Preparation method of surface doped modified copper sulfide material

Abstract

The invention discloses a preparation method of a surface doped modified copper sulfide material, which comprises the following steps: S1, fully mixing a dopant source, a copper source, a sulfur source, a structure regulator and a solvent to form a uniform mixed solution; s2, performing solvothermal reaction on the solution to obtain doped modified sulfide; and S3, the obtained metal-doped sulfide is subjected to closed calcination under the protective atmosphere condition, and the surface-doped modified copper sulfide material is obtained. The invention aims to prepare a doped modified copper sulfide material by a simple method, the material has a micron / submicron / nano multilevel structure, the electron oxygen reduction catalytic performance can be effectively improved, and an important solution is provided for the design of a surface accurate doped modified electrocatalyst; the method has huge potential application value in the fields of in-situ hydrogen peroxide production, sewage degradation and the like. The scheme has the following advantages: 1, the prepared submicron microspheres are formed by arranging the regular hexagonal nanosheets in a staggered manner, so that a rich electrochemical interface can be provided, and the catalytic activity can be enhanced; and 2, the regular hexagonal nanosheet presents discontinuous heterogeneous doping and edge defects, so that the electronic structure is improved, the two-electron oxygen reduction activity is remarkably improved, and the hydrogen peroxide selectivity is remarkably improved. And 3, the concentration of the surface dopant and the edge defect can be accurately regulated by the addition amount of the structure regulator in the preparation process, and the two-electron oxygen reduction catalytic performance is regulated and controlled by regulating and controlling the electronic structure.

Description

Technical Field

[0001] The present invention relates to the preparation of nanomaterials, production of hydrogen peroxide by electrocatalytic oxygen reduction reaction, treatment of small molecule pollutants and other related fields, and has broad application prospects in the fields of reducing energy consumption and degrading pollutants. Background Art

[0002] Hydrogen peroxide is a versatile oxidant and an emerging sustainable energy carrier that is widely used in pulp bleaching, pathogen sterilization, and wastewater treatment. However, despite the wide range of uses of hydrogen peroxide, current large-scale production methods still use the anthraquinone process, which is hindered by high operating costs, large energy consumption, and significant environmental and safety issues. In recent years, the electrochemical synthesis of hydrogen peroxide via a two-electron electrocatalytic oxygen reduction reaction (using O2 and H2O as precursors) has emerged as a safer, simpler, and more environmentally friendly alternative to traditional methods. In addition, this method is also characterized by small equipment and flexibility, and can produce hydrogen peroxide in situ and be applied in real time in areas such as pollutant degradation.

[0003] Transition metal sulfides have better intrinsic activity in the field of electrocatalysis due to their excellent electronic conductivity, making them suitable for electrocatalysis. However, transition metal sulfides still have a large gap compared to precious metal catalysts in the process of electrocatalytic oxygen reduction reaction. Taking copper sulfide catalyst as an example, it is a p-type semiconductor with a unique band gap structure. How to increase its d-band center to the Fermi level, regulate its electronic structure, and improve the intrinsic activity of the two-electron oxygen reduction reaction is a key problem that needs to be solved. Innovative methods such as surface engineering, composition regulation and structural optimization have made some research progress in regulating the d-band center, but how to further accurately achieve structural regulation and establish the structure-performance relationship between structure and performance is the focus and difficulty of current research. By precisely adjusting the electronic structure and exposing a large number of active sites, the catalytic performance can be precisely regulated. Therefore, it is an urgent issue to invent a surface-doped modified copper sulfide catalyst that is simple, safe and effective in improving the selectivity of hydrogen peroxide.

[0004] The present invention proposes a method for preparing a surface-doped modified copper sulfide material. The material can present a variety of morphologies: nano-microspheres assembled by staggered arrangement of hexagonal nanosheets and hollow submicron tubes assembled by orderly arrangement of nano-microspheres. The material has a simple preparation procedure and has potential application value in the fields of electrocatalysis and wastewater degradation. Summary of the invention

[0005] The present invention provides a method for preparing a surface-doped modified copper sulfide material, and a catalytic material having both high two-electron oxygen reduction selectivity and adjustable morphology is obtained through a simple one-step hydrothermal method.

[0006] 1. A method for preparing a surface-doped modified copper sulfide material proposed by the present invention comprises the following steps:

[0007] S1. Fully mix the dopant source, copper source, sulfur source, structure regulator and solvent to form a uniform mixed solution;

[0008] S2, obtaining heterogeneous doped copper sulfide by subjecting the solution to a hydrothermal reaction process;

[0009] S3. The obtained heterogeneous doped copper sulfide is calcined in a closed environment under protective atmosphere conditions to obtain a heterogeneous doped copper sulfide catalytic material with edge defects.

[0010] Preferably, in the specific operation of S1: the molar mass ratio of the dopant source, the copper source and the sulfur source is (2 to 5): 1: (4 to 7), and the mixing time is 0.5 hour to 1 hour.

[0011] Preferably, in the specific operation of S1: the concentration range of the structure regulator hydrogen peroxide is between 20% and 30%, the added amount is between 0.5 mL and 2.0 mL, and the mixing time is between 10 minutes and 30 minutes.

[0012] Preferably, in the specific operation of S2: pour the mixed solution into a 100 mL polytetrafluoroethylene reactor lining, and put it into an oven for solvent thermal reaction.

[0013] Preferably, in the specific operation of S2: the solvent thermal synthesis preparation temperature is between 120° C. and 150° C., and the reaction time is between 8 hours and 10 hours.

[0014] Preferably, in the specific operation of S3: calcining the dried powder under a protective atmosphere to obtain a heterogeneous doped copper sulfide compound.

[0015] Preferably, in the specific operation of S3: the heating rate is 1°C / min to 10°C / min, the heat treatment temperature is between 150°C and 300°C, and the temperature is maintained between 2 hours and 6 hours.

[0016] Preferably, in the specific operation of S3: the protective atmosphere is nitrogen, argon or a mixture of the two.

[0017] The present invention realizes the surface doping modification of copper sulfide nanomaterials that can be precisely controlled, nano-microspheres assembled by staggered arrangement of hexagonal nanosheets, and hollow submicron tubes assembled by orderly arrangement of nano-microspheres through solvent thermal combined with calcination post-treatment. The electronic structure of the material is optimized by surface doping modification, and the active sites are increased by improving the electrochemical interface, thereby improving the electrocatalytic performance. The preparation method of the present invention is simple and easy to operate, low in cost, has potential application value in the field of electrochemical production of hydrogen peroxide for degrading sewage, and is suitable for large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 Example 1 XRD spectrum of heterogeneous doped copper sulfide

[0019] Figure 2 Example 1 Scanning electron microscope image of heterogeneous doped copper sulfide

[0020] Figure 3 Example 1 Scanning transmission electron microscope image of heterogeneous doped copper sulfide

[0021] Figure 4 Example 1 Transmission electron microscope image of heterogeneous doped copper sulfide and the corresponding energy spectrum scanning image

[0022] Figure 5 Example 2 XRD spectrum of heterogeneous doped copper sulfide

[0023] Figure 6 Example 2 SEM image of heterogeneous doped copper sulfide

[0024] Figure 7 Example 2 Transmission electron microscope image of heterogeneous doped copper sulfide

[0025] Figure 8 This is the XRD spectrum of heterogeneous doped copper sulfide in Example 3

[0026] Fig. 9 This is a scanning electron microscope image of heterogeneous doped copper sulfide in Example 3

[0027] Fig.10 This is the transmission electron microscope image of the heterogeneous doped copper sulfide in Example 3

[0028] Fig.11 The transmission electron microscope image and energy spectrum scanning image of the heterogeneous doped copper sulfide in Example 3 are

[0029] Fig.12 This is a comparison of the hydrogen peroxide selectivity of Example 3 and Example 1.

[0030] Fig.13 This is a comparison chart of the Faraday efficiency of Example 3 and Examples 2, 4, and 5.

[0031] Fig.14 This is a comparison of the hydrogen peroxide selectivity of Example 3 and Examples 2, 4, and 5.

[0032] Fig.15 The comparison of the number of transferred electrons between Example 3 and Examples 2, 4, and 5 is shown in FIG.

[0033] Fig.16 Example 4 XRD spectrum of heterogeneous doped copper sulfide

[0034] Fig.17 Example 4 SEM image of heterogeneous doped copper sulfide

[0035] Fig.18 Example 5 XRD spectrum of heterogeneous doped copper sulfide

[0036] Fig.19 Example 5 SEM image of heterogeneous doped copper sulfide

[0037] Fig. 20 This is the XRD spectrum of heterogeneous doped copper sulfide in Example 6

[0038] Fig.21 This is a scanning electron microscope image of heterogeneous doped copper sulfide in Example 6

[0039] Fig. 22 This is a comparison of the hydrogen peroxide selectivity of Example 6 and Examples 7 and 8.

[0040] Fig.23 Example 7 XRD spectrum of heterogeneous doped copper sulfide

[0041] Fig.24 Example 8 XRD spectrum of heterogeneous doped copper sulfide

[0042] Fig.25 This is the XRD spectrum of heterogeneous doped copper sulfide in Example 9

[0043] Fig.26 This is a scanning electron microscope image of heterogeneous doped copper sulfide in Example 9

[0044] Fig. 27 This is a comparison of the hydrogen peroxide selectivity of Example 9 and Examples 10 and 11.

[0045] Fig.28 This is the XRD spectrum of heterogeneous doped copper sulfide in Example 10

[0046] Fig.29 This is a scanning electron microscope image of heterogeneous doped copper sulfide in Example 10

[0047] Fig.30 This is the XRD spectrum of heterogeneous doped copper sulfide in Example 11

[0048] Fig.31 This is a scanning electron microscope image of heterogeneous doped copper sulfide in Example 11

[0049] Fig.32 This is a scanning electron microscope image of heterogeneous doped copper sulfide in Example 12

[0050] Fig.33 This is a scanning electron microscope image of heterogeneous doped copper sulfide in Example 13

[0051] Fig.34 This is a scanning electron microscope image of heterogeneous doped copper sulfide in Example 14 DETAILED DESCRIPTION

[0052] The technical solution of the present invention is described in detail below through specific embodiments.

[0053] Example 1

[0054] The present invention provides a method for preparing a surface-doped modified copper sulfide material, comprising the following steps:

[0055] S1. Fully mix the dopant source, copper source, sulfur source, structure regulator and solvent to form a uniform mixed solution;

[0056] S2, obtaining heterogeneous doped copper sulfide by subjecting the solution to a hydrothermal reaction process;

[0057] S3. The obtained heterogeneous doped copper sulfide is calcined in a closed environment under protective atmosphere conditions to obtain a heterogeneous doped copper sulfide catalytic material with edge defects.

[0058] Preferably, the specific operation of S1 is: the dopant source, the copper source, and the sulfur source are selected from cobalt chloride, copper chloride, and thioacetamide, respectively.

[0059] Preferably, in the specific operation of S1: the molar mass ratio of the dopant source, the copper source and the sulfur source is 2:1:4, and the mixing time is 0.5 hour.

[0060] Preferably, in the specific operation of S2: pour the mixed solution into a 100 mL polytetrafluoroethylene reactor lining, and put it into an oven for hydrothermal reaction.

[0061] Preferably, in the specific operation of S2: the solvent thermal synthesis preparation temperature is 140° C., and the reaction time is 10 hours.

[0062] Preferably, in the specific operation of S3: calcining the dried powder under a protective atmosphere to obtain a heterogeneous doped copper sulfide compound.

[0063] Preferably, in the specific operation of S3: the heating rate is 5°C / min, the heat treatment temperature is 200°C, and it is maintained for 2 hours.

[0064] Preferably, in the specific operation of S3: the protective atmosphere is nitrogen.

[0065] Example 2

[0066] The present invention provides a method for preparing a surface-doped modified copper sulfide material, comprising the following steps:

[0067] S1. Fully mix the dopant source, copper source, sulfur source, structure regulator and solvent to form a uniform mixed solution;

[0068] S2, obtaining heterogeneous doped copper sulfide by subjecting the solution to a hydrothermal reaction process;

[0069] S3. The obtained heterogeneous doped copper sulfide is calcined in a closed environment under protective atmosphere conditions to obtain a heterogeneous doped copper sulfide catalytic material with edge defects.

[0070] Preferably, the specific operation of S1 is: the dopant source, the copper source, and the sulfur source are selected from cobalt chloride, copper chloride, and thioacetamide, respectively.

[0071] Preferably, in the specific operation of S1: the molar mass ratio of the dopant source, the copper source and the sulfur source is 2:1:4, and the mixing time is 0.5 hour.

[0072] Preferably, in the specific operation of S1: the concentration range of the structure regulator hydrogen peroxide is 30%, the added amount is 0.5 mL, and the mixing time is 10 minutes.

[0073] Preferably, in the specific operation of S2: pour the mixed solution into a 100 mL polytetrafluoroethylene reactor lining, and put it into an oven for hydrothermal reaction.

[0074] Preferably, in the specific operation of S2: the solvent thermal synthesis preparation temperature is 140° C., and the reaction time is 10 hours.

[0075] Preferably, in the specific operation of S3: calcining the dried powder under a protective atmosphere to obtain a heterogeneous doped copper sulfide compound.

[0076] Preferably, in the specific operation of S3: the heating rate is 5°C / min, the heat treatment temperature is 200°C, and it is maintained for 2 hours.

[0077] Preferably, in the specific operation of S3: the protective atmosphere is nitrogen.

[0078] Example 3

[0079] The present invention provides a method for preparing a surface-doped modified copper sulfide material, comprising the following steps:

[0080] S1. Fully mix the dopant source, copper source, sulfur source, structure regulator and solvent to form a uniform mixed solution;

[0081] S2, obtaining heterogeneous doped copper sulfide by subjecting the solution to a hydrothermal reaction process;

[0082] S3. The obtained heterogeneous doped copper sulfide is calcined in a closed environment under protective atmosphere conditions to obtain a heterogeneous doped copper sulfide catalytic material with edge defects.

[0083] Preferably, the specific operation of S1 is: the dopant source, the copper source, and the sulfur source are selected from cobalt chloride, copper chloride, and thioacetamide, respectively.

[0084] Preferably, in the specific operation of S1: the molar mass ratio of the dopant source, the copper source and the sulfur source is 2:1:4, and the mixing time is 0.5 hour.

[0085] Preferably, in the specific operation of S1: the concentration range of the structure regulator hydrogen peroxide is 30%, the addition amount is 1.0 mL, and the mixing time is 10 minutes.

[0086] Preferably, in the specific operation of S2: pour the mixed solution into a 100 mL polytetrafluoroethylene reactor lining, and put it into an oven for hydrothermal reaction.

[0087] Preferably, in the specific operation of S2: the solvent thermal synthesis preparation temperature is 140° C., and the reaction time is 10 hours.

[0088] Preferably, in the specific operation of S3: calcining the dried powder under a protective atmosphere to obtain a heterogeneous doped copper sulfide compound.

[0089] Preferably, in the specific operation of S3: the heating rate is 5°C / min, the heat treatment temperature is 200°C, and it is maintained for 2 hours.

[0090] Preferably, in the specific operation of S3: the protective atmosphere is nitrogen.

[0091] Example 4

[0092] The present invention provides a method for preparing a surface-doped modified copper sulfide material, comprising the following steps:

[0093] S1. Fully mix the dopant source, copper source, sulfur source, structure regulator and solvent to form a uniform mixed solution;

[0094] S2, obtaining heterogeneous doped copper sulfide by subjecting the solution to a hydrothermal reaction process;

[0095] S3. The obtained heterogeneous doped copper sulfide is calcined in a closed environment under protective atmosphere conditions to obtain a heterogeneous doped copper sulfide catalytic material with edge defects.

[0096] Preferably, the specific operation of S1 is: the dopant source, the copper source, and the sulfur source are selected from cobalt chloride, copper chloride, and thioacetamide, respectively.

[0097] Preferably, in the specific operation of S1: the molar mass ratio of the dopant source, the copper source and the sulfur source is 2:1:4, and the mixing time is 0.5 hour.

[0098] Preferably, in the specific operation of S1: the concentration range of the structure regulator hydrogen peroxide is 30%, the added amount is 1.5 mL, and the mixing time is 10 minutes.

[0099] Preferably, in the specific operation of S2: pour the mixed solution into a 100 mL polytetrafluoroethylene reactor lining, and put it into an oven for hydrothermal reaction.

[0100] Preferably, in the specific operation of S2: the solvent thermal synthesis preparation temperature is 140° C., and the reaction time is 10 hours.

[0101] Preferably, in the specific operation of S3: calcining the dried powder under a protective atmosphere to obtain a heterogeneous doped copper sulfide compound.

[0102] Preferably, in the specific operation of S3: the heating rate is 5°C / min, the heat treatment temperature is 200°C, and it is maintained for 2 hours.

[0103] Preferably, in the specific operation of S3: the protective atmosphere is nitrogen.

[0104] Example 5

[0105] The present invention provides a method for preparing a surface-doped modified copper sulfide material, comprising the following steps:

[0106] S1. Fully mix the dopant source, copper source, sulfur source, structure regulator and solvent to form a uniform mixed solution;

[0107] S2, obtaining heterogeneous doped copper sulfide by subjecting the solution to a hydrothermal reaction process;

[0108] S3. The obtained heterogeneous doped copper sulfide is calcined in a closed environment under protective atmosphere conditions to obtain a heterogeneous doped copper sulfide catalytic material with edge defects.

[0109] Preferably, the specific operation of S1 is: the dopant source, the copper source, and the sulfur source are selected from cobalt chloride, copper chloride, and thioacetamide, respectively.

[0110] Preferably, in the specific operation of S1: the molar mass ratio of the dopant source, the copper source and the sulfur source is 2:1:4, and the mixing time is 0.5 hour.

[0111] Preferably, in the specific operation of S1: the concentration range of the structure regulator hydrogen peroxide is 30%, the addition amount is 2.0 mL, and the mixing time is 10 minutes.

[0112] Preferably, in the specific operation of S2: pour the mixed solution into a 100 mL polytetrafluoroethylene reactor lining, and put it into an oven for hydrothermal reaction.

[0113] Preferably, in the specific operation of S2: the solvent thermal synthesis preparation temperature is 140° C., and the reaction time is 10 hours.

[0114] Preferably, in the specific operation of S3: calcining the dried powder under a protective atmosphere to obtain a heterogeneous doped copper sulfide compound.

[0115] Preferably, in the specific operation of S3: the heating rate is 5°C / min, the heat treatment temperature is 200°C, and it is maintained for 2 hours.

[0116] Preferably, in the specific operation of S3: the protective atmosphere is nitrogen.

[0117] Example 6

[0118] The present invention provides a method for preparing a surface-doped modified copper sulfide material, comprising the following steps:

[0119] S1. Fully mix the dopant source, copper source, sulfur source, structure regulator and solvent to form a uniform mixed solution;

[0120] S2, obtaining heterogeneous doped copper sulfide by subjecting the solution to a hydrothermal reaction process;

[0121] S3. The obtained heterogeneous doped copper sulfide is calcined in a closed environment under protective atmosphere conditions to obtain a heterogeneous doped copper sulfide catalytic material with edge defects.

[0122] Preferably, the specific operation of S1 is: the dopant source, the copper source, and the sulfur source are selected from cobalt chloride, copper nitrate, and thioacetamide, respectively.

[0123] Preferably, in the specific operation of S1: the molar mass ratio of the dopant source, the copper source and the sulfur source is 2:1:4, and the mixing time is 0.5 hour.

[0124] Preferably, in the specific operation of S2: pour the mixed solution into a 100 mL polytetrafluoroethylene reactor lining, and put it into an oven for hydrothermal reaction.

[0125] Preferably, in the specific operation of S2: the solvent thermal synthesis preparation temperature is 140° C., and the reaction time is 10 hours.

[0126] Preferably, in the specific operation of S3: calcining the dried powder under a protective atmosphere to obtain a heterogeneous doped copper sulfide compound.

[0127] Preferably, in the specific operation of S3: the heating rate is 5°C / min, the heat treatment temperature is 200°C, and it is maintained for 2 hours.

[0128] Preferably, in the specific operation of S3: the protective atmosphere is nitrogen.

[0129] Example 7

[0130] The present invention provides a method for preparing a surface-doped modified copper sulfide material, comprising the following steps:

[0131] S1. Fully mix the dopant source, copper source, sulfur source, structure regulator and solvent to form a uniform mixed solution;

[0132] S2, obtaining heterogeneous doped copper sulfide by subjecting the solution to a hydrothermal reaction process;

[0133] S3. The obtained heterogeneous doped copper sulfide is calcined in a closed environment under protective atmosphere conditions to obtain a heterogeneous doped copper sulfide catalytic material with edge defects.

[0134] Preferably, the specific operation of S1 is: the dopant source, the copper source, and the sulfur source are selected from cobalt chloride, copper acetate, and thioacetamide, respectively.

[0135] Preferably, in the specific operation of S1: the molar mass ratio of the dopant source, the copper source and the sulfur source is 2:1:4, and the mixing time is 0.5 hour.

[0136] Preferably, in the specific operation of S2: pour the mixed solution into a 100 mL polytetrafluoroethylene reactor lining, and put it into an oven for hydrothermal reaction.

[0137] Preferably, in the specific operation of S2: the solvent thermal synthesis preparation temperature is 140° C., and the reaction time is 10 hours.

[0138] Preferably, in the specific operation of S3: calcining the dried powder under a protective atmosphere to obtain a heterogeneous doped copper sulfide compound.

[0139] Preferably, in the specific operation of S3: the heating rate is 5°C / min, the heat treatment temperature is 200°C, and it is maintained for 2 hours.

[0140] Preferably, in the specific operation of S3: the protective atmosphere is nitrogen.

[0141] Example 8

[0142] The present invention provides a method for preparing a surface-doped modified copper sulfide material, comprising the following steps:

[0143] S1. Fully mix the dopant source, copper source, sulfur source, structure regulator and solvent to form a uniform mixed solution;

[0144] S2, obtaining heterogeneous doped copper sulfide by subjecting the solution to a hydrothermal reaction process;

[0145] S3. The obtained heterogeneous doped copper sulfide is calcined in a closed environment under protective atmosphere conditions to obtain a heterogeneous doped copper sulfide catalytic material with edge defects.

[0146] Preferably, the specific operation of S1 is: the dopant source, the copper source, and the sulfur source are selected from cobalt chloride, copper acetylacetonate, and thioacetamide, respectively.

[0147] Preferably, in the specific operation of S1: the molar mass ratio of the dopant source, the copper source and the sulfur source is 2:1:4, and the mixing time is 0.5 hour.

[0148] Preferably, in the specific operation of S2: pour the mixed solution into a 100 mL polytetrafluoroethylene reactor lining, and put it into an oven for hydrothermal reaction.

[0149] Preferably, in the specific operation of S2: the solvent thermal synthesis preparation temperature is 140° C., and the reaction time is 10 hours.

[0150] Preferably, in the specific operation of S3: calcining the dried powder under a protective atmosphere to obtain a heterogeneous doped copper sulfide compound.

[0151] Preferably, in the specific operation of S3: the heating rate is 5°C / min, the heat treatment temperature is 200°C, and it is maintained for 2 hours.

[0152] Preferably, in the specific operation of S3: the protective atmosphere is nitrogen.

[0153] Example 9

[0154] The present invention provides a method for preparing a surface-doped modified copper sulfide material, comprising the following steps:

[0155] S1. Fully mix the dopant source, copper source, sulfur source, structure regulator and solvent to form a uniform mixed solution;

[0156] S2, obtaining heterogeneous doped copper sulfide by subjecting the solution to a hydrothermal reaction process;

[0157] S3. The obtained heterogeneous doped copper sulfide is calcined in a closed environment under protective atmosphere conditions to obtain a heterogeneous doped copper sulfide catalytic material with edge defects.

[0158] Preferably, the specific operation of S1 is: the dopant source, the copper source, and the sulfur source are selected from cobalt chloride, copper nitrate, and thioacetamide, respectively.

[0159] Preferably, in the specific operation of S1: the molar mass ratio of the dopant source, the copper source and the sulfur source is 2:1:4, and the mixing time is 0.5 hour.

[0160] Preferably, in the specific operation of S1: the concentration range of the structure regulator hydrogen peroxide is 30%, the addition amount is 1.0 mL, and the mixing time is 10 minutes.

[0161] Preferably, in the specific operation of S2: pour the mixed solution into a 100 mL polytetrafluoroethylene reactor lining, and put it into an oven for hydrothermal reaction.

[0162] Preferably, in the specific operation of S2: the solvent thermal synthesis preparation temperature is 140° C., and the reaction time is 10 hours.

[0163] Preferably, in the specific operation of S3: calcining the dried powder under a protective atmosphere to obtain a heterogeneous doped copper sulfide compound.

[0164] Preferably, in the specific operation of S3: the heating rate is 5°C / min, the heat treatment temperature is 200°C, and it is maintained for 2 hours.

[0165] Preferably, in the specific operation of S3: the protective atmosphere is nitrogen.

[0166] Example 10

[0167] The present invention provides a method for preparing a surface-doped modified copper sulfide material, comprising the following steps:

[0168] S1. Fully mix the dopant source, copper source, sulfur source, structure regulator and solvent to form a uniform mixed solution;

[0169] S2, obtaining heterogeneous doped copper sulfide by subjecting the solution to a hydrothermal reaction process;

[0170] S3. The obtained heterogeneous doped copper sulfide is calcined in a closed environment under protective atmosphere conditions to obtain a heterogeneous doped copper sulfide catalytic material with edge defects.

[0171] Preferably, the specific operation of S1 is: the dopant source, the copper source, and the sulfur source are selected from cobalt chloride, copper acetate, and thioacetamide, respectively.

[0172] Preferably, in the specific operation of S1: the molar mass ratio of the dopant source, the copper source and the sulfur source is 2:1:4, and the mixing time is 0.5 hour.

[0173] Preferably, in the specific operation of S1: the concentration range of the structure regulator hydrogen peroxide is 30%, the addition amount is 1.0 mL, and the mixing time is 10 minutes.

[0174] Preferably, in the specific operation of S2: pour the mixed solution into a 100 mL polytetrafluoroethylene reactor lining, and put it into an oven for hydrothermal reaction.

[0175] Preferably, in the specific operation of S2: the solvent thermal synthesis preparation temperature is 140° C., and the reaction time is 10 hours.

[0176] Preferably, in the specific operation of S3: calcining the dried powder under a protective atmosphere to obtain a heterogeneous doped copper sulfide compound.

[0177] Preferably, in the specific operation of S3: the heating rate is 5°C / min, the heat treatment temperature is 200°C, and it is maintained for 2 hours.

[0178] Preferably, in the specific operation of S3: the protective atmosphere is nitrogen.

[0179] Embodiment 11

[0180] The present invention provides a method for preparing a surface-doped modified copper sulfide material, comprising the following steps:

[0181] S1. Fully mix the dopant source, copper source, sulfur source, structure regulator and solvent to form a uniform mixed solution;

[0182] S2, obtaining heterogeneous doped copper sulfide by subjecting the solution to a hydrothermal reaction process;

[0183] S3. The obtained heterogeneous doped copper sulfide is calcined in a closed environment under protective atmosphere conditions to obtain a heterogeneous doped copper sulfide catalytic material with edge defects.

[0184] Preferably, the specific operation of S1 is: the dopant source, the copper source, and the sulfur source are selected from cobalt chloride, copper acetylacetonate, and thioacetamide, respectively.

[0185] Preferably, in the specific operation of S1: the molar mass ratio of the dopant source, the copper source and the sulfur source is 2:1:4, and the mixing time is 0.5 hour.

[0186] Preferably, in the specific operation of S1: the concentration range of the structure regulator hydrogen peroxide is 30%, the addition amount is 1.0 mL, and the mixing time is 10 minutes.

[0187] Preferably, in the specific operation of S2: pour the mixed solution into a 100 mL polytetrafluoroethylene reactor lining, and put it into an oven for hydrothermal reaction.

[0188] Preferably, in the specific operation of S2: the solvent thermal synthesis preparation temperature is 140° C., and the reaction time is 10 hours.

[0189] Preferably, in the specific operation of S3: calcining the dried powder under a protective atmosphere to obtain a heterogeneous doped copper sulfide compound.

[0190] Preferably, in the specific operation of S3: the heating rate is 5°C / min, the heat treatment temperature is 200°C, and it is maintained for 2 hours.

[0191] Preferably, in the specific operation of S3: the protective atmosphere is nitrogen.

[0192] Example 12

[0193] The present invention provides a method for preparing a surface-doped modified copper sulfide material, comprising the following steps:

[0194] S1. Fully mix the dopant source, copper source, sulfur source, structure regulator and solvent to form a uniform mixed solution;

[0195] S2, obtaining heterogeneous doped copper sulfide by subjecting the solution to a hydrothermal reaction process;

[0196] S3. Dry the obtained heterogeneous doped copper sulfide in a vacuum drying oven for 24 hours.

[0197] Preferably, the specific operation of S1 is: the dopant source, the copper source, and the sulfur source are selected from cobalt chloride, copper chloride, and thiourea, respectively.

[0198] Preferably, in the specific operation of S1: the molar mass ratio of the dopant source, the copper source and the sulfur source is 1:3:6, and the mixing time is 0.5 hour.

[0199] Preferably, in the specific operation of S2: pour the mixed solution into a 100 mL polytetrafluoroethylene reactor lining, and put it into an oven for hydrothermal reaction.

[0200] Preferably, in S2, the solvent thermal synthesis preparation temperature is 140° C. and the reaction time is 15 hours.

[0201] Preferably, in the specific operation of S3: drying the centrifuged sample in a vacuum drying oven at 60° C. for 24 hours.

[0202] Example 13

[0203] The present invention provides a method for preparing a surface-doped modified copper sulfide material, comprising the following steps:

[0204] S1. Fully mix the dopant source, copper source, sulfur source, structure regulator and solvent to form a uniform mixed solution;

[0205] S2, obtaining heterogeneous doped copper sulfide by subjecting the solution to a hydrothermal reaction process;

[0206] S3. Dry the obtained heterogeneous doped copper sulfide in a vacuum drying oven for 24 hours.

[0207] Preferably, the specific operation of S1 is: the dopant source, the copper source, and the sulfur source are selected from cobalt chloride, copper chloride, and thiourea, respectively.

[0208] Preferably, in the specific operation of S1: the molar mass ratio of the dopant source, the copper source and the sulfur source is 1:4:8, and the mixing time is 0.5 hour.

[0209] Preferably, in the specific operation of S2: pour the mixed solution into a 100 mL polytetrafluoroethylene reactor lining, and put it into an oven for hydrothermal reaction.

[0210] Preferably, in S2, the solvent thermal synthesis preparation temperature is 140° C. and the reaction time is 15 hours.

[0211] Preferably, in the specific operation of S3: drying the centrifuged sample in a vacuum drying oven at 60° C. for 24 hours.

[0212] Embodiment 14

[0213] The present invention provides a method for preparing a surface-doped modified copper sulfide material, comprising the following steps:

[0214] S1. Fully mix the dopant source, copper source, sulfur source, structure regulator and solvent to form a uniform mixed solution;

[0215] S2, obtaining heterogeneous doped copper sulfide by subjecting the solution to a hydrothermal reaction process;

[0216] S3. Dry the obtained heterogeneous doped copper sulfide in a vacuum drying oven for 24 hours.

[0217] Preferably, the specific operation of S1 is: the dopant source, the copper source, and the sulfur source are selected from cobalt chloride, copper chloride, and thiourea, respectively.

[0218] Preferably, in the specific operation of S1: the molar mass ratio of the dopant source, the copper source and the sulfur source is 1:5:10, and the mixing time is 0.5 hour.

[0219] Preferably, in the specific operation of S2: pour the mixed solution into a 100 mL polytetrafluoroethylene reactor lining, and put it into an oven for hydrothermal reaction.

[0220] Preferably, in S2, the solvent thermal synthesis preparation temperature is 140° C. and the reaction time is 15 hours.

[0221] Preferably, in the specific operation of S3: drying the centrifuged sample in a vacuum drying oven at 60° C. for 24 hours.

Claims

1. A method for preparing a surface-doped modified copper sulfide material, characterized in that: The steps include: S1. Fully mix the dopant source, copper source, sulfur source, structure regulator and solvent to form a uniform mixed solution; S2, obtaining a doped modified sulfide by subjecting the solution to a solvothermal reaction process; S3. The obtained metal-doped sulfide is calcined in a closed environment under protective atmosphere conditions to obtain a surface-doped modified copper sulfide material.

2. The method for preparing a surface-doped modified copper sulfide material according to claim 1, characterized in that: In step S1, the dopant source is one of cobalt chloride, cobalt nitrate, and cobalt acetate, the copper source is one of copper chloride, copper nitrate, copper acetate, and copper acetylacetonate, and the sulfur source is one of thioacetamide, thiourea, sodium thiosulfate, and elemental sulfur.

3. The method for preparing a surface-doped modified copper sulfide material according to claim 1, characterized in that: The structure regulator in step S1 is selected from hydrogen peroxide; the concentration range of the structure regulator hydrogen peroxide in step S1 is between 10% and 30%, the added amount is between 0.5mL and 2.0mL, and the mixing time is 10 minutes to 60 minutes.

4. The method for preparing a surface-doped modified copper sulfide material according to claim 1, characterized in that: In step S1, the solvent is selected from one of isopropanol, ethylene glycol, and ethanol, or a mixture of the two; the volume ratio of isopropanol or ethanol to ethylene glycol in the mixed solvent is (0.5 to 1): (2 to 5).

5. The method for preparing a surface-doped modified copper sulfide material according to claim 1, characterized in that: In step S1, the molar mass ratio of the dopant source, the copper source, and the sulfur source is (2 to 10):1:(3 to 7), and the mixing time is 0.5 hour to 1 hour.

6. The method for preparing a surface-doped modified copper sulfide material according to claim 1, characterized in that: In the step S2, the solvent thermal synthesis preparation temperature is between 120° C. and 150° C., and the reaction time is between 8 hours and 15 hours.

7. The method for preparing a surface-doped modified copper sulfide material according to claim 1, characterized in that: In step S3, the heating rate is 1°C / min to 10°C / min, the heat treatment temperature is between 150°C and 300°C, and the temperature is maintained between 2 hours and 10 hours.

8. The method for preparing a surface-doped modified copper sulfide material according to claim 1, characterized in that: The protective atmosphere in step S3 is nitrogen, argon or a mixture of the two.

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