CN109136983B - Mo/Ni/Co/P/C composite material and preparation method and application thereof - Google Patents
Mo/Ni/Co/P/C composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of composite materials, and particularly relates to a Mo/Ni/Co/P/C composite material as well as a preparation method and application thereof. The material is prepared by the following method: in a three-electrode system, a carbon-based substrate is used as a working electrode, a platinum mesh is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode, the three-electrode system is connected with an electrochemical workstation, constant potential deposition is carried out in a mixed solution of 30-70 g/L nickel sulfate, 20-40 g/L sodium hypophosphite, 10-20 g/L nickel chloride, 30-35 g/L boric acid, 30-50 g/L cobalt chloride and 40-50 g/L sodium molybdate, magnetic stirring is carried out all the time in the deposition process, the initial potential during electroplating is set to be-1.5V-1V, the electroplating time is 5-30 min, the electroplating temperature is set to be 25-35 ℃, and finally a power supply is turned off, so that the Mo/Ni/Co/P/C composite material is prepared. The Mo/Ni/Co/P/C composite material is used as a cathode material of a microbial electrolytic cell for treating coking wastewater to synchronously produce hydrogen, changes waste into valuable, and provides a new idea and a new visual angle for the imminent coking wastewater treatment.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a Mo/Ni/Co/P/C composite material as well as a preparation method and application thereof.
Background
Energy is considered the lifeline of the era. In order to meet the world energy demand, non-renewable energy sources such as coal, petroleum and natural gas are excessively used, and the exhaustion speed of natural resources is rapidly accelerated. People are eagerly searching for green renewable energy sources capable of replacing fossil energy sources. Hydrogen is favored because of its high calorific value, high thermal efficiency, and no environmental pollution. The Microbial Electrolysis Cell (MEC) hydrogen production technology is a leading topic and a hot spot of domestic and foreign research due to the advantages of low energy consumption, high efficiency, cleanness and environmental protection. Due to global energy shortage and increasingly serious pollution, the development of microbial electrolytic cell hydrogen production technology becomes necessary. The innovative technology integrating wastewater treatment and hydrogen production can bring remarkable economic benefits for developed countries and developing countries.
In MECs, the primary role of the cathode is to combine the electrons and hydrogen ions generated and transported from the anode to produce hydrogen, the most direct location for hydrogen production. Therefore, the cathode plays a very important role in the MEC hydrogen production process. The electrode materials in the conventional MEC mainly comprise stainless steel, carbon materials, noble metal platinum and the like. The Pt catalyst has better catalytic performance and smaller hydrogen production overpotential, but Pt is difficult to extract and expensive in nature, and in addition, because the coking wastewater contains sulfur element, Pt is easy to be poisoned in the using process and can cause secondary pollution to the environment, the initial purpose of energy conservation and environmental protection in the MEC hydrogen production process is violated, so the popularization and the application of the Pt catalyst in the MEC system are limited. The carbon material has larger hydrogen evolution overpotential and larger energy consumption. Therefore, a large number of inexpensive and highly efficient non-noble metal cathode catalysts with good stability need to be vigorously developed. The patent (CN108048885A) researches a nickel-phosphorus alloy electroplating method based on a levulinic acid-choline chloride eutectic solvent, and the prepared nickel-phosphorus alloy plating layer is smooth, compact and crack-free by adopting ultrasonic-assisted electroplating. But levulinic acid is slightly toxic and flammable. The choline chloride pure product is colorless crystal or white crystalline powder, has trimethylamine smell and alkali bitter taste and hygroscopicity, and 70% aqueous solution is colorless to light yellow transparent viscous liquid and has special fishy smell. It is easy to absorb carbon dioxide in air, and release ammonia odor, and can be decomposed by heat. The patent (CN105903483A) researches the preparation of molybdenum disulfide-nickel phosphorus composite material, the composite material has excellent lubricating, wear-resisting and corrosion-resisting properties, the electro-catalysis hydrogen evolution performance is excellent, the reusability is good, but the operation process is complex and the time consumption is long. Patent (CN103290425A) has studied domesticated microorganisms as cathode material of MEC, but it has disadvantages of complicated domestication operation of cathode and anode microorganisms, long domestication period, difficult control of activity, etc., and cannot ensure stable and efficient hydrogen production effect.
Disclosure of Invention
The invention aims to provide a Mo/Ni/Co/P/C composite material and a preparation method and application thereof.
The technical scheme of the invention is as follows:
a Mo/Ni/Co/P/C composite material is prepared by the following steps: in a three-electrode system, a carbon-based substrate is used as a working electrode, a platinum mesh is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode, the three-electrode system is connected with an electrochemical workstation, constant potential deposition is carried out in a mixed solution of 30-70 g/L nickel sulfate, 20-40 g/L sodium hypophosphite, 10-20 g/L nickel chloride, 30-35 g/L boric acid, 30-50 g/L cobalt chloride and 40-50 g/L sodium molybdate, magnetic stirring is carried out all the time in the deposition process, the initial potential during electroplating is set to be-1.5V-1V, the electroplating time is 5-30 min, the electroplating temperature is set to be 25-35 ℃, and finally a power supply is turned off, so that the Mo/Ni/Co/P/C composite material is prepared.
The cathode carbon-based substrate is carbon paper, carbon cloth, carbon felt, carbon fiber, carbon rods, carbon nanotubes, carbon particles, glassy carbon, porous carbon, natural graphite, graphene and fullerene.
As a preferred embodiment of the present invention, the carbon-based substrate of the present invention is pretreated as follows:
the first step is washed by distilled water;
secondly, soaking the mixture in 0.5mol/L HCL solution for 2-3 h;
thirdly, soaking the mixture in 0.5mol/L NaOH solution for 2-3 h;
fourthly, soaking the fabric in deionized water for 5-6 hours;
fifthly, ultrasonically cleaning the mixture in distilled water until the pH value is 6.8-7.2;
and sixthly, drying at the temperature of 120 ℃ for 12-13 hours.
The invention relates to a preparation method of a Mo/Ni/Co/P/C composite material, in a three-electrode system, a carbon-based substrate is taken as a working electrode, a platinum net is taken as an auxiliary electrode, Ag/AgCl is taken as a reference electrode and is connected with an electrochemical workstation, performing constant potential deposition in a mixed solution of 30-70 g/L nickel sulfate, 20-40 g/L sodium hypophosphite, 10-20 g/L nickel chloride, 30-35 g/L boric acid, 30-50 g/L cobalt chloride and 40-50 g/L sodium molybdate, performing magnetic stirring in the deposition process, setting the initial potential of-1.5V to-1V during electroplating on the working electrode, setting the electroplating time to be 5-30 min, setting the electroplating temperature to be 25-35 ℃, and finally turning off the power supply to obtain the Mo/Ni/Co/P/C composite material.
As a preferred embodiment of the present invention, the carbon-based substrate of the present invention is pretreated as follows:
the first step is washed by distilled water;
secondly, soaking the substrate in 0.5mol/L HCl solution for 2-3 h;
thirdly, soaking the mixture in 0.5mol/L NaOH solution for 2-3 h;
fourthly, soaking the fabric in deionized water for 5-6 hours;
fifthly, ultrasonically cleaning the mixture in distilled water until the pH value is 6.8-7.2;
and sixthly, drying at the temperature of 120 ℃ for 12-13 hours.
In a preferred embodiment of the present invention, the preparation method of the mixed solution of 30-70 g/L nickel sulfate, 20-40 g/L sodium hypophosphite, 10-20 g/L nickel chloride, 30-35 g/L boric acid, 30-50 g/L cobalt chloride and 40-50 g/L sodium molybdate comprises: firstly, sequentially adding a proper amount of nickel sulfate, nickel chloride, sodium hypophosphite, cobalt chloride and sodium molybdate into a beaker filled with distilled water, and placing the beaker on a magnetic stirrer to completely dissolve the added reagent; secondly, adding a proper amount of boric acid into a beaker filled with boiling water, placing the beaker on a magnetic stirrer to completely dissolve the added reagent, and mixing the two to prepare a mixed solution of 30-70 g/L of nickel sulfate, 20-40 g/L of sodium hypophosphite, 10-20 g/L of nickel chloride, 30-35 g/L of boric acid, 30-50 g/L of cobalt chloride and 40-50 g/L of sodium molybdate.
The Mo/Ni/Co/P/C composite material is used as a cathode material of a microbial electrolytic cell, and meanwhile, a domesticated carbon felt attached with a biological membrane is used as an anode, 20mL of bacterial sludge of a coking plant and 80mL of nutrient solution are used as electrolyte, and a direct current voltage of 0.3-0.9V is applied to form the microbial electrolytic cell.
In a preferred embodiment of the present invention, the nutrient solution is C6H12O6·H2O 1g/L、NH4Cl 0.31g/L、 KCl 0.13mg/L、NaH2PO4·2H2O 5.62g/L、Na2HPO4·12H2O 6.16g/L、CaCl20.01g/L；MgSO41.2g/L； NaCl 0.002g/L；FeSO46mg/L；MnSO40.76mg/L；AlCl30.5mg/L；(NH4)6Mo7O243mg/L；H3BO31mg/L；NiCl2·6H2O 0.1mg/L；CuCl20.53816mg/L；ZnCl21mg/L；CoCl2·2H2Adjusting the pH of the mixed solution of O1 mg/L to 6.8-7.2.
As a preferred embodiment of the invention, the running condition of the microbial electrolytic cell is that if the current is less than 1mA, the nutrient solution of the microbial electrolytic cell is replaced until the output current reaches 7-8 mA, and the microbial electrolytic cell can run stably.
Compared with the published documents in the background art, the invention has the following beneficial effects:
(1) one method of electroplating nickel-phosphorus alloys has been studied in the literature, but the use of the chemical levulinic acid is very toxic and flammable. The choline chloride pure product is colorless crystal or white crystalline powder, has trimethylamine smell and alkali bitterness, and the 70% aqueous solution is colorless to light yellow transparent viscous liquid and has special fishy smell. It is easy to absorb carbon dioxide in air, and release ammonia odor, and can be decomposed by heat. The medicines used in the invention are all nontoxic and harmless substances, and the defect of special odor in the literature is changed.
(2) In the literature, domesticated microorganisms are studied as cathode materials of MECs, but the domestication of microorganisms of the cathode and the anode is complex, the domestication period is long, the activity is difficult to control, and the like, so that a stable and efficient hydrogen production effect cannot be ensured. The Mo/Ni/Co/P/C composite material is used as the cathode of the microbial electrolytic cell, and has high chemical stability and toxicity resistance. The price of the raw materials is low, and compared with the Pt noble metal electrode used in the background technology, the cost is greatly reduced; compared with the common carbon cathode material, the carbon cathode material has lower hydrogen evolution overpotential, and has high hydrogen generation efficiency while reducing the cost. Overcomes the defects of complex operation, longer domestication period, difficult control of activity, and incapability of ensuring stable and high-efficiency hydrogen production efficiency in the literature.
(3) The preparation of the molybdenum disulfide-nickel phosphorus composite material is researched in the literature, and the composite material has a complex operation process and long time consumption. The operation method is simple and easy to obtain, is easy to widely apply and popularize, and overcomes the defects of complex operation process and time consumption in documents.
(4) The preparation of the Ni-Cr-Mo-Co-W composite material is researched in the literature, and the temperature for heating and forging is 1200-1220 ℃, the heat preservation time is 3-5 h, the temperature for start forging is 1170-1200 ℃, and the temperature for stop forging is 1040 ℃. And thus is greatly affected by temperature and high temperature operating conditions are not easily controlled. The reaction temperature is close to room temperature, the operation condition is mild to 25-35 ℃, and the defects of large influence of temperature condition and large energy consumption under high-temperature operation condition are overcome.
Therefore, the Mo/Ni/Co/P/C composite material is used for replacing a Pt catalyst in the prior art, has performance similar to that of the Pt catalyst, and has very high hydrogen production efficiency. Compared with a metal Ni catalyst with moderate price and high hydrogen production efficiency, the Mo/Ni/Co/P/C composite material has a plurality of unique effects as a cathode catalyst: can change the components of the alloy in a large range to achieve the required electronic structure, form the optimal electrocatalytic activity, simultaneously have high mechanical strength, excellent corrosion resistance and the like, and is an excellent electrode material.
Compared with a chemical method, the Mo/Ni/Co/P/C material prepared by the electrodeposition method has the advantages of high speed, low cost, good electrolyte stability, continuous operation and the like. The invention relates to a Mo/Ni/Co/P composite material obtained by reducing molybdate ions, nickel ions, cobalt ions and hypophosphite ions in an electrolyte solution on a cathode, belonging to a cathode electrodeposition process. The Mo/Ni/Co/P/C composite material is used as a cathode of a microbial electrolytic cell for treating coking wastewater to synchronously produce hydrogen, changes waste into valuable, and provides a new idea and a new visual angle for the imminent coking wastewater treatment.
Drawings
FIG. 1 is an X-ray diffraction pattern of a Mo/Ni/Co/P/C composite material prepared in the invention.
FIG. 2 is a scanning electron microscope image of the Mo/Ni/Co/P/C composite material prepared by the invention.
FIG. 3 is a diagram showing the effect of Mo/Ni/Co/P/C composite materials prepared in different embodiments of the present invention on the current generated by a microbial electrolytic cell.
FIG. 4 is a graph showing the effect of Mo/Ni/Co/P/C composite materials prepared in different embodiments of the present invention on the cathode and anode potentials of a microbial electrolytic cell.
FIG. 5 is a graph showing the influence of Mo/Ni/Co/P/C composite materials prepared in different embodiments of the present invention on the gas production rate of a microbial electrolytic cell.
FIG. 6 is a graph showing the gas generation composition of Mo/Ni/Co/P/C composite materials prepared according to different embodiments of the present invention.
FIG. 7 is a graph of chronoamperometry of Mo/Ni/Co/P/C composites prepared according to various embodiments of the present invention.
FIG. 8 is a chronopotentiometric graph of Mo/Ni/Co/P/C composites prepared according to various examples of the present invention.
FIG. 9 is a diagram showing the effect of coking wastewater treatment.
Detailed Description
Example 1
A Mo/Ni/Co/P/C composite material is prepared by the following steps: in a three-electrode system, a carbon-based substrate is used as a working electrode, a platinum mesh is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode, the three-electrode system is connected with an electrochemical workstation, constant potential deposition is carried out in a mixed solution of 30g/L nickel sulfate, 20g/L sodium hypophosphite, 10g/L nickel chloride, 30g/L boric acid, 30g/L cobalt chloride and 40g/L sodium molybdate, magnetic stirring is carried out all the time in the deposition process, an initial potential during electroplating is set to be-1.5V on the working electrode, the electroplating time is 5min, the electroplating temperature is set to be 25 ℃, and finally a power supply is turned off, so that the Mo/Ni/Co/P/C composite material is prepared.
In order to further characterize the Mo/Ni/Co/P composite material in this example, the prepared composite material was subjected to X-ray diffraction test, specifically, as shown in FIG. 1, an amorphous diffraction peak was observed at 45 ° 2 θ, which indicates that the Mo-Ni-Co-P composite material is an amorphous structure, and has excellent physical and chemical properties when compared with a crystalline structure. The prepared Mo/Ni/Co/P composite material is analyzed by a scanning electron microscope, specifically shown in FIG. 2, the shape is spherical, the particle size is 200-300 nm, and the larger specific surface area is beneficial to increasing hydrogen evolution active sites.
The carbon paper is pretreated by the following steps:
the first step is washed by distilled water;
secondly, soaking the mixture in 0.5mol/L HCL solution for 2 hours;
thirdly, soaking the mixture in 0.5mol/L NaOH solution for 2 hours;
fourthly, soaking the mixture in deionized water for 5 hours;
fifthly, ultrasonically cleaning the mixture in distilled water until the pH value is 6.8;
and sixthly, drying at the temperature of 120 ℃ for 12 hours.
The preparation method of the mixed solution of 30g/L nickel sulfate, 20g/L sodium hypophosphite, 10g/L nickel chloride, 30g/L boric acid, 30g/L cobalt chloride and 40g/L sodium molybdate comprises the following steps: firstly, sequentially adding a proper amount of nickel sulfate, nickel chloride, sodium hypophosphite, cobalt chloride and sodium molybdate into a beaker filled with distilled water, and placing the beaker on a magnetic stirrer to completely dissolve the added reagent; secondly, adding a proper amount of boric acid into a beaker filled with boiling water, placing the beaker on a magnetic stirrer to completely dissolve the added reagent, and mixing the two to prepare a mixed solution of 30g/L nickel sulfate, 20g/L sodium hypophosphite, 10g/L nickel chloride, 30g/L boric acid, 30g/L cobalt chloride and 40g/L sodium molybdate.
Example 2
A Mo/Ni/Co/P/C composite material is prepared by the following steps: in a three-electrode system, a carbon-based substrate is used as a working electrode, a platinum mesh is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode, the three-electrode system is connected with an electrochemical workstation, constant potential deposition is carried out in a mixed solution of 50g/L nickel sulfate, 30g/L sodium hypophosphite, 15g/L nickel chloride, 33g/L boric acid, 40g/L cobalt chloride and 45g/L sodium molybdate, magnetic stirring is carried out all the time in the deposition process, an initial potential during electroplating is set to be-1.2V on the working electrode, the electroplating time is 20min, the electroplating temperature is set to be 30 ℃, and finally a power supply is turned off, so that the Mo/Ni/Co/P/C composite material is prepared.
The carbon nano tube is pretreated by the following steps:
the first step is washed by distilled water;
secondly, soaking the mixture in 0.5mol/L HCL solution for 2.5 hours;
thirdly, soaking the mixture in 0.5mol/L NaOH solution for 2.5 hours;
fourthly, soaking the mixture in deionized water for 5.5 hours;
fifthly, ultrasonically cleaning in distilled water until the pH value is 7;
and sixthly, drying at the temperature of 120 ℃ for 12.5 hours.
The preparation method of the mixed solution of 50g/L nickel sulfate, 30g/L sodium hypophosphite, 15g/L nickel chloride, 33g/L boric acid, 40g/L cobalt chloride and 45g/L sodium molybdate comprises the following steps: firstly, sequentially adding a proper amount of nickel sulfate, nickel chloride, sodium hypophosphite, cobalt chloride and sodium molybdate into a beaker filled with distilled water, and placing the beaker on a magnetic stirrer to completely dissolve the added reagent; secondly, adding a proper amount of boric acid into a beaker filled with boiling water, placing the beaker on a magnetic stirrer to completely dissolve the added reagent, and mixing the two to prepare a mixed solution of 50g/L of nickel sulfate, 30g/L of sodium hypophosphite, 15g/L of nickel chloride, 33g/L of boric acid, 40g/L of cobalt chloride and 45g/L of sodium molybdate.
Example 3
A Mo/Ni/Co/P/C composite material is prepared by the following steps: in a three-electrode system, a carbon-based substrate is used as a working electrode, a platinum mesh is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode, the three-electrode system is connected with an electrochemical workstation, constant potential deposition is carried out in a mixed solution of 70g/L nickel sulfate, 40g/L sodium hypophosphite, 20g/L nickel chloride, 35g/L boric acid, 50g/L cobalt chloride and 50g/L sodium molybdate, magnetic stirring is carried out all the time in the deposition process, an initial potential during electroplating is set to be-1V on the working electrode, the electroplating time is 30min, the electroplating temperature is set to be 35 ℃, and finally a power supply is turned off, so that the Mo/Ni/Co/P/C composite material is prepared.
The natural graphite is pretreated by the following steps:
the first step is washed by distilled water;
secondly, soaking the mixture in 0.5mol/L HCL solution for 3 hours;
thirdly, soaking the mixture in 0.5mol/L NaOH solution for 3 hours;
fourthly, soaking the mixture in deionized water for 6 hours;
fifthly, ultrasonically cleaning the mixture in distilled water until the pH value is 7.2;
and sixthly, drying for 13 hours at the temperature of 120 ℃.
The preparation method of the mixed solution of the nickel sulfate with the concentration of 70g/L, the sodium hypophosphite with the concentration of 40g/L, the nickel chloride with the concentration of 20g/L, the boric acid with the concentration of 35g/L, the cobalt chloride with the concentration of 50g/L and the sodium molybdate with the concentration of 50g/L comprises the following steps: firstly, sequentially adding a proper amount of nickel sulfate, nickel chloride, sodium hypophosphite, cobalt chloride and sodium molybdate into a beaker filled with distilled water, and placing the beaker on a magnetic stirrer to completely dissolve the added reagent; secondly, adding a proper amount of boric acid into a beaker filled with boiling water, placing the beaker on a magnetic stirrer to completely dissolve the added reagent, and mixing the two to prepare a mixed solution of nickel sulfate with the concentration of 70g/L, sodium hypophosphite with the concentration of 40g/L, nickel chloride with the concentration of 20g/L, boric acid with the concentration of 35g/L, cobalt chloride with the concentration of 50g/L and sodium molybdate with the concentration of 50 g/L.
The cathode carbon-based substrate in this embodiment may also be carbon cloth, carbon felt, carbon fiber, carbon rod, or carbon particle, glassy carbon, porous carbon, graphene, or fullerene.
The Mo/Ni/Co/P/C composite materials prepared in different examples are used as cathodes of microbial electrolysis cells, and the electro-catalytic performance and the hydrogen production performance of the Mo/Ni/Co/P/C composite materials are compared and examined, and the results show that the Mo/Ni/Co/P/C composite materials prepared in example 2 have the best performance. As can be seen from FIG. 3, as time increases, the generated current increases and then decreases, and the Mo/Ni/Co/P/C composite material prepared in example 2 has the largest current density, which is 23.02A/m 2; as can be seen from FIG. 4, the Mo/Ni/Co/P/C composite material prepared in example 2 has the largest potential difference between the cathode and the anode; from FIGS. 5 and 6, the Mo/Ni/Co/P/C composite material prepared in example 2 has the highest gas production rate (0.354mL/cm2/h) and the hydrogen gas content is higher (69.53%); FIG. 7 is a chronoamperometric test, in which the Mo/Ni/Co/P/C composite material prepared in example 2 has the highest current density (215.32A/m2) and the highest electrocatalytic activity; FIG. 8 is a chronopotentiometric test, in which the overpotential of the Mo/Ni/Co/P/C composite material prepared in example 2 is the lowest (0.8314V) and the electrocatalytic activity is the highest.
Example 4
Taking a cathode material of a microbial electrolytic cell as a cathode, taking an acclimated carbon felt attached with a biological membrane as an anode, taking 20mL of bacterial sludge of a coking plant and 80mL of nutrient solution as electrolyte, and applying a direct current voltage of 0.3-0.9V to form a microbial electrolytic cell; the nutrient solution is C6H12O6·H2O 1g/L、NH4Cl 0.31g/L、KCl 0.13mg/L、NaH2PO4·2H2O 5.62g/L、Na2HPO4·12H2O 6.16g/L、CaCl20.01g/L；MgSO41.2g/L；NaCl 0.002g/L；FeSO46mg/L；MnSO40.76mg/L； AlCl30.5mg/L；(NH4)6Mo7O243mg/L；H3BO31mg/L；NiCl2·6H2O 0.1mg/L；CuCl20.53816mg/L； ZnCl21mg/L；CoCl2·2H2Adjusting the pH of the O1 mg/L mixed aqueous solution to 6.8-7.2.
And the running condition of the microbial electrolytic cell is that if the current is less than 1mA, the nutrient solution of the microbial electrolytic cell is replaced until the output current reaches 7-8 mA, and the microbial electrolytic cell can run stably.
The prepared Mo/Ni/Co/P composite material is used as a cathode of a microbial electrolytic cell to treat wastewater of a coking plant and produce hydrogen synchronously, and the treatment effect is shown in figure 9. After running for 3 days, the degradation rates of COD, sulfide, volatile phenol, ammonia nitrogen and cyanide are all over 90 percent.
Claims (6)
1. The Mo/Ni/Co/P/C composite material is characterized by being prepared by the following method: in a three-electrode system, a carbon-based substrate is used as a working electrode, a platinum mesh is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode, the three-electrode system is connected with an electrochemical workstation, constant potential deposition is carried out in a mixed solution of 30-70 g/L nickel sulfate, 20-40 g/L sodium hypophosphite, 10-20 g/L nickel chloride, 30-35 g/L boric acid, 30-50 g/L cobalt chloride and 40-50 g/L sodium molybdate, magnetic stirring is carried out all the time in the deposition process, the initial potential during electroplating is set to be-1.5V-1V, the electroplating time is 5-30 min, the electroplating temperature is set to be 25-35 ℃, and finally a power supply is turned off, so that the Mo/Ni/Co/P/C composite material is prepared;
the carbon-based substrate is any one of carbon paper, carbon nano tubes or natural graphite;
the carbon-based substrate is pretreated by the following steps:
the first step is washed by distilled water;
secondly, soaking the substrate in 0.5mol/L HCl solution for 2-3 h;
thirdly, soaking the mixture in 0.5mol/L NaOH solution for 2-3 h;
fourthly, soaking the fabric in deionized water for 5-6 hours;
fifthly, ultrasonically cleaning the mixture in distilled water until the pH value is 6.8-7.2;
and sixthly, drying at the temperature of 120 ℃ for 12-13 hours.
2. The method for preparing the Mo/Ni/Co/P/C composite material according to claim 1, wherein the preparation method of the mixed solution of 30-70 g/L nickel sulfate, 20-40 g/L sodium hypophosphite, 10-20 g/L nickel chloride, 30-35 g/L boric acid, 30-50 g/L cobalt chloride and 40-50 g/L sodium molybdate comprises the following steps: firstly, sequentially adding a proper amount of nickel sulfate, nickel chloride, sodium hypophosphite, cobalt chloride and sodium molybdate into a beaker filled with distilled water, and placing the beaker on a magnetic stirrer to completely dissolve the added reagent; secondly, adding a proper amount of boric acid into a beaker filled with boiling water, placing the beaker on a magnetic stirrer to completely dissolve the added reagent, and mixing the two to prepare a mixed solution of 30-70 g/L of nickel sulfate, 20-40 g/L of sodium hypophosphite, 10-20 g/L of nickel chloride, 30-35 g/L of boric acid, 30-50 g/L of cobalt chloride and 40-50 g/L of sodium molybdate.
3. The use of the Mo/Ni/Co/P/C composite material of claim 1, which is characterized by being used as a cathode material of a microbial electrolysis cell.
4. The application of the Mo/Ni/Co/P/C composite material as claimed in claim 3, wherein a microbial electrolytic cell is formed by using a cathode material of the microbial electrolytic cell as a cathode, an acclimated carbon felt with a biological membrane as an anode, 20mL of bacterial sludge of a coking plant and 80mL of nutrient solution as electrolyte and applying a direct current voltage of 0.3-0.9V.
5. The use of the Mo/Ni/Co/P/C composite material of claim 4, wherein the nutrient solution is C6H12O6·H2O 1g/L、NH4Cl 0.31g/L、KCl 0.13mg/L、NaH2PO4·2H2O 5.62g/L、Na2HPO4·12H2O6.16g/L、CaCl20.01g/L；MgSO41.2g/L；NaCl 0.002g/L；FeSO46mg/L；MnSO40.76mg/L；AlCl30.5mg/L；(NH4)6Mo7O243mg/L；H3BO31mg/L；NiCl2·6H2O 0.1mg/L；CuCl20.53816 mg/L；ZnCl21mg/L；CoCl2·2H2Adjusting the pH of the O1 mg/L mixed solution to 6.8-7.2.
6. The application of the Mo/Ni/Co/P/C composite material as claimed in claim 4, wherein the running condition of the microbial electrolytic cell is that if the generated current is less than 1mA, the nutrient solution of the microbial electrolytic cell is replaced until the output current reaches 7-8 mA, and the microbial electrolytic cell can run stably.
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