CN110732332B - Method for preparing phosphorus-nickel sulfide hollow spheres by adopting single-cell biological template - Google Patents
Method for preparing phosphorus-nickel sulfide hollow spheres by adopting single-cell biological template Download PDFInfo
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- VLQMASGMVDYLER-UHFFFAOYSA-N [S].[P].[Ni] Chemical compound [S].[P].[Ni] VLQMASGMVDYLER-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 20
- 241000081271 Phaffia rhodozyma Species 0.000 claims abstract description 75
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 47
- 239000001257 hydrogen Substances 0.000 claims abstract description 47
- 230000004913 activation Effects 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 38
- 230000002829 reductive effect Effects 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 229910052763 palladium Inorganic materials 0.000 claims description 19
- 239000012153 distilled water Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims description 15
- 229910001453 nickel ion Inorganic materials 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 238000011085 pressure filtration Methods 0.000 claims description 7
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 3
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 235000011083 sodium citrates Nutrition 0.000 claims description 3
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 4
- -1 nickel sulfide phosphate Chemical compound 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 35
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- AOLMGDPIQZITEU-UHFFFAOYSA-N [P]=S.[Ni] Chemical compound [P]=S.[Ni] AOLMGDPIQZITEU-UHFFFAOYSA-N 0.000 description 6
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000003929 acidic solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- JEBFVOLFMLUKLF-IFPLVEIFSA-N Astaxanthin Natural products CC(=C/C=C/C(=C/C=C/C1=C(C)C(=O)C(O)CC1(C)C)/C)C=CC=C(/C)C=CC=C(/C)C=CC2=C(C)C(=O)C(O)CC2(C)C JEBFVOLFMLUKLF-IFPLVEIFSA-N 0.000 description 3
- 229910001096 P alloy Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- MQZIGYBFDRPAKN-ZWAPEEGVSA-N astaxanthin Chemical compound C([C@H](O)C(=O)C=1C)C(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)C(=O)[C@@H](O)CC1(C)C MQZIGYBFDRPAKN-ZWAPEEGVSA-N 0.000 description 3
- 229940022405 astaxanthin Drugs 0.000 description 3
- 235000013793 astaxanthin Nutrition 0.000 description 3
- 239000001168 astaxanthin Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- OTYNBGDFCPCPOU-UHFFFAOYSA-N phosphane sulfane Chemical compound S.P[H] OTYNBGDFCPCPOU-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- NTTTWMWMAGSQOK-UHFFFAOYSA-N P(=O)(=O)SP(=O)=O.[Ni] Chemical compound P(=O)(=O)SP(=O)=O.[Ni] NTTTWMWMAGSQOK-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- B01J35/33—
-
- B01J35/51—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/36—Biochemical methods
-
- 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
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a method for preparing a phosphorus-nickel sulfide hollow sphere by using a single-cell biological template, and relates to a method for preparing a phosphorus-nickel sulfide hollow sphere serving as an acid solution electrolytic hydrogen production catalyst by using a single-cell organism as a template. The invention aims to solve the problems that the hydrogen evolution overpotential of the existing non-noble metal catalyst in an acid solution is high, the size and the performance are unstable, the preparation method is not easy to scale, and the like. A method for preparing phosphorus-nickel sulfide hollow spheres by adopting a single-cell biological template comprises the following steps: (1) dispersing the chemical wall breaking of the unicellular phaffia rhodozyma; (2) activation of unicellular phaffia rhodozyma; (3) preparing a single-cell phaffia rhodozyma intermediate; (4) and (2) performing heat treatment, namely preparing the nickel sulfide phosphate hollow spheres by taking the unicellular phaffia rhodozyma as a template, wherein the obtained nickel sulfide phosphate hollow spheres can show high catalytic activity, and the unique hollow structure can maintain the stability of the size and the activity of the nickel sulfide phosphate hollow spheres, so that the key technical problems of high hydrogen evolution overpotential, unstable performance and size and the like of a non-noble metal catalyst in an acid solution in the actual electrolytic hydrogen production are solved.
Description
Technical Field
The invention belongs to the field of hydrogen evolution material preparation, and relates to a preparation method of a phosphorus-sulfur nickel hollow sphere used as a high-activity electrolytic hydrogen evolution material.
Background
With the continuous consumption of global petroleum resources, the result of exhaustion is encountered all the day after all, and then a plurality of problems are caused, especially the global serious shortage of energy caused by the disappearance of petrochemical energy fuels such as gasoline, diesel oil and the like. Therefore, people are continuously searching for alternatives to fossil fuels such as gasoline and diesel oil, so as to cope with exhaustion and update of energy resources in the future. Among all the new energy sources replacing fossil fuels such as gasoline, hydrogen is the most ideal, and when human needs energy, the hydrogen can release the chemical energy stored in the hydrogen in the form of electric energy in a primary battery or in the form of heat energy in an internal combustion engine, and the product of the energy release mode is water without any pollution. Therefore, hydrogen is considered by humans as the cleanest, most desirable, and most likely new energy source that may overwhelm the energy world. However, although the hydrogen on earth is abundant, there is no hydrogen resource which can be directly exploited, and hydrogen must be produced by other methods. Among the various hydrogen preparation modes, the electrolytic hydrogen production has unique advantages, is the only hydrogen production mode which can be combined with solar energy utilization, and does not need to consume other non-renewable resources. Therefore, the electrolytic hydrogen production has attracted wide attention in the world, and how to effectively utilize photogenerated electrons and efficiently store electric energy converted from solar energy in hydrogen has a very important meaning for the sustainable development strategy of human social energy.
The reactant for hydrogen production by electrolysis is water, and the catalyst surface on the cathode catalyzes the water to crack so as to produce hydrogen. However, in the process of hydrogen production by electrolysis, the efficiency of energy conversion is not one hundred percent due to the existence of hydrogen evolution overpotential of the catalyst, and the higher the hydrogen evolution overpotential is, the higher the polarization resistance is, and the higher the loss rate in the energy conversion process is. Therefore, the search for a catalyst with low hydrogen evolution overpotential is very important for the energy conversion efficiency of the hydrogen production by electrolysis. The catalyst for electrolytic hydrogen production prepared from platinum group metal has very low hydrogen evolution overpotential, and the hydrogen evolution activity of noble metal platinum is the most excellent. However, the platinum-based catalyst has high price and low cost performance, and is not suitable for large-scale application. Therefore, the preparation of the catalyst for electrolytic hydrogen production by selecting non-noble metal elements of platinum group is the most effective way to improve the cost performance of the catalyst at present. Among various platinum group non-noble metal catalysts, nickel phosphide and nickel sulfide both show good catalytic hydrogen evolution activity in alkaline solution, and the energy conversion efficiency is even close to that of the platinum-based catalyst. However, the catalytic activity of nickel phosphide and nickel sulfide in acidic solutions is not satisfactory. Moreover, the preparation of nickel phosphide and nickel sulfide catalysts adopts organic solvents, which is not suitable for large-scale production, and the huge surface energy of the prepared nanoparticles also easily causes the agglomeration of the catalysts and the gradual attenuation of the performance. Therefore, the development of a novel preparation method of nickel phosphide and nickel sulfide can prepare a catalyst with large specific surface area, good catalytic performance in an acid solution and stable size and behavior, is a key technical problem of solving the problems that the preparation method of the nickel-based catalyst is difficult to expand and the performance of the obtained product is unstable at present, and has obvious significance on the sustainable development of energy.
Disclosure of Invention
The invention provides a preparation method of a nickel phosphide sulfide hollow sphere for electrolytic hydrogen production in an acidic solution, aiming at solving the problems that a nickel-based catalyst in the existing electrolytic hydrogen production process has high hydrogen evolution overpotential, unstable size and performance, difficult large-scale preparation method and the like.
The method for preparing the phosphorus-nickel sulfide hollow spheres by adopting the single-cell biological template comprises the following steps:
(1) chemical wall breaking dispersion of unicellular phaffia rhodozyma: a. collecting the unicellular phaffia rhodozyma in the culture solution, centrifuging and washing the collected unicellular phaffia rhodozyma for 1 to 5 minutes by using distilled water, and then carrying out freeze drying for 24 to 36 hours at the temperature of minus 170 ℃; b. taking out the freeze-dried unicellular phaffia rhodozyma, immediately immersing the freeze-dried unicellular phaffia rhodozyma into 1-6 mol/L NaOH solution, stirring for 15-60 minutes, performing ultrasonic treatment for 10-60 minutes, then performing reduced pressure filtration, and washing for 1-5 minutes by using distilled water under reduced pressure; c. repeating the step b for 0-5 times to complete the chemical wall-breaking dispersion of the unicellular phaffia rhodozyma;
(2) activation of unicellular phaffia rhodozyma: d. immersing 0.05-0.3 g/L of the unicellular phaffia rhodozyma processed in the step (1) into a palladium sulfate solution, stirring for 1-5 minutes at the temperature of 30-50 ℃, then carrying out reduced pressure filtration, and washing for 1-5 minutes by using distilled water and absolute ethyl alcohol respectively under reduced pressure to complete palladium activation of the unicellular phaffia rhodozyma;
(3) Preparing a single-cell phaffia rhodozyma intermediate: e. freeze-drying the unicellular phaffia rhodozyma processed in the step (2) at the temperature of-170 ℃ for 24-36 hours, taking out the unicellular phaffia rhodozyma, immediately immersing the unicellular phaffia rhodozyma into an ammonium hypophosphite solution at the temperature of 0 ℃, stirring for 10-120 minutes, and filtering under reduced pressure; f. adding 0.1-5.0 g/L of the unicellular phaffia rhodozyma processed in the step e into a nickel ion complex solution with the temperature of 60-95 ℃ and the pH value of 4.5-8.0, stirring for 0.5-20 minutes, adding 20-100 g/L of thiourea into the solution, continuously stirring for 10-120 minutes, and filtering under reduced pressure to obtain a unicellular phaffia rhodozyma intermediate for preparing the phosphorus-nickel sulfide hollow spheres;
(4) and (3) heat treatment: g. calcining the sample treated in the step (3) for 1-5 hours at 300-600 ℃ in a hydrogen atmosphere, calcining for 1-6 hours at 650-1000 ℃ in an inert atmosphere, taking out, stirring for 2-30 minutes in a 5% hydrochloric acid solution to remove impurities, washing for 1-5 minutes by using distilled water under reduced pressure, and finally freeze-drying for 24 hours at-170 ℃ to finish the preparation of the phosphorus-nickel sulfide hollow sphere.
The composition of the palladium sulfate solution in the step (2) d is 0.1-1.0 g/L palladium sulfate and 1-10 mL/L sulfuric acid; the ammonium hypophosphite solution in the step (3) e comprises 6-20 g/L of ammonium hypophosphite and 0.1-5.0 g/L of ammonium bifluoride, nickel ions in the nickel ion complex solution are derived from nickel acetate, the concentration of the nickel ions is 0.5-6.0 g/L, and the complex is derived from one of potassium sodium tartrate, sodium citrate or lactic acid, and the concentration of the complex is 2-30 g/L.
According to the method for preparing the nickel-phosphorus sulfide hollow spheres by adopting the single-cell biological template, the palladium activation on the surface of the single-cell phaffia rhodozyma is realized by utilizing rich reductive astaxanthin in the single-cell phaffia rhodozyma, a nickel-phosphorus alloy thin layer is obtained on the surface of the single-cell phaffia rhodozyma in a chemical nickel plating mode by utilizing the water absorption characteristic of dehydrated single-cell phaffia rhodozyma after the activation, and the nickel-phosphorus sulfide hollow spheres can be obtained by further carrying out heat treatment on ammonium hypophosphite and thiourea absorbed by the single-cell phaffia rhodozyma. The phosphorus-nickel sulfide hollow sphere not only has excellent electrocatalytic hydrogen evolution activity of nickel phosphide and nickel sulfide, but also can show higher activity after phosphorus-sulfur doping, and the unique hollow structure can provide more catalytic active sites and can maintain the stability of the size and the activity of the catalytic active sites, thereby solving the problems of high hydrogen evolution overpotential, unstable performance and size and the like of a non-noble metal catalyst in an acidic solution in the actual electrolytic hydrogen production.
Drawings
FIG. 1 is a schematic diagram of a method for preparing hollow spheres of nickel sulfide phosphate by using a single-cell Phaffia rhodozyma template;
FIG. 2 is a graph showing the size distribution of hollow nickel phosphosulfide spheres prepared in experiment one;
FIG. 3 shows that the hollow balls of phosphorus-nickel sulfide prepared in the first test are 0.5M H2SO4The current density of the cathode in the solution is 200 mA/cm2The supported amount was 5 mg/cm2The time-potential curve measured under the conditions of (1).
Detailed Description
The first embodiment is as follows: the method for preparing the phosphorus-nickel sulfide hollow spheres by adopting the single-cell biological template comprises the following steps:
(1) chemical wall breaking dispersion of unicellular phaffia rhodozyma: a. collecting the unicellular phaffia rhodozyma in the culture solution, then centrifugally washing the collected unicellular phaffia rhodozyma for 1 to 5 minutes by using distilled water, and then carrying out freeze drying on the unicellular phaffia rhodozyma for 24 to 36 hours at the temperature of minus 170 ℃; b. taking out the freeze-dried unicellular phaffia rhodozyma, immediately immersing the freeze-dried unicellular phaffia rhodozyma into 1-6 mol/L NaOH solution, stirring for 15-60 minutes, performing ultrasonic treatment for 10-60 minutes, then performing reduced pressure filtration, and washing for 1-5 minutes by using distilled water under reduced pressure; c. repeating the step b for 0-5 times to complete the dispersion of the chemical wall breaking of the unicellular phaffia rhodozyma;
(2) activation of unicellular phaffia rhodozyma: d. immersing 0.05-0.3 g/L of the unicellular phaffia rhodozyma processed in the step (1) into a palladium sulfate solution, stirring for 1-5 minutes at the temperature of 30-50 ℃, then carrying out reduced pressure filtration, and washing for 1-5 minutes by using distilled water and absolute ethyl alcohol respectively under reduced pressure to complete palladium activation of the unicellular phaffia rhodozyma;
(3) Preparing a single-cell phaffia rhodozyma intermediate: e. freeze-drying the unicellular phaffia rhodozyma processed in the step (2) at-170 ℃ for 24-36 hours, taking out, immediately immersing into an ammonium hypophosphite solution at the temperature of 0 ℃, stirring for 10-120 minutes, and filtering under reduced pressure; f. adding 0.1-5.0 g/L of the unicellular phaffia rhodozyma processed in the step e into a nickel ion complex solution with the temperature of 60-95 ℃ and the pH value of 4.5-8.0, stirring for 0.5-20 minutes, adding 20-100 g/L of thiourea into the solution, continuously stirring for 10-120 minutes, and filtering under reduced pressure to obtain a unicellular phaffia rhodozyma intermediate for preparing the phosphorus-nickel sulfide hollow spheres;
(4) and (3) heat treatment: g. calcining the sample treated in the step (3) for 1-5 hours at 300-600 ℃ in a hydrogen atmosphere, calcining for 1-6 hours at 650-1000 ℃ in an inert atmosphere, taking out, stirring for 2-30 minutes in a 5% hydrochloric acid solution to remove impurities, washing for 1-5 minutes by using distilled water under reduced pressure, and finally freeze-drying for 24 hours at-170 ℃ to finish the preparation of the phosphorus-nickel sulfide hollow sphere.
According to the method for preparing the nickel-phosphorus sulfide hollow spheres by using the unicellular biological template, the palladium activation on the surface of the unicellular phaffia rhodozyma is realized by using rich reductive astaxanthin in the unicellular phaffia rhodozyma, a nickel-phosphorus alloy thin layer is obtained on the surface of the unicellular phaffia rhodozyma in a chemical nickel plating mode by using the water absorption characteristic of dehydrated unicellular phaffia rhodozyma after the activation, and the nickel-phosphorus sulfide hollow spheres can be obtained by further performing heat treatment by using ammonium hypophosphite and thiourea absorbed by the unicellular phaffia rhodozyma. The phosphorus-nickel sulfide hollow sphere not only has excellent electrocatalytic hydrogen evolution activity of nickel phosphide and nickel sulfide, but also can show higher activity after phosphorus-sulfur doping, and the unique hollow structure can provide more catalytic active sites and can maintain the stability of the size and the activity of the catalytic active sites, thereby solving the key technical problems of high hydrogen evolution overpotential, unstable performance and size and the like of a non-noble metal catalyst in an acidic solution in the actual electrolytic hydrogen production.
The second embodiment is as follows: the difference between the present embodiment and the first embodiment is that the composition of the palladium sulfate solution in step (2) is 0.1-1.0 g/L palladium sulfate and 1-10 mL/L sulfuric acid. The rest is the same as the first embodiment.
The third concrete implementation mode: the difference between the present embodiment and the first or second embodiment is that the composition of the ammonium hypophosphite solution in step (3) is 6-20 g/L ammonium hypophosphite and 0.1-5.0 g/L ammonium bifluoride. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is that the nickel ion in the nickel ion complex solution in step (3) e is derived from nickel acetate and has a concentration of 0.5 to 6.0 g/L, and the complex is derived from one of potassium sodium tartrate, sodium citrate or lactic acid and has a concentration of 2 to 30 g/L. The others are the same as in one of the first to third embodiments.
The beneficial effects of the invention were verified by the following tests:
test one: the method for preparing the phosphorus-nickel sulfide hollow spheres by adopting the single-cell biological template comprises the following steps:
(1) chemical wall breaking dispersion of unicellular phaffia rhodozyma: a. collecting the unicellular phaffia rhodozyma in the culture solution, centrifuging and washing for 5 minutes by using distilled water, and then carrying out freeze drying for 36 hours at the temperature of-170 ℃; b. taking out the freeze-dried unicellular phaffia rhodozyma, immediately immersing the frozen unicellular phaffia rhodozyma into a 1 mol/L NaOH solution, stirring the solution for 60 minutes, then carrying out ultrasonic treatment for 60 minutes, then carrying out reduced pressure filtration, and washing the solution for 5 minutes by using distilled water under reduced pressure; c. repeating the step b 1 times to complete the chemical wall-breaking dispersion of the unicellular phaffia rhodozyma;
(2) Activation of unicellular phaffia rhodozyma: d. soaking 0.3 g/L of the unicellular phaffia rhodozyma processed in the step (1) into a palladium sulfate solution, stirring for 2 minutes at 50 ℃, then filtering under reduced pressure, and washing for 5 minutes by using distilled water and absolute ethyl alcohol under reduced pressure respectively to complete palladium activation of the unicellular phaffia rhodozyma;
(3) preparing a single-cell phaffia rhodozyma intermediate: e. freeze-drying the unicellular phaffia rhodozyma processed in the step (2) at-170 ℃ for 36 hours, taking out, immediately immersing into an ammonium hypophosphite solution at the temperature of 0 ℃, stirring for 90 minutes, and filtering under reduced pressure; f. adding 1.5 g/L of the unicellular phaffia rhodozyma processed in the step e into a nickel ion complex solution with the temperature of 92 ℃ and the pH value of 6.5, stirring for 3 minutes, adding 30 g/L of thiourea into the solution, continuously stirring for 15 minutes, and filtering under reduced pressure to obtain a unicellular phaffia rhodozyma intermediate for preparing the phosphorus-nickel sulfide hollow spheres;
(4) and (3) heat treatment: g. and (3) calcining the sample treated in the step (3) at 400 ℃ for 2 hours in a hydrogen atmosphere, calcining the sample at 700 ℃ for 1 to 6 hours in an inert atmosphere, taking the calcined sample out, stirring the calcined sample in a 5% hydrochloric acid solution for 3 minutes to remove impurities, washing the calcined sample with distilled water under reduced pressure for 5 minutes, and finally freeze-drying the washed sample at-170 ℃ for 24 hours to complete the preparation of the phosphorus-nickel sulfide hollow sphere.
The composition of the palladium sulfate solution in the step (2) d is 0.6 g/L palladium sulfate and 5 mL/L sulfuric acid; the ammonium hypophosphite solution in the step (3) e consists of 16 g/L ammonium hypophosphite and 2.0 g/L ammonium bifluoride, nickel ions in the nickel ion complex solution are derived from nickel acetate, the concentration of the nickel ions is 3.0 g/L, and the complex is derived from lactic acid, and the concentration of the complex is 2 g/L.
The schematic diagram of the method for preparing the nickel-phosphorus sulfide hollow spheres by using the single-cell phaffia rhodozyma template in the test is shown in fig. 1, the palladium activation on the surface of the single-cell phaffia rhodozyma is realized by using rich reductive astaxanthin in the single-cell phaffia rhodozyma, a nickel-phosphorus alloy thin layer is obtained on the surface of the single-cell phaffia rhodozyma in a chemical nickel plating mode by using the water absorption characteristic of dehydrated single-cell phaffia rhodozyma after the activation, and the nickel-phosphorus sulfide hollow spheres can be obtained by further performing heat treatment by using ammonium hypophosphite and thiourea absorbed by the single-cell phaffia rhodozyma. The size distribution of the nickel phosphide sulfide hollow spheres prepared in the test is shown in fig. 2, and it can be seen from fig. 2 that the size distribution of the nickel phosphide hollow spheres is uniform, and the specific surface area of the gold hollow spheres obtained by the BET method is 763 m2The prepared phosphorus nickel sulfide hollow spheres have huge specific surface area. The hollow nickel phosphide sulfide ball prepared in the test is 0.5M H 2SO4The current density of the cathode in the solution is 200 mA/cm2The loading amount is 5 mg/cm2The time-potential curve measured under the conditions (2) is shown in FIG. 3. As can be seen from FIG. 3, the hydrogen evolution overpotential of the hollow spheres of nickel phosphide sulfide prepared by the test is only about 200 mV, which effectively reduces the energy consumption of hydrogen production by electrolysis.
After 480 hours of continuous electrolytic hydrogen production, the hydrogen evolution overpotential of the phosphorus-nickel sulfide hollow sphere prepared by the test is still about 200 mV, which shows that the prepared phosphorus-nickel sulfide hollow sphere has stable performance.
Claims (4)
1. A method for preparing a phosphorus-nickel sulfide hollow sphere by adopting a single-cell biological template is characterized in that the method for preparing the phosphorus-nickel sulfide hollow sphere by adopting the single-cell biological template comprises the following steps:
(1) chemical wall breaking dispersion of unicellular phaffia rhodozyma: a. collecting the unicellular phaffia rhodozyma in the culture solution, centrifuging and washing the collected unicellular phaffia rhodozyma for 1 to 5 minutes by using distilled water, and then carrying out freeze drying for 24 to 36 hours at the temperature of minus 170 ℃; b. taking out the freeze-dried unicellular phaffia rhodozyma, immediately immersing the freeze-dried unicellular phaffia rhodozyma into 1-6 mol/L NaOH solution, stirring for 15-60 minutes, performing ultrasonic treatment for 10-60 minutes, then performing reduced pressure filtration, and washing for 1-5 minutes by using distilled water under reduced pressure; c. repeating the step b for 0-5 times to complete the chemical wall-breaking dispersion of the unicellular phaffia rhodozyma;
(2) Activation of unicellular phaffia rhodozyma: d. immersing 0.05-0.3 g/L of the unicellular phaffia rhodozyma processed in the step (1) into a palladium sulfate solution, stirring for 1-5 minutes at the temperature of 30-50 ℃, then carrying out reduced pressure filtration, and washing for 1-5 minutes by using distilled water and absolute ethyl alcohol respectively under reduced pressure to complete palladium activation of the unicellular phaffia rhodozyma;
(3) preparing a single-cell phaffia rhodozyma intermediate: e. freeze-drying the unicellular phaffia rhodozyma processed in the step (2) at-170 ℃ for 24-36 hours, taking out, immediately immersing into an ammonium hypophosphite solution at the temperature of 0 ℃, stirring for 10-120 minutes, and filtering under reduced pressure; f. adding 0.1-5.0 g/L of the unicellular phaffia rhodozyma processed in the step e into a nickel ion complex solution with the temperature of 60-95 ℃ and the pH value of 4.5-8.0, stirring for 0.5-20 minutes, adding 20-100 g/L of thiourea into the solution, continuously stirring for 10-120 minutes, and filtering under reduced pressure to obtain a unicellular phaffia rhodozyma intermediate for preparing the phosphorus-nickel sulfide hollow spheres;
(4) and (3) heat treatment: g. calcining the sample treated in the step (3) for 1-5 hours at 300-600 ℃ in a hydrogen atmosphere, calcining for 1-6 hours at 650-1000 ℃ in an inert atmosphere, taking out, stirring for 2-30 minutes in a 5% hydrochloric acid solution to remove impurities, washing for 1-5 minutes by using distilled water under reduced pressure, and finally freeze-drying for 24 hours at-170 ℃ to finish the preparation of the phosphorus-nickel sulfide hollow sphere.
2. The method for preparing the phosphorus-nickel sulfide hollow spheres by using the single-cell biological template as claimed in claim 1, wherein the composition of the palladium sulfate solution in the step (2) d is 0.1-1.0 g/L palladium sulfate and 1-10 mL/L sulfuric acid.
3. The method for preparing the phosphorus-nickel sulfide hollow spheres by using the single-cell biological template as claimed in claim 1, wherein the ammonium hypophosphite solution in the step (3) e comprises 6-20 g/L ammonium hypophosphite and 0.1-5.0 g/L ammonium bifluoride.
4. The method for preparing the phosphorus-nickel sulfide hollow spheres by using the single-cell biological template as claimed in claim 1, wherein the nickel ions in the nickel ion complex solution in the step (3) are derived from nickel acetate and have a concentration of 0.5-6.0 g/L, and the complex is derived from one of potassium sodium tartrate, sodium citrate or lactic acid and has a concentration of 2-30 g/L.
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