurfural and NH with prolonged reaction time3The yield of (a) is steadily increasing, again demonstrating the potential utility of TMDs containing defects (denoted as V-TMDs). Among the foregoing several defect-containing metal sulfide catalysts, Zn-deficient-Cd0.75Zn0.25S shows better activity, and the activity of the S is further coupled with benzyl alcohol for nitrogen fixation, so that the activity of the S is obviously superior to that of a pure water system; further conversion of benzyl alcohol to a broader range of biomass alcohols such as glucose found Zn defect-Cd0.75Zn0.25S can also realize glucose and N2Coupling reaction of reduction.

Claims (7)

1. A preparation method of a surface defect state modified metal sulfide catalyst for a photocatalytic nitrogen fixation coupled biomass selective conversion bifunctional reaction system is characterized by comprising the following steps of: the method comprises the following steps:
(1) respectively weighing zinc nitrate, indium nitrate hydrate and cysteine; or cadmium nitrate, zinc nitrate and cysteine; or cadmium nitrate, lanthanum nitrate and cysteine; or cadmium nitrate, indium nitrate hydrate and cysteine, placing the three raw materials into a beaker filled with deionized water, and stirring and dissolving to obtain a mixed solution;
(2) respectively transferring the mixed solution obtained in the step (1) into a polytetrafluoroethylene lining, sealing, washing by using deionized water after hydrothermal treatment, and drying in vacuum to obtain a surface defect state modified metal sulfide catalyst;
the temperature of the hydrothermal treatment in the step (2) is 200 ℃, and the time is 20 hours.
2. The method for producing a surface-defect-state-modified metal sulfide catalyst according to claim 1, characterized in that: the molar weight of the zinc nitrate, the indium nitrate hydrate and the cysteine in the step (1) are respectively 1.5mmol, 1mmol and 3 mmol.
3. The method for producing a surface-defect-state-modified metal sulfide catalyst according to claim 1, characterized in that: the molar weight of the zinc nitrate, the indium nitrate hydrate and the cysteine in the step (1) are respectively 2mmol, 1mmol and 3.5 mmol.
4. The method for producing a surface-defect-state-modified metal sulfide catalyst according to claim 1, characterized in that: the molar weight of the zinc nitrate, the indium nitrate hydrate and the cysteine in the step (1) are respectively 2.5mmol, 1mmol and 4 mmol.
5. The method for producing a surface-defect-state-modified metal sulfide catalyst according to claim 1, characterized in that: the molar weight of the cadmium nitrate, the indium nitrate hydrate and the cysteine in the step (1) are respectively 0.5mmol, 1mmol and 2 mmol.
6. The method for producing a surface-defect-state-modified metal sulfide catalyst according to claim 1, characterized in that: the molar weight of the cadmium nitrate, the lanthanum nitrate and the cysteine in the step (1) are respectively 0.5mmol, 1mmol and 2 mmol.
7. The method for producing a surface-defect-state-modified metal sulfide catalyst according to claim 1, characterized in that: the molar weight of the cadmium nitrate, the zinc nitrate and the cysteine in the step (1) are respectively 0.75mmol, 0.25mmol and 2 mmol.
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