CN111905743A - Preparation method of rice husk-based carbon-nickel composite catalyst - Google Patents
Preparation method of rice husk-based carbon-nickel composite catalyst Download PDFInfo
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- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 11
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- 238000000034 method Methods 0.000 claims description 10
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- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
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- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 19
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/33—Electric or magnetic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a preparation method of a rice hull-based carbon nickel composite catalyst, which comprises the following steps: soaking the rice hulls in a mixed acid solution to prepare soaked rice hulls; cleaning the soaked rice hulls, soaking the rice hulls in a nickel-containing solution, continuously oscillating, cleaning, drying and grinding to obtain powder; sintering the powder under the protection of non-oxidizing atmosphere to obtain a sintered product; and soaking the sintered product in an acid solution, performing ultrasonic treatment, filtering, washing and drying to obtain the rice hull-based carbon nickel composite catalyst. The preparation method of the invention utilizes the rice hull waste as a resource, effectively inhibits metal loss during the catalyst reaction, and the prepared catalyst shows good catalytic performance and stability in electrocatalytic water decomposition reaction and pollutant adsorption degradation.
Description
Technical Field
The invention relates to a preparation method of a carbon-nickel composite catalyst, in particular to a preparation method of a rice hull-based carbon-nickel composite catalyst.
Background
In the energy and environment fields of electro-catalysis water decomposition hydrogen production, pollutant adsorption and the like, noble metals, transition metals and compounds thereof can obviously reduce the reaction energy barrier and have excellent catalytic performance, but the noble metals, the transition metals and the compounds thereof have high cost and low stability, so that the problems of performance attenuation, metal loss pollution and the like after long-time reaction are caused. The development of cheap and efficient electrocatalytic materials is crucial to improve the energy conversion efficiency (j. mater. chem. a 2015,3, 14942-. The rice hull is an ideal catalyst component as a cheap, abundant and non-toxic biomass carbon material, but lacks an sp2 hybrid structure like graphene after carbonization, and has low conductivity and limited intrinsic catalytic activity (chem.Soc.Rev.2019,48, 4791-4822). The 3d orbital transition metal (especially Ni series material) has high catalytic activity, so the material is often compounded with carbon material to be used as a hydrogen evolution and oxygen generation catalyst in the electrocatalytic water decomposition reaction. The metal Ni can be used as a catalytic carrier for growing graphene and has good contact with carbon materials (chem.Soc.Rev.2017,46, 4417-4449). When the carbon material and the metal are combined and exposed in the solution, the metal can face the problems of ion loss, structural rearrangement and the like to reduce the catalytic activity (Energy environ. Sci.2018,11, 407-.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a preparation method of a rice hull-based carbon-nickel composite catalyst, which utilizes rice hull wastes as resources and effectively inhibits metal loss during catalyst reaction.
The technical scheme is as follows: the preparation method of the rice hull-based carbon nickel composite catalyst comprises the following steps:
(1) soaking the rice hulls in a mixed acid solution to prepare soaked rice hulls;
(2) cleaning the soaked rice hulls, soaking the rice hulls in a nickel-containing solution, continuously oscillating, cleaning, drying and grinding to obtain powder;
(3) sintering the powder under the protection of non-oxidizing atmosphere to obtain a sintered product;
(4) and soaking the sintered product in an acid solution, performing ultrasonic treatment, filtering, washing and drying to obtain the rice hull-based carbon-nickel composite catalyst.
Preferably, in the step (1), the soaking time is 5 hours; in the step (2), the dipping time is 1-48 hours; in the step (3), the sintering time is 6 hours.
Further, the mixed acid in the step (1) is a mixture of two or three of sulfuric acid, nitric acid or phosphoric acid. The concentration range of sulfuric acid, nitric acid or phosphoric acid in the mixed acid solution is 0.001-5 mol/L, and the soaking temperature is maintained at 20-90 ℃. In the step (2), the nickel-containing solution is Ni (NO)3)2、NiSO4、NiCl2Or Ni (CH)3COO)2One of the solutions. In the step (2), the concentration of nickel ions in the nickel-containing solution is 0.001-5 mol/L.
And (3) the non-oxidizing atmosphere in the step (3) is one or two of nitrogen and argon. The volume ratio of the mixed gas of nitrogen and argon is 1: 10-10: 1. The sintering temperature in the step (3) is 500-1200 ℃. In the step (4), the drying temperature is 60-90 ℃.
Preferably, the temperature rise and holding time for the sintering in step (3) is 5 hours or more.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the rice hull waste is recycled, oxygen-containing active groups are introduced to the surface of the rice hulls through mixed acid treatment to promote metal ion adsorption, and the novel carbon-nickel composite catalyst powder is prepared through a simple process by controlling the components of carbon and nickel precursors, the feed ratio, the sintering temperature and the like; the material has good performance in the aspects of electrochemical catalytic decomposition of water and adsorption of pollutants.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a catalyst of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a catalyst of the present invention;
FIG. 3 shows the results of the electrocatalytic hydrogen evolution performance test of the catalyst of the present invention on a glassy carbon Rotating Disk Electrode (RDE);
FIG. 4 shows the results of the electrocatalytic oxygen evolution performance of the catalyst of the present invention on a glassy carbon Rotating Disk Electrode (RDE);
FIG. 5 shows the results of the adsorption test of the catalyst of the present invention on phenol contaminants in a water body.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
To 500mL of a mixed solution of sulfuric acid and nitric acid at a molar ratio of 1:1 (concentration: 1mol/L), 10g of dried rice hulls were added, soaked for 5 hours and maintained at a temperature of 35 ℃. The sample is washed with deionized water and then washed with 0.001mol/LNi (NO)3)2The solution was immersed for 12 hours with shaking table followed by deionized water rinse, drying and grinding. The powder obtained is heated from room temperature to 800 ℃ in a tube furnace under the protection of nitrogen and sintered for 6 hours. Soaking the sintered product in 0.2mol/L dilute sulfuric acid solution, performing ultrasonic treatment, performing suction filtration and washing with deionized water, and drying at 60 deg.C for 8 hr to obtain carbon-nickel composite catalyst powder, wherein the X-ray diffraction (XRD) pattern of the obtained catalyst is shown in FIG. 1, and the hydrogen evolution performance is 10mA/cm2The overpotential was 0.69V.
Example 2
To 500mL of a mixed solution of sulfuric acid and phosphoric acid at a molar ratio of 1:1 (concentration of 0.001mol/L), 10g of dried rice hulls were added, soaked for 5 hours and maintained at a temperature of 20 ℃. Washing the obtained sample with deionized water, and then washing the sample with 0.1mol/L NiSO4The solution was immersed for 12 hours with shaking table followed by deionized water rinse, drying and grinding. The powder obtained is heated from room temperature to 500 ℃ in a tube furnace under the protection of argon and sintered for 6 hours. Soaking the sintered product in 0.2mol/L dilute sulfuric acid solution, performing ultrasonic treatment, performing suction filtration and washing with deionized water, and drying at 90 deg.C for 4 hr to obtain carbon-nickel composite catalyst powder, wherein the X-ray diffraction (XRD) pattern of the obtained catalyst is shown in figure 1, and the hydrogen evolution performance is 10mA/cm2The overpotential was 0.58V.
Example 3
To 500mL of a mixed solution of sulfuric acid, nitric acid and phosphoric acid (concentration: 5mol/L) at a molar ratio of 1:1:1 was added 10g of dried rice husk, and the mixture was soaked for 5 hours while maintaining the temperature at 90 ℃. The sample is washed by deionized water and then is washed by 5mol/LNiCl2The solution was immersed for 12 hours with shaking table followed by deionized water rinse, drying and grinding. The powder is heated to 1200 ℃ from room temperature in a tube furnace under the protection of nitrogen and argon, and is sintered for 6 hours, wherein the volume ratio of the nitrogen to the argon is 1: 10. Soaking the sintered product in 0.2mol/L dilute sulfuric acid solution, performing ultrasonic treatment, performing suction filtration and washing by using deionized water, and drying at 80 ℃ for 6 hours to obtain the carbon-nickel composite catalyst powder, wherein an X-ray diffraction (XRD) diagram of the obtained catalyst is shown in figure 1, a Scanning Electron Microscope (SEM) diagram is shown in figure 2, and an adsorption test result of the obtained catalyst on phenol pollutants in a water body is shown in figure 5.
Example 4
To 500mL of a mixed solution of sulfuric acid and nitric acid at a molar ratio of 1:1 (concentration: 1mol/L), 10g of dried rice hulls were added, soaked for 5 hours and maintained at a temperature of 35 ℃. The sample is washed with deionized water and then washed with 1mol/LNi (CH)3COO)2The solution was immersed for 12 hours with shaking table followed by deionized water rinse, drying and grinding. Heating the obtained powder to 800 ℃ from room temperature in a tube furnace under the protection of nitrogen and argon, and sintering for 6 hours, wherein the nitrogen and argon are used for heatingIs 10: 1. Soaking the sintered product in 0.2mol/L dilute sulfuric acid solution, performing ultrasonic treatment, performing suction filtration and washing with deionized water, and drying at 60 deg.C for 8 hr to obtain carbon-nickel composite catalyst powder, wherein the X-ray diffraction (XRD) pattern of the obtained catalyst is shown in FIG. 1, and the hydrogen evolution performance is 10mA/cm2The overpotential was 0.39V.
Example 5
To 500mL of a mixed solution of sulfuric acid and nitric acid at a molar ratio of 1:1 (concentration: 1mol/L), 10g of dried rice hulls were added, soaked for 5 hours and maintained at a temperature of 35 ℃. The sample is washed with deionized water and then washed with 0.5mol/L Ni (NO)3)2The solution was immersed for 12 hours with shaking table followed by deionized water rinse, drying and grinding. The powder is heated to 600 ℃ from room temperature in a tube furnace under the protection of nitrogen and argon, and is sintered for 6 hours, wherein the volume ratio of the nitrogen to the argon is 4: 6. Soaking the sintered product in 0.2mol/L dilute sulfuric acid solution, performing ultrasonic treatment, performing suction filtration and washing by using deionized water, and drying for 8 hours at the temperature of 60 ℃ to obtain the carbon-nickel composite catalyst powder with the hydrogen evolution performance of 10mA/cm2The overpotential was 0.62V.
Example 6
To 500mL of a mixed solution of sulfuric acid and nitric acid at a molar ratio of 1:1 (concentration: 1mol/L), 10g of dried rice hulls were added, soaked for 5 hours and maintained at a temperature of 35 ℃. The sample is washed with deionized water and then washed with 0.5mol/L Ni (NO)3)2The solution was immersed for 12 hours with shaking table followed by deionized water rinse, drying and grinding. The powder obtained is heated from room temperature to 1000 ℃ in a tube furnace under the protection of nitrogen and sintered for 6 hours. Soaking the sintered product in 0.2mol/L dilute sulfuric acid solution, performing ultrasonic treatment, performing suction filtration and washing by using deionized water, and drying for 8 hours at the temperature of 60 ℃ to obtain the carbon-nickel composite catalyst powder with the hydrogen evolution performance of 10mA/cm2The overpotential was 0.48V.
Example 7
To 500mL of a mixed solution of sulfuric acid and nitric acid at a molar ratio of 1:1 (concentration: 1mol/L), 10g of dried rice hulls were added, soaked for 5 hours and maintained at a temperature of 35 ℃. The sample is washed with deionized water and then washed with 0.5mol/L Ni (NO)3)2The solution was immersed for 12 hours with shaking table followed by deionized water rinse, drying and grinding. The powder obtained is heated from room temperature to 800 ℃ in a tube furnace under the protection of nitrogen and sintered for 10 hours. Soaking the sintered product in 0.2mol/L dilute sulfuric acid solution, performing ultrasonic treatment, performing suction filtration and washing by using deionized water, and drying for 8 hours at the temperature of 60 ℃ to obtain the carbon-nickel composite catalyst powder with the hydrogen evolution performance of 10mA/cm2The overpotential was 0.49V.
Example 8
10mg of the carbon-nickel composite catalyst powder prepared in example 3 was added to 400. mu.L of an ethanol solution, and 50. mu.L of a 10 wt% Nafion solution was added to prepare a slurry. The slurry was ultrasonically dispersed for 30 minutes. Dropping 3 μ L of test solution on glassy carbon of rotary disk electrode with a loading amount of about 0.3mg/cm2. In a three-electrode system with a 1mol/L NaOH solution, Pt filaments as a counter electrode and HgO | Hg as a reference electrode, a cathodic polarization curve test (hydrogen evolution test) is carried out, the rotating speed of a working electrode (a rotating disc) is 1500 rpm, the electrocatalytic hydrogen evolution performance test result on the Rotating Disc Electrode (RDE) is shown in FIG. 3, and the hydrogen evolution performance is 10mA/cm2The overpotential was 0.45V.
Example 9
10mg of the carbon-nickel composite catalyst powder prepared in example 3 was added to 400. mu.L of an ethanol solution, and 50. mu.L of a 10 wt% Nafion solution was added to prepare a slurry. The slurry was ultrasonically dispersed for 30 minutes. Dropping 3 μ L of test solution on glassy carbon of rotary disk electrode with a loading amount of about 0.3mg/cm2. In a three-electrode system with a 1mol/L NaOH solution, Pt filaments as a counter electrode and HgO | Hg as a reference electrode, an anode polarization curve test (oxygen generation test) is carried out, the rotating speed of a working electrode (a rotating disc) is 1500 rpm, and the results of the electrocatalytic oxygen generation performance test on the Rotating Disc Electrode (RDE) are shown in FIG. 4, wherein the oxygen generation performance is 10mA/cm2The overpotential was 0.21V.
Example 10
10mg of the nickel-carbon composite catalyst prepared according to example 3 was added to 50mL of deionized water, the suspension was magnetically stirred continuously at a speed of 500 rpm, and a pre-formed phenol solution was added to a concentration such that the phenol concentration in the suspension was 0.5 mg/L. 1mL of the sample was filtered through a 0.22 μm filter at different reaction time intervals, and the residual concentration of phenol was measured by liquid chromatography and plotted, and the results are shown in FIG. 5.
Comparative example 1
The rice hull of the comparative example is not soaked in the mixed solution of the sulfuric acid and the nitric acid, other raw materials, the proportion, the operation steps and the detection method are the same as those of the example 1, and the hydrogen evolution performance is 10mA/cm2The overpotential was 0.74V. When the biomass carbon material is treated by the acid-free solution, the surface functionalization is lacked, the adsorption effect on metal ions is limited, and the catalytic performance of a final product is reduced.
Comparative example 2
In the comparative example, the soaking temperature is maintained at 15 ℃, other raw materials, proportion, operation steps and detection methods are the same as those in example 1, and the hydrogen evolution performance is 10mA/cm2The overpotential was 0.71V. The surface functionalization modification capability of the acid-treated carbon material is limited in a low-temperature environment, and the adsorption capability of the carbon material to metal is weakened, so that the activity of the composite catalyst is reduced.
Comparative example 3
In the comparative example, the soaking temperature is maintained at 95 ℃, other raw materials, proportion, operation steps and detection methods are the same as those in example 1, and the hydrogen evolution performance is 10mA/cm2The overpotential was 0.68V. At higher temperatures, the acid-treated surface functionalization modification capacity tends to saturate, the catalyst performance is not significantly improved, and additional energy consumption is added by high-temperature treatment.
Comparative example 4
Ni (NO) in this comparative example3)2The concentration of the solution is 0.0005mol/L, other raw materials, mixture ratio, operation steps and detection method are the same as those in example 1, and the hydrogen evolution performance is 10mA/cm2The overpotential was 0.73V. When the concentration of the metal salt solution is low, the biomass carbon material has slow adsorption kinetics and reduced adsorption quantity, and reduces the active sites of the composite catalyst, thereby reducing the catalytic performance.
Comparative example 5
Ni (NO) in this comparative example3)2The solution concentration is 6mol/L, and other raw materialsThe proportion, the operation steps and the detection method are the same as those of the embodiment 1, and the hydrogen evolution performance is 10mA/cm2The overpotential was 0.67V. The adsorption sites of the metal ions on the biomass carbon material are limited, the adsorption capacity is saturated when the concentration of the metal salt solution is too high, and the catalytic performance of the composite catalyst is not remarkably improved.
Comparative example 6
In the comparative example, the sintering temperature was 480 ℃, other raw materials, mixture ratio, operation steps and detection method were the same as those in example 1, and the hydrogen evolution performance was 10mA/cm2The overpotential was 0.75V. The lower sintering temperature causes insufficient carbonization degree of the biomass carbon material, the electrical conductivity of the catalyst is reduced, and the binding capacity between the metal and the carbon substrate is weakened, thereby weakening the catalytic performance.
Comparative example 7
In the comparative example, the sintering temperature is 1250 ℃, other raw materials, mixture ratio, operation steps and detection methods are the same as those in example 1, and the hydrogen evolution performance is 10mA/cm2The overpotential was 0.67V. The high-temperature sintering is beneficial to carbonization of biomass carbon materials and composition of metals and carbon materials, but the performance improvement capability is limited due to the overhigh sintering temperature, and the energy consumption in the material preparation link is increased.
Claims (10)
1. A preparation method of a rice husk-based carbon nickel composite catalyst is characterized by comprising the following steps:
(1) soaking the rice hulls in a mixed acid solution to prepare soaked rice hulls;
(2) cleaning the soaked rice hulls, soaking the rice hulls in a nickel-containing solution, continuously oscillating, cleaning, drying and grinding to obtain powder;
(3) sintering the powder under the protection of non-oxidizing atmosphere to obtain a sintered product;
(4) and soaking the sintered product in an acid solution, performing ultrasonic treatment, filtering, washing and drying to obtain the rice hull-based carbon nickel composite catalyst.
2. The method for preparing the rice hull-based carbon-nickel composite catalyst according to claim 1, which is characterized in that: the mixed acid in the step (1) is a mixture of two or three of sulfuric acid, nitric acid or phosphoric acid.
3. The method for preparing the rice hull-based carbon-nickel composite catalyst according to claim 2, characterized in that: the concentration range of sulfuric acid, nitric acid or phosphoric acid in the mixed acid solution is 0.001-5 mol/L.
4. The method for preparing the rice hull-based carbon-nickel composite catalyst according to claim 1, which is characterized in that: in the step (1), the soaking temperature is maintained at 20-90 ℃.
5. The method for preparing the rice hull-based carbon-nickel composite catalyst according to claim 1, which is characterized in that: in the step (2), the nickel-containing solution is Ni (NO)3)2、NiSO4、NiCl2Or Ni (CH)3COO)2One of the solutions.
6. The method for preparing the rice hull-based carbon-nickel composite catalyst according to claim 1, which is characterized in that: in the step (2), the concentration of nickel ions in the nickel-containing solution is 0.001-5 mol/L.
7. The method for preparing the rice hull-based carbon-nickel composite catalyst according to claim 1, which is characterized in that: and (3) the non-oxidizing atmosphere in the step (3) is one or two of nitrogen and argon.
8. The method for preparing the rice hull-based carbon-nickel composite catalyst according to claim 7, characterized in that: the volume ratio of the mixed gas of the nitrogen and the argon is 1: 10-10: 1.
9. the method for preparing the rice hull-based carbon-nickel composite catalyst according to claim 1, which is characterized in that: in the step (3), the sintering temperature is 500-1200 ℃.
10. The method for preparing the rice hull-based carbon-nickel composite catalyst according to claim 1, which is characterized in that: in the step (4), the drying temperature is 60-90 ℃.
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