CN113881965B - Metal nanoparticle supported catalyst with biomass carbon source as template and preparation method and application thereof - Google Patents
Metal nanoparticle supported catalyst with biomass carbon source as template and preparation method and application thereof Download PDFInfo
- Publication number
- CN113881965B CN113881965B CN202111061514.4A CN202111061514A CN113881965B CN 113881965 B CN113881965 B CN 113881965B CN 202111061514 A CN202111061514 A CN 202111061514A CN 113881965 B CN113881965 B CN 113881965B
- Authority
- CN
- China
- Prior art keywords
- yeast
- catalyst
- zif
- npc
- template
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
-
- 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 metal nanoparticle-loaded catalyst taking a biomass carbon source as a template, and a preparation method and application thereof, and belongs to the fields of new energy material technology and electrochemical catalysis. The invention takes saccharomycetes as a carbon template, and coats a Metal Organic Framework (MOF) on the surface of the saccharomycetes as a precursor. The method can effectively prevent the active sites from falling off the substrate, thereby enhancing the stability of the catalyst. The performance of the final product can be adjusted by controlling the parameters such as the loading capacity, the carbonization temperature and the like of the metal organic framework. The catalyst prepared by the invention is in 1mol/L KOH electrolyte, and when the current density is 10mA/cm 2 And after the reaction is carried out for 20 hours, the catalytic activity of the catalyst is hardly attenuated, and the catalyst has good stability.
Description
Technical Field
The invention relates to a metal nanoparticle-loaded catalyst taking a biomass carbon source as a template, and a preparation method and application thereof, and belongs to the fields of new energy material technology and electrochemical catalysis.
Background
Hydrogen energy is a promising clean energy, and hydrogen production by water electrolysis is a green pollution-free production mode. The electrolyzed water reaction includes a Hydrogen Evolution Reaction (HER) at the cathode and an Oxygen Evolution Reaction (OER) at the anode. Although theoretically, only 1.23V is needed to smoothly perform the water electrolysis reaction, since OER is a complicated four-electron transfer process, the reaction is slow, and a high overpotential is needed to smoothly perform the water electrolysis. The current commercial OER catalyst mainly comprises IrO 2 And RuO 2 However, these precious metals are scarce in natural reserves, expensive, unstable under acidic or basic conditions, and therefore, it is necessary to develop a stable non-precious metal catalyst.
The preparation method of the prior non-noble metal catalyst comprises the following steps: and (3) carrying out high-temperature calcination treatment on the precursor with the pre-designed morphology to obtain the micro-nano carbon material. After high-temperature carbonization treatment, the electron transmission capability of the material is improved, the catalytic activity is improved, and the method has great application value in the fields of energy conversion/storage and the like. However, the preparation method has high requirements on the selection of precursors.
The transition metal nano-particles are a material capable of replacing a noble metal catalyst, and the transition metal has the following characteristics: compared with precious metal, the natural reserve is rich, the price is low, the preparation is easy, the environment is friendly, and the like. The carbon material widely exists in nature, has high specific surface area, high conductivity, good chemical stability and low cost, and is especially sp 2 Graphite, graphene, carbon nanotubes and the like formed in a hybrid form have good conductivity and are often used as a conductive substrate for preparing an OER composite catalyst. However, in the composite catalyst, the metal nanoparticles are unevenly distributed in the carbon material, and have the problems of small specific surface area, low catalytic performance and the like.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a metal nanoparticle catalyst loaded by using a biomass carbon source as a template, and a preparation method and application thereof.
The technical scheme of the invention is as follows:
a biomass carbon source is used as a template to load a metal nanoparticle catalyst, yeast is used as a template, ZIF-67 is coated on the outer surface of the yeast to obtain a precursor ZIF-67@ yeast, and then the ZIF-67@ yeast is heated and carbonized to obtain the metal NPs @ NPC catalyst with biomass carbon, nitrogen and phosphorus sources as templates to load metal nanoparticles.
The preparation method of the supported metal nanoparticle catalyst by taking the biomass carbon source as the template comprises the following steps:
dispersing Angel yeast into deionized water, culturing at room temperature for 24h, discarding the upper layer turbid liquid, centrifuging and cleaning with deionized water, centrifuging, and lyophilizing to obtain purified yeast;
dispersing the purified yeast obtained in the step 1 in a transition metal salt solution, stirring for 24 hours, and centrifuging to obtain the yeast with metal ions adsorbed on the surface;
step 3, preparing ZIF-67@ yeast;
mixing the yeast with the metal ions adsorbed on the surface obtained in the step 2 with a 2-methylimidazole solution, stirring for 8-12 h, carrying out centrifugal cleaning by using deionized water, and finally centrifuging and freeze-drying to obtain a precursor ZIF-67@ yeast;
step 4, preparing metal NPs @ NPC;
grinding the precursor ZIF-67@ yeast obtained in the step 3 into powder, placing the powder in a porcelain boat, placing the porcelain boat in a tubular furnace, heating and carbonizing the powder in an argon atmosphere, and cooling the carbonized powder to room temperature along with the furnace after carbonization to obtain the metal NPs @ NPC catalyst.
Further limited, the transition metal salt solution in step 2 is cobalt nitrate and/or a mixed solution of cobalt nitrate and nickel nitrate.
Further limiting, the processing conditions of the heating carbonization in the step 4 are as follows: heating at a heating rate of 3 ℃/min to 350-1000 ℃, and keeping the temperature for 2h.
Further, the particle size of the metal NPs @ NPC catalyst is 25 nm-35 nm.
The catalyst taking the biomass carbon source as the template to load the metal nanoparticles is applied to the alkaline electrolyzed water anode OER.
The invention has the following beneficial effects:
the invention takes saccharomycetes as a carbon template, and coats a Metal Organic Framework (MOF) on the surface of the saccharomycetes as a precursor. The method can effectively prevent the active sites from falling off the substrate, thereby enhancing the stability of the catalyst. The performance of the final product can be adjusted by controlling the parameters such as the loading capacity, the carbonization temperature and the like of the metal organic framework. In addition, the invention also has the following advantages:
(1) The invention adopts the yeast containing rich N, P, C element as the template carrier to prepare the metal NPs @ yeast catalyst, which not only improves the distribution uniformity of metal nano particles and reduces the overpotential of OER catalytic reaction, but also can effectively fix catalytic active sites and improve the stability of the catalyst, thus being an ideal catalyst.
(2) The catalyst prepared by the method is a non-noble metal composite material, the used raw materials are easy to purchase, obtain and prepare, the resource is rich, the price is low, and the method is suitable for large-scale preparation.
(3) The catalyst prepared by the invention is in KOH electrolyte of 1mol/L, and when the current density is 10mA/cm 2 And after the reaction is carried out for 20 hours, the catalytic activity of the catalyst is hardly attenuated, and the catalyst has good stability.
(4) The catalyst prepared by the invention takes a biomass carbon nitrogen phosphorus source as a carrier, and the composite material loaded with metal nano particles has better catalytic activity compared with the non-noble metal OER catalyst reported in the current research.
Drawings
FIG. 1 is an XRD spectrum of ZIF-67@ yeast obtained in example 1 and ZIF-67 obtained in comparative example 2;
FIG. 2 is XRD patterns of CoNi NPs @ NPC-350 obtained in example 2, coNi NPs @ NPC-800 obtained in example 3, and CoNi NPs @ NPC-1000 obtained in example 4;
FIG. 3 is a Fourier transform infrared spectrum of the ZIF-67@ yeast obtained in example 1 and the yeast obtained in comparative example 2;
FIG. 4 is an SEM photograph (at different magnifications) of ZIF-67@ yeast obtained in example 1;
FIG. 5 is an SEM image (different positions) of CoNi NPs @ NPC-350 obtained in example 2;
FIG. 6 is an OER linear voltammogram of CoNi NPs @ NPC-350 obtained in example 2, yeast-350 obtained in comparative example 1, ZIF-67-350 obtained in comparative example 3, and bare carbon paper electrode;
FIG. 7 is a Tafel plot of CoNi NPs @ NPC-350 obtained in example 2, yeast-350 obtained in comparative example 1, ZIF-67-350 obtained in comparative example 3, and bare carbon paper electrode;
FIG. 8 is a CV curve of CoNi NPs @ NPC-350 obtained in example 2;
FIG. 9 is a diagram of the double-layer capacitance fit estimation of CoNi NPs @ NPC-350 obtained in example 2;
FIG. 10 is an impedance plot of CoNi NPs @ NPC-350, yeast-350 obtained in comparative example 1, ZIF-67-350 obtained in comparative example 3, and bare carbon paper electrodes;
FIG. 11 shows CoNi NPs @ NPC-350 modified carbon paper electrode at 10mA · cm -2 The following i-t plot.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
Example 1:
preparation of ZIF-67@ yeast
(a) Purification of yeasts
Prepared according to the method and conditions of step (a) in example 1.
(b)Co 2+ 、Ni 2+ Preparation of yeast
Collecting 300mg of the purified yeast obtained in step (a), and dispersing into 50mL of a solution containing 5mmol of Co (NO) 3 ) 2 ·6H 2 O and 5mmol of Ni (NO) 3 ) 2 ·6H 2 Stirring for 24 hours in the O solution to ensure that Co is added 2+ 、Ni 2+ Adsorbed on the surface of yeast. And finally, centrifuging at a certain rotating speed to remove the unadsorbed metal salt solution.
(c) Preparation of ZIF-67@ yeast
Adsorbing Co in the step (b) 2+ 、Ni 2+ The yeast is dispersed in 50mL solution containing 1g of 2-methylimidazole, stirred for 12h, and finally repeatedly centrifuged and cleaned for 3 times by deionized water at the rotating speed of 3000rpm, and the solution is frozen and dried to obtain the ZIF-67@ yeast after freeze drying.
Example 2:
preparation of CoNiNPs @ NPC-350
(a) Purification of yeasts
Prepared according to the method and conditions of step (a) in example 1.
(b)Co 2+ 、Ni 2+ Preparation of yeast
Taking 300mg of the purified yeast obtained in step (a), dispersing it into 50mL of a solution containing 5mmol of Co (NO) 3 ) 2 ·6H 2 O and 5mmol of Ni (NO) 3 ) 2 ·6H 2 Stirring in O solution for 24h to make Co 2+ 、Ni 2+ Adsorbed on the surface of yeast. And finally, centrifuging at a certain rotating speed to remove the unadsorbed metal salt solution.
(c) Preparation of ZIF-67@ yeast
Adsorbing Co in the step (b) 2+ 、Ni 2+ The yeast is dispersed in 50mL solution containing 1g of 2-methylimidazole, stirred for 12h, and finally repeatedly centrifuged and cleaned for 3 times by deionized water at the rotating speed of 3000rpm, and the solution is frozen and dried to obtain the ZIF-67@ yeast after freeze drying.
(d) CoNiNPs @ NPC-350 preparation
And (c) putting a certain amount of the ZIF-67@ yeast precursor obtained in the step (c) into a porcelain boat in a tube furnace, heating to 350 ℃ at the heating rate of 3 ℃/min in the argon atmosphere, then preserving heat for 2h, and cooling to room temperature along with the furnace to obtain CoNi NPs @ NPC-350.
Example 3:
preparation of CoNiNPs-800
The difference between this example and example 2 is that the temperature in step (d) was maintained at 800 ℃ for 2h, and the rest of the operation steps and the parameter settings were the same.
The resulting CoNi NPs-800 catalyst is inThe current density is 10mAcm -2 The overpotential was 292mV.
Example 4:
CoNiNPs@NPC-1000
the difference between this example and example 2 is only that in step (d) the temperature is maintained at 1000 ℃ for 2h, and the rest of the operation steps and the parameter settings are the same.
The obtained CoNi NPs-1000 catalyst has a current density of 10mAcm -2 Next, the overpotential was 305mV.
Comparative example 1:
preparation of Yeast-350
(a) Purification of yeast
Dispersing a certain amount of Angel yeast (containing yeast nutrient matrix) into a certain amount of deionized water, and culturing at room temperature for 24h to consume nutrient substances to obtain relatively pure yeast. And then pouring out the upper layer turbid liquid, repeatedly centrifuging and cleaning the yeast by using deionized water at a certain rotating speed, and then freeze-drying the yeast to obtain the purified yeast after freeze-drying.
(b) Preparation of Yeast-350
Putting a certain amount of the 'pure yeast' precursor obtained in the step (a) into a porcelain boat in a tube furnace, heating to 350 ℃ at the heating rate of 3 ℃/min in the argon atmosphere, then preserving heat for 2h, and cooling to room temperature along with the furnace to obtain the yeast-350.
Comparative example 2:
preparation of ZIF-67
(a) Preparing solution
Preparing a solution A:2.5mmol Co (NO) 3 ) 3 ·6H 2 Dissolving O in 50mL of methanol;
preparing a solution B:10mmol of 2-methylimidazole in 50mL of methanol;
(b) ZIF-67 preparation
And slowly adding the solution B into the solution A, stirring at room temperature for 30min, standing at room temperature for 12h, centrifuging to obtain a purple precipitate, washing with methanol for 3 times, placing in a vacuum drying oven, and drying to obtain ZIF-67.
Comparative example 3:
preparation of ZIF-67-350
(a) Preparing solution
Preparing a solution A:2.5mmol Co (NO) 3 ) 3 ·6H 2 Dissolving O in 50mL of methanol;
preparing a solution B:10mmol of 2-methylimidazole in 50mL of methanol;
(b) ZIF-67 preparation
And slowly adding the solution B into the solution A, stirring at room temperature for 30min, standing at room temperature for 12h, centrifuging to obtain a purple precipitate, washing with methanol for 3 times, placing in a vacuum drying oven, and drying to obtain ZIF-67.
(c) ZIF-67-350 preparation
And (3) placing a certain amount of the prepared precursor in a porcelain boat in a tube furnace, heating at the heating rate of 3 ℃/min to 350 ℃ in the argon atmosphere, then preserving heat for 2h, and cooling to room temperature along with the furnace to obtain ZIF-67-350.
The products obtained in the above examples were tested for performance and analyzed:
all electrochemical tests were done on Chenghua electrochemical workstation. A three-electrode system is adopted for testing in a 1M KOH solution as electrolyte, catalytic powder is loaded on carbon paper to serve as a working electrode, a saturated Ag/AgCl electrode serves as a reference electrode, a carbon rod serves as a counter electrode, and potential values given by the method are relative to a reversible hydrogen electrode. N is required to be carried out on the electrolyte before OER performance test 2 And (5) saturation treatment.
5mg of the catalysts obtained in example 1, example 2, comparative example 1 and comparative example 2, which were uniformly ground, were dispersed in 970. Mu.L of absolute ethanol and 30. Mu.L of Nafion solution, and uniformly mixed by sonication for 30min, and 100. Mu.L of the mixed liquid was uniformly applied to 1X 1cm 2 After they were completely dried, the OER performance was measured on an electrochemical workstation.
FIG. 1 is an XRD pattern of ZIF-67@ yeast obtained in example 1 and ZIF-67 obtained in comparative example 2. FIG. 2 is XRD patterns of CoNiNPs @ NPC-350 obtained in example 2, coNiNPs @ NPC-800 obtained in example 3, and CoNi NPs @ NPC-1000 obtained in example 4. As can be seen from fig. 1, distinct ZIF-67 characteristic diffraction peaks appear in the maps 2 θ =7.52 °, 10.53 °, 12.87 °, 14.86 °, 16.61 ° and 18.16 °, indicating that ZIF-67 is successfully complexed with yeast. After calcination, the characteristic diffraction peak of ZIF-67 is lost, and then diffraction peaks of simple substance Co and simple substance Ni appear, which shows that CoNi nanoparticles (CoNi NPs) are synthesized and loaded on yeast derivative (CNP) materials through calcination, namely CoNi NPs @ NPC.
FIG. 3 is a Fourier transform infrared spectrum of ZIF-67@ yeast obtained in example 1 and ZIF-67 obtained in comparative example 2. The FT-IR showed that the wavelengths were 3357, 2930, 1648, 1538, 1400, 1240, and 1066cm -1 All belong to characteristic absorption peaks of yeast surface functional groups, wherein the absorption peak is 3357cm -1 The signal peak of (A) corresponds to the stretching vibration of-OH \ NH overlapped on the surface of the saccharomycete; 2930cm -1 The signal peak of (2) corresponds to CH stretching vibration; 1400cm -1 The signal peak of (a) corresponds to C = O stretching vibration of the carboxyl group; 1648. 1538 and 1240cm -1 The signal peaks of (a) correspond to the oscillations of amide I, amide II and amide III, respectively, indicating the presence of protein in the yeast cell; 1066cm -1 The signal peak of (b) corresponds to the stretching vibration of P = O. The abundant functional groups on the surface of the yeast play an important role in the adsorption of metal ions. The wavelength is 1305, 1143, 745, 685cm -1 Both belonging to the characteristic absorption peaks of stretching vibration and bending vibration of the ZIF-67-related functional group, wherein 1305 and 1143cm -1 The signal peak of (a) corresponds to the bending vibration of the imidazole ring; 745cm -1 The signal peak of (a) corresponds to the stretching vibration of Co-N. Through Fourier infrared spectrum analysis, the signal peaks of the two samples are basically completely matched, and the success of compounding the ZIF-67 and the yeast is further proved.
FIG. 4 is an SEM photograph of ZIF-67@ yeast obtained in example 1. As can be seen from the figure, the spherical morphology of the yeast was maintained while the ZIF-67 was loaded on the yeast surface, and the yeast surface became rough. FIG. 5 is an SEM photograph of CoNi NPs @ NPC-350 obtained in example 2. As can be seen from the figure, the yeast and ZIF-67 derivatives have finely dispersed metal nanoparticles distributed on the surface, and these finely uniform nanoparticles play an important role in oxygen evolution catalytic reactions.
FIG. 6 is CoNi NPs @ NPC-350 obtained in example 2OER linear voltammograms for yeast-350 obtained in comparative example 1, ZIF-67-350 obtained in comparative example 3, and bare carbon paper electrode. As shown in FIG. 6, the current density was 10mAcm -2 Under the conditions, NPC obtained by calcining pure yeast has poor OER activity and the initial overpotential is 417mV. When ZIF-67 is compounded with yeast, the initial overpotential of CoNiNPs @ NPC-350 is reduced to 296mV after calcination treatment. The main reason is that in the compounding process, metal ions are uniformly adsorbed on the surface of the yeast, and then the metal ions are coordinated with the 2-methylimidazole organic ligand, so that a ZIF-67 'coat' is formed on the surface of the yeast, and the metal ions serving as active sites can be well anchored on the surface of the yeast. High temperature calcination in an inert atmosphere, co 2+ And Ni 2+ The carbon is converted into CoNi alloy nano particles under the reduction action of carbon, and the conductivity and the electrocatalytic performance are greatly improved due to the existence of the alloy nano particles, so that the low overpotential is shown.
FIG. 7 is a Tafel plot of CoNi NPs @ NPC-350 obtained in example 2, yeast-350 obtained in comparative example 1, ZIF-67-350 obtained in comparative example 3, and bare carbon paper electrode. The slope of the Tafel curve was used to treat the low current region of the resulting LSV polarization curve to evaluate catalyst kinetic performance. As shown in FIG. 7, the Tafel slope of CoNi nanoparticles loaded on yeast derivative NPC is the minimum, and is 58mVdec -1 . The fitting result of Tafel slope further verifies the rule obtained by the LSV polarization curve.
FIGS. 8 and 9 are graphs of CV curves and double layer capacitance fit estimates of CoNiNPs @ NPC-350 obtained in example 2, respectively. Cyclic voltammograms at different sweep rates (40 mV/s, 60mV/s, 80mV/s, 100mV/s, 120 mV/s) for the CoNiNPs @ NPC-350 sample. As can be seen from FIG. 8, as the sweep rate increases, the current density of CoNi NPs @ NPC-350 increases; the electric double layer capacitance can be used for reflecting the size of an electrochemical active area, and under the same sweeping speed, the larger the rectangular area reflects that the larger the electric double layer capacitance is, the reaction active surface area is in direct proportion to the electric double layer capacitance value. The electric double layer capacitance value can pass at 1.362V
The slope value of the curve linearly fitted to the scanning rate was estimated, and it can be seen from FIG. 9 that the electric double layer capacitance value of CoNi NPs @ NPC-350 was 6.16 mF-cm -2 。
FIG. 11 shows CoNiNPs @ NPC-800 electrode obtained in example 2 at 10mA · cm -2 Constant current test pattern below. As shown in the figure, after a continuous oxygen evolution process of 20h, the OER potential of CoNiNPs @ NPC-350 is only slightly changed, mainly because oxygen bubbles are continuously evolved to continuously scour the surface of an electrode, and the electrode material is slightly fallen off, so that the CoNi NPs @ NPC shows good OER catalytic stability in an alkaline solution and has long service life.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (3)
1. A preparation method of a catalyst with biomass carbon source as a template and loaded with metal nanoparticles is characterized in that the catalyst takes yeast as a template, ZIF-67 is coated on the outer surface of the yeast to obtain a precursor ZIF-67@ yeast, and then the ZIF-67@ yeast is heated and carbonized to obtain a catalyst with biomass carbon, nitrogen and phosphorus sources as templates and loaded with metal nanoparticles, namely NPs @ NPC;
the method comprises the following steps:
step 1, purifying yeast;
dispersing Angel yeast into deionized water, culturing at room temperature for 24h, discarding the upper layer turbid liquid, centrifuging and cleaning with deionized water, centrifuging, and lyophilizing to obtain purified yeast;
step 2, preparing metal ions/yeast;
dispersing the purified yeast obtained in the step 1 in a transition metal salt solution, stirring for 24 hours, and centrifuging to obtain the yeast with metal ions adsorbed on the surface;
the transition metal salt solution in the step 2 is a cobalt nitrate solution and a nickel nitrate solution;
step 3, preparing ZIF-67@ yeast;
mixing the yeast with the metal ions adsorbed on the surface obtained in the step 2 with a 2-methylimidazole solution, stirring for 8-12 h, carrying out centrifugal cleaning by using deionized water, and finally centrifuging and freeze-drying to obtain a precursor ZIF-67@ yeast;
step 4, preparing metal NPs @ NPC;
grinding the precursor ZIF-67@ yeast obtained in the step 3 into powder, placing the powder in a porcelain boat, placing the porcelain boat in a tubular furnace, heating and carbonizing the powder in the argon atmosphere, and cooling the carbonized powder to room temperature along with the furnace after the carbonization is finished to obtain the metal NPs @ NPC catalyst, wherein the catalyst is applied to an alkaline electrolyzed water anode OER.
2. The method for preparing the catalyst with the biomass carbon source as the template and the supported metal nanoparticles as claimed in claim 1, wherein the treatment conditions of the heating carbonization in the step 4 are as follows: heating at a heating rate of 3 ℃/min to 350-1000 ℃, and keeping the temperature for 2h.
3. The method for preparing the catalyst of claim 1, wherein the particle size of the catalyst is 25 nm-35 nm, and the catalyst is NPs @ NPC.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111061514.4A CN113881965B (en) | 2021-09-10 | 2021-09-10 | Metal nanoparticle supported catalyst with biomass carbon source as template and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111061514.4A CN113881965B (en) | 2021-09-10 | 2021-09-10 | Metal nanoparticle supported catalyst with biomass carbon source as template and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113881965A CN113881965A (en) | 2022-01-04 |
| CN113881965B true CN113881965B (en) | 2023-03-14 |
Family
ID=79008681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111061514.4A Active CN113881965B (en) | 2021-09-10 | 2021-09-10 | Metal nanoparticle supported catalyst with biomass carbon source as template and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113881965B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114768848B (en) * | 2022-04-12 | 2023-09-19 | 齐鲁工业大学 | Preparation method of high-load single-atom catalyst based on zeolite imidazole ester skeleton-67/yeast composite structure |
| CN116078413B (en) * | 2022-12-13 | 2023-07-18 | 青岛科技大学 | Low-noble metal phosphide electrocatalyst based on microbial template derivatization and preparation method and application thereof |
| CN117486264B (en) * | 2023-12-29 | 2024-04-02 | 洛阳理工学院 | Carbon nano-sheet loaded cobalt-based heterojunction material and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105107536A (en) * | 2015-10-09 | 2015-12-02 | 清华大学 | Preparation method of polyhedral cobalt phosphide catalyst for hydrogen production through water electrolysis |
| CN108452817A (en) * | 2017-02-17 | 2018-08-28 | 中国科学院化学研究所 | A kind of carrier-borne transition metal phosphide and preparation method thereof and its application on catalyzing manufacturing of hydrogen |
| CN109019783A (en) * | 2018-08-30 | 2018-12-18 | 浙江大学 | Carbon-based catalysis electrode of cobalt hydroxide/ZIF-67 and its preparation method and application |
| CN109289894A (en) * | 2018-10-19 | 2019-02-01 | 浙江大学 | A kind of phosphatization cobalt/nitrogen mixes porous carbon composite catalytic material and its preparation method and application |
| CN110124704A (en) * | 2019-06-19 | 2019-08-16 | 哈尔滨工业大学 | A kind of preparation method for the cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate |
| CN111346642A (en) * | 2020-02-05 | 2020-06-30 | 临沂大学 | High-dispersion metal nanoparticle/biomass carbon composite electrode material and preparation method and application thereof |
| CN111545208A (en) * | 2020-05-26 | 2020-08-18 | 福州大学 | Cobalt-nickel bimetallic catalyst and preparation method thereof |
| CN112058296A (en) * | 2020-08-19 | 2020-12-11 | 浙江工业大学 | Preparation method and application of carbonized wood-loaded cobalt and nitrogen co-doped carbon nanotube composite material |
| CN112264068A (en) * | 2020-10-17 | 2021-01-26 | 中南大学 | Nitrogen and phosphorus co-doped carbon-based CoFe alloy nano material and preparation method and application thereof |
| CN112892593A (en) * | 2021-01-18 | 2021-06-04 | 广东工业大学 | MOFs/water hyacinth derived material, preparation method thereof and degradation method of organic pollutants |
-
2021
- 2021-09-10 CN CN202111061514.4A patent/CN113881965B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105107536A (en) * | 2015-10-09 | 2015-12-02 | 清华大学 | Preparation method of polyhedral cobalt phosphide catalyst for hydrogen production through water electrolysis |
| CN108452817A (en) * | 2017-02-17 | 2018-08-28 | 中国科学院化学研究所 | A kind of carrier-borne transition metal phosphide and preparation method thereof and its application on catalyzing manufacturing of hydrogen |
| CN109019783A (en) * | 2018-08-30 | 2018-12-18 | 浙江大学 | Carbon-based catalysis electrode of cobalt hydroxide/ZIF-67 and its preparation method and application |
| CN109289894A (en) * | 2018-10-19 | 2019-02-01 | 浙江大学 | A kind of phosphatization cobalt/nitrogen mixes porous carbon composite catalytic material and its preparation method and application |
| CN110124704A (en) * | 2019-06-19 | 2019-08-16 | 哈尔滨工业大学 | A kind of preparation method for the cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate |
| CN111346642A (en) * | 2020-02-05 | 2020-06-30 | 临沂大学 | High-dispersion metal nanoparticle/biomass carbon composite electrode material and preparation method and application thereof |
| CN111545208A (en) * | 2020-05-26 | 2020-08-18 | 福州大学 | Cobalt-nickel bimetallic catalyst and preparation method thereof |
| CN112058296A (en) * | 2020-08-19 | 2020-12-11 | 浙江工业大学 | Preparation method and application of carbonized wood-loaded cobalt and nitrogen co-doped carbon nanotube composite material |
| CN112264068A (en) * | 2020-10-17 | 2021-01-26 | 中南大学 | Nitrogen and phosphorus co-doped carbon-based CoFe alloy nano material and preparation method and application thereof |
| CN112892593A (en) * | 2021-01-18 | 2021-06-04 | 广东工业大学 | MOFs/water hyacinth derived material, preparation method thereof and degradation method of organic pollutants |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113881965A (en) | 2022-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108736031B (en) | Self-supporting PtCo alloy nanoparticle catalyst and preparation method and application thereof | |
| CN108579788B (en) | Composite cobalt vanadium nitride nanowire electrocatalyst and preparation method and application thereof | |
| CN113881965B (en) | Metal nanoparticle supported catalyst with biomass carbon source as template and preparation method and application thereof | |
| CN108816258B (en) | Hollow carbon material doped with hollow cobalt phosphide nanoparticles in situ, preparation method and application of hollow carbon material in hydrogen production by catalytic electrolysis of water | |
| CN109675599B (en) | Nitrogen-doped carbon-coated molybdenum carbide and preparation method and application thereof | |
| CN108963276A (en) | Non-precious metal catalyst and preparation method thereof for catalytic oxidation-reduction | |
| CN109701545B (en) | Electro-catalytic material loaded with vanadium-cobalt alloy nanoparticles and preparation method thereof | |
| CN110075853B (en) | Electrocatalytic fully-decomposed water CoZn-LDHs-ZIF @ C composite structure material, and preparation method and application thereof | |
| CN113363514A (en) | Carbon aerogel supported cobalt monoatomic catalyst for metal air battery, preparation method and application thereof | |
| CN110767914B (en) | Co-N doped porous carbon-coated carbon nanotube core-shell structure catalyst and preparation method and application thereof | |
| CN112968185B (en) | Preparation method of plant polyphenol modified manganese-based nano composite electrocatalyst with supermolecular network framework structure | |
| CN103413951A (en) | Nitrogen-doped graphene-loaded Pt-based alloy nanometre electrocatalyst and preparation method thereof | |
| CN113437314B (en) | Nitrogen-doped carbon-supported low-content ruthenium and Co 2 Three-function electrocatalyst of P nano particle and preparation method and application thereof | |
| CN109908938A (en) | A kind of preparation method of Novel electrolytic water Oxygen anodic evolution catalyst Co@NC/CNT | |
| CN112652780B (en) | Fe/Fe 3 Preparation method of C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst | |
| CN111215056B (en) | Preparation method and application of low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst | |
| CN110694693A (en) | Carbon cloth loaded MoSx/UiO-66 composite material, preparation method and application | |
| CN112968184B (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
| Shi et al. | Biomass-derived precious metal-free porous carbon: Ca-N, P-doped carbon materials and its electrocatalytic properties | |
| CN113862693A (en) | Preparation method and application of nitrogen-doped mesoporous carbon-loaded high-dispersion Ru nanoparticle catalyst | |
| CN111957336A (en) | Preparation method of ZIF-8-derived Fe-N-C oxygen reduction electrocatalyst | |
| CN108579718B (en) | Preparation method and application of indium-doped nano porous carbon material | |
| CN109449448B (en) | Fuel cell cathode catalyst and preparation method and application thereof | |
| CN111841616A (en) | Preparation method of bifunctional atom dispersed iron-nitrogen coordination material catalyst | |
| He et al. | Black phosphorous dots phosphatized bio-based carbon nanofibers/bimetallic organic framework as catalysts for oxygen evolution reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |