CN110707332B - Preparation method and application of bromine-regulated biomass-derived oxygen reduction and hydrogen evolution catalyst - Google Patents
Preparation method and application of bromine-regulated biomass-derived oxygen reduction and hydrogen evolution catalyst Download PDFInfo
- Publication number
- CN110707332B CN110707332B CN201910931573.9A CN201910931573A CN110707332B CN 110707332 B CN110707332 B CN 110707332B CN 201910931573 A CN201910931573 A CN 201910931573A CN 110707332 B CN110707332 B CN 110707332B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxygen reduction
- hydrogen evolution
- biomass
- preparation
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/886—Powder spraying, e.g. wet or dry powder spraying, plasma spraying
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inert Electrodes (AREA)
- Hybrid Cells (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of energy materials, and particularly relates to a preparation method of a bromine-regulated biomass-derived oxygen reduction and hydrogen evolution catalyst, and an application of the catalyst material as a cathode material in a metal (zinc) -air battery. Fully mixing 5,10,15, 20-tetra (4-bromophenyl) porphyrin cobalt compound and mushroom powder by adopting a one-pot co-pyrolysis method to obtain a precursor, calcining the precursor in a nitrogen atmosphere, and obtaining the product with a large specific surface area (604 m) due to the leaving of bromine species in the pyrolysis process2Per g), catalyst material with uniform pore size distribution. The catalyst material of the invention shows high-efficiency oxygen reduction performance (the half-wave potential is 0.85V, which is superior to that of commercial platinum carbon by 0.83V, vs. RHE), and hydrogen evolution performance (the current density is 10mA cm‑2Small overpotential 0.22V, vs. rhe) and higher stability than commercial platinum carbon. The catalyst material is assembled into a zinc-air battery with the maximum output power of 100mW/cm2Is superior to commercial platinum carbon (the maximum output power is 78 mW/cm)2)。
Description
Technical Field
The invention belongs to the field of energy materials, and particularly relates to a preparation method of a bromine-regulated biomass-derived oxygen reduction and hydrogen evolution catalyst, and an application of the catalyst material as an air cathode material in a metal (zinc) -air battery.
Background
High energy consumption, severe pollution and non-renewable fossil fuels do not meet the requirements of sustainable development in human society. With the development of human society, clean, high-capacity and renewable energy storage and conversion technologies, such as fuel cells, metal-air batteries and water-splitting systems, are expected to become alternatives to conventional fossil fuels. Electrochemical oxygen reduction reaction (1/2O) due to the presence of large overpotentials and slow kinetics2+2H+→H2O, ORR) and hydrogen evolution reaction (H)2O→1/2O2+H2HER) as a renewable energy source as mentioned aboveThe core reaction of the technology determines the efficiency of the overall conversion system. However, an effective catalyst is required to overcome these disadvantages. The noble metals platinum (Pt) and platinum-based catalysts are by far the most desirable ORR and HER catalysts, but their large-scale use is severely hampered by the scarcity of Pt resources (37 ppb in the crust), high price (over 55% of the total equipment cost), poor stability and poor methanol tolerance. Therefore, the development of a non-noble metal catalyst with low cost, environmental friendliness and high efficiency to replace the Pt-based catalyst for ORR and HER is considered to be a feasible path for ultimately realizing large-scale application, and has important practical application value.
Currently, transition metal nitride/carbide (TMN/TMCs) modified carbon materials are among the non-noble metal catalysts being the most promising catalyst to replace Pt-based catalysts for ORR and HER because their density of states (DOS) is closer to the fermi level due to the shrinkage of the d-band of the transition metal in TMN/TMCs, thus making the electron donor more prone to adsorb oxygen. Besides good physical properties such as high hardness, high melting point and corrosion resistance, the materials also have good conductivity and stability, and the advantages enable the materials to have catalytic properties not only under single electrolyte conditions (only under alkaline conditions or only under acidic conditions), but also under the full pH value range, which provides a research basis for various energy conversion systems. However, the methods for preparing TMN and TMC are complex, and have very strict requirements on the conditions of instruments, and the cost of the instruments is high, and besides, the specific surface areas of the TMN and TMC are small, so that the mass transfer and electron transfer processes are not facilitated, therefore, the carbon material with large specific surface area and TMN/TMCs modification is developed and prepared by using biomass with low cost through a simple one-pot method, the precursor source is wide, and the prepared catalyst has high catalytic property under the condition of multiple pH values.
Disclosure of Invention
Aiming at the problems in the prior art and the application requirements in the research field, the invention provides a preparation method and application of a non-noble metal-based catalyst which has low cost, simple preparation process, large specific surface area and high catalytic activity (ORR and HER) in the full pH value range without additional activating agent.
The preparation method of the catalyst comprises the steps of firstly designing and synthesizing bromine-substituted phenyl porphyrin as an active center, selecting biomass mushroom as a main carbon source precursor, and dispersing uniform porphyrin compounds in a lamella structure of mushroom powder through a simple self-assembly process to obtain uniformly mixed porphyrin and mushroom powder precursor. The precursor is pyrolyzed, during the pyrolysis process, a uniform pore structure is generated in a mushroom lamellar structure due to volatilization of bromine species, and a bromine substituent is arranged at the periphery of a porphyrin activity center, so that active sites are exposed to the maximum degree while pores are generated, and the prepared catalyst has high-efficiency oxygen reduction and hydrogen precipitation capabilities. It can be applied to a metal (zinc) -air battery or the like as a catalyst for an air electrode.
The molecular structure schematic diagram of 5,10,15, 20-tetra (4-bromophenyl) porphyrin cobalt is as follows:
synthesis of 5,10,15, 20-tetrakis (4-bromophenyl) porphyrin cobalt (CoTBrPP):
step 1: 0.16mmol (149mg) of tetrabromobenzenyl free porphyrin and 1.60mmol (399mg) of cobalt acetate tetrahydrate are taken and added into a 250ml three-necked flask, and 80ml of N, N-dimethylformamide is added;
step 2: starting stirring and heating to 155 ℃, refluxing for eleven hours, stopping heating, and cooling the reaction to room temperature;
and step 3: carrying out reduced pressure distillation by using an oil pump, evaporating N, N-dimethylformamide in the flask to dryness, adding deionized water into the evaporated flask, and generating a brownish red precipitate in the flask;
and 4, step 4: carrying out suction filtration on the obtained precipitate, washing with deionized water until the filtrate becomes colorless, and carrying out vacuum drying on the obtained crude product at 60 ℃;
and 5: the crude product was further recrystallized from chloroform/methanol (volume ratio 1:8) and then filtered, the red-brown precipitate on filter paper was collected, this recrystallization step was carried out twice, and the resulting product was dried overnight in a vacuum oven at 40 ℃ to give cobalt tetrabromophenylporphyrin (CoTBrPP) in 79% yield.
A method of preparing a bromine-conditioned biomass-derived carbon-based catalyst material, comprising the steps of:
step 1: grinding mushroom with planetary ball mill, sieving with 100 mesh sieve to obtain mushroom powder, washing mushroom powder with distilled water and ethanol respectively, and drying at 120 deg.C for 24 hr;
step 2: preparation of porphyrin and mushroom powder precursor: weighing CoTBrPP (50-200mg) and dissolving in a dichloromethane solvent (20ml), uniformly stirring, weighing mushroom powder (800-950mg) and adding into the solvent, stirring the mixture overnight so that the two can be fully assembled, uniformly dispersing porphyrin molecules on a mushroom powder nanosheet layer, and performing rotary evaporation on the obtained mixture to remove the solvent, thus obtaining precursor solid powder;
and step 3: preparation of the carbon-based catalyst: weighing a certain amount of precursor powder, placing the precursor powder into a clean magnetic boat, placing the magnetic boat into a high-temperature tube furnace, performing nitrogen protection in the whole pyrolysis process, firstly performing temperature programming at the rate of 5 ℃ per minute to 700-.
The invention relates to application of a bromine-regulated biomass-derived oxygen reduction and hydrogen evolution catalyst, which is mainly applied to a metal (zinc) -air battery as an air cathode electrode material.
The preparation method of the air cathode electrode comprises the following steps: mixing isopropanol and 5 wt% Nafion solution in a volume ratio of 10-25 to obtain a mixed solution, adding a small amount of ultrapure water for mixing, then weighing a biomass-derived carbon-based catalyst, dispersing the biomass-derived carbon-based catalyst in the mixed solution, spraying the biomass-derived carbon-based catalyst on an electrode substrate (the substrate is carbon paper or carbon cloth generally), and drying at room temperature to obtain the air cathode electrode, wherein the loading amount of the catalyst is as follows: 1mg/cm2。
The invention has the beneficial effects that: (1) the activating agent and the active center are designed on one porphyrin molecule for the first time, bromine species are evaporated from the porphyrin molecule along with the rise of temperature in the pyrolysis process, and the porphyrin molecule is uniformly dispersed in the mushroom powder lamellar structure, so that a uniform pore structure is formed on the mushroom powder lamellar structure, and the specific surface area of the carbon material is increased (604m2And/g) is more beneficial to mass transfer and electronic transmission processes. (2) The bromine substituent is arranged at the periphery of the porphyrin macrocycle, and the formed pore structure is near the active center of the macrocycle, so that the active sites are more effectively exposed while pores are formed, the active sites are more exposed, and the catalytic activity of the catalyst is increased. (3) The presence of bromine species promotes the formation of more transition metal nitrides and transition metal carbides in the carbon material, and the presence of this stable phase gives the catalyst higher stability and high catalytic activity over a variety of pH ranges. (4) The catalyst material of the invention shows high-efficiency oxygen reduction and hydrogen evolution performance, and the preferred half-wave potential of the oxygen reduction reaction of the catalyst is as follows: RHE of 0.85V vs. s is superior to that of commercial Pt-C catalyst of 0.83V, vs. RHE, the stability is much higher than that of commercial Pt-C catalyst, and the hydrogen evolution is carried out at the current density of 10mA cm-2Has small over potential of 0.22V (vs. RHE), and the zinc-air battery assembled by the catalyst has maximum output power of 100mW/cm2Is superior to commercial platinum carbon (the maximum output power is 78 mW/cm)2)。
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a mass spectrum of cobalt tetrabromophenylporphyrin (CoTBrPP);
FIG. 2 is an SEM image of a biomass-derived carbon-based catalyst material of example 3 of the present invention;
FIG. 3 is a linear scan plot of oxygen reduction at 0.1M KOH for a biomass-derived carbon-based catalyst material in example 4 of the present invention;
FIG. 4 is a graph of stability time versus current (i-t) for a biomass-derived carbon-based catalyst material of example 4 of the present invention;
FIG. 5 is a plot of hydrogen evolution polarization at 1M KOH for the biomass-derived carbon-based catalyst material of example 4 of the present invention;
fig. 6 is a polarization curve of a zinc-air battery fabricated in example 5 of the present invention;
Detailed Description
Example 1: weighing mushroom powder 300mg, placing into a clean magnetic boat, placing the magnetic boat into a high temperature tube furnace, and performing nitrogen protection (nitrogen flow rate: 50-60mL min) in the whole pyrolysis process-1) Firstly, raising the temperature to 800 ℃ at the rate of 5 ℃ per minute, keeping the temperature at 800 ℃ for 2 hours, and then lowering the temperature to 25 ℃ at the rate of 5 ℃ per minute to obtain the unmodified biomass mushroom powder catalyst material.
Example 2: preparation of porphyrin and mushroom powder precursor: weighing CoTBrPP (150mg) and dissolving in dichloromethane solvent (20ml), uniformly stirring, weighing mushroom powder (850mg) and adding into the solvent, stirring the mixture overnight so that the mixture and the mushroom powder can be fully assembled, uniformly dispersing porphyrin molecules on a mushroom powder nanosheet layer, and performing rotary evaporation on the obtained mixture to remove the solvent, thereby obtaining precursor solid powder.
Example 3: preparation of the carbon-based catalyst: 300mg of precursor powder is weighed and placed in a clean magnetic boat, the magnetic boat is placed in a high-temperature tube furnace, and the whole process of pyrolysis is protected by nitrogen (nitrogen flow rate: 50-60mL min)-1) Firstly, the temperature is programmed to 800 ℃ at the rate of 5 ℃ per minute, the temperature is kept at 800 ℃ for 2 hours, and then the temperature is programmed to 25 ℃ at the rate of 5 ℃ per minute, so as to obtain the carbon-based catalyst material, which is named as: CoTBrPP @ bio-C. Fig. 2 is an SEM image of the corresponding catalyst material, showing a pronounced uniformly distributed pore structure.
Example 4: preparation of electrode material for oxygen reduction and hydrogen evolution: weighing 5mg of the prepared catalyst material, dispersing the catalyst material in 800 microliters of isopropanol solvent, carrying out ultrasonic treatment for 10 minutes, adding 40 microliters of 5 wt% Nafion solution into the solution, continuing the ultrasonic treatment for 30 minutes to obtain uniform catalyst dispersion liquid, dripping 10 microliters of the dispersion liquid onto a rotating disc electrode (the diameter of the rotating disc electrode is 5mm), naturally drying at room temperature, and testingThe oxygen reduction and hydrogen evolution properties of the catalytic material. FIG. 3 is a linear scan curve of oxygen reduction obtained in this example under 0.1M KOH oxygen saturated solution, corresponding to a half-wave potential of 0.85V (vs. RHE) over 20 wt% commercial platinum carbon catalyst (0.83V, vs. RHE). FIG. 4 is an i-t curve of the stability of the catalyst of this example, which is significantly better than that of the commercial Pt-C catalyst, the material can maintain 98% of the original current density after 15000s of operation, while the Pt-C catalyst has decayed to 65% after 10000 s. FIG. 5 shows the hydrogen evolution curve of the catalyst material of this example in 1M KOH solution at 1600rpm with a current density of 10mA cm-2The material has small over potential of 0.22V (vs. RHE), which indicates that the material also has high hydrogen evolution activity.
Example 5: preparing an air cathode electrode: 5 wt% of Nafion solution, ultrapure water and isopropyl alcohol were mixed at a volume ratio of 3:30:70, and the catalyst material obtained in example 3 (catalyst supporting amount: 1 mg/cm) was added to the mixed solution2) And carrying out ultrasonic dispersion on the mixed solution for 30 minutes to obtain a uniform mixed solution, spraying the mixed solution on an electrode substrate (carbon cloth or carbon paper), and drying at room temperature to obtain the air cathode electrode. For comparison, 20 wt% of commercial platinum carbon was sprayed on the electrode substrate in the same manner. And (3) taking the prepared air cathode electrode as the positive electrode of the zinc-air battery, taking a zinc plate as the negative electrode, taking 6M KOH as electrolyte, and finally assembling the battery. FIG. 6 is a plot of the polarization measured after the electrodes were fabricated in this example, resulting in a catalyst fabricated electrode from example 3 having a higher maximum power density of 100mW/cm2Obviously higher than the maximum power density of commercial platinum carbon (78 mW/cm)2)。
In summary, the invention provides a preparation method and application of a bromine-regulated biomass-derived oxygen reduction and hydrogen evolution catalyst, biomass mushrooms which are low in price and environment-friendly are used as a main carbon source, macrocyclic compound porphyrin is used as an active substance, halogen bromine which is used as an activator is designed to the periphery of a porphyrin macrocyclic active center, and the uniformly mixed mushrooms and porphyrin precursors are calcined through a simple one-pot pyrolysis method to obtain the biomass-derived oxygen reduction and hydrogen evolution catalystThe carbon-based catalyst of (2) is used for oxygen reduction and hydrogen evolution. As the temperature rises during the pyrolysis process, bromine species are evaporated and simultaneously generate a large amount of pore structures on the mushroom sheet layer, so that the obtained catalyst has a large specific surface area (604 m)2Per gram) and the bromine species are evaporated near the active center, so that the active sites are exposed to the maximum extent, and the bromine species are evaporated to promote the formation of more transition metal nitrides and carbides, and the effects are synergistic to ensure that the material has efficient oxygen reduction and hydrogen evolution properties.
The foregoing is illustrative of the preferred embodiments of the present invention, and is not to be construed as limiting the invention in any way; the present invention can be smoothly implemented by those skilled in the art in the light of the accompanying drawings and the above description; however, those skilled in the art should, upon attaining an understanding of the present disclosure, appreciate that many changes, modifications, and equivalents may be made to the invention without departing from the spirit and scope of the invention; meanwhile, any changes, modifications, evolutions, etc. of the equivalent changes made to the above embodiments according to the implementation technology of the present invention are within the protection scope of the technical solution of the present invention.
Claims (3)
1. A preparation method of a bromine-regulated biomass-derived oxygen reduction and hydrogen evolution catalyst is characterized in that the catalyst is prepared by self-assembling halogen bromine-substituted cobalt tetraphenylporphyrin on a nanosheet layer of biomass mushroom powder and further performing one-pot pyrolysis under the protection of inert gas;
the preparation method of the oxygen reduction and hydrogen evolution catalyst comprises the following specific steps:
(1) preparation of a porphyrin and mushroom powder self-assembly precursor: weighing 50-200mg of cobalt tetrabromophenylporphyrin (CoTBrPP) and dissolving in 20mL of dichloromethane solvent, after uniformly stirring, weighing 800-950mg of mushroom powder and adding into the solution, stirring the mixture overnight so that the two can be fully assembled, uniformly dispersing porphyrin molecules on a mushroom powder nanosheet layer, and performing rotary evaporation on the obtained mixture to remove the solvent, thus obtaining precursor solid powder;
(2) preparation of the carbon-based catalyst: weighing a certain amount of precursor powder, placing the precursor powder in a clean magnetic boat, placing the magnetic boat in a high-temperature tube furnace, performing nitrogen protection in the whole pyrolysis process, firstly performing temperature programming to 700-900 ℃ at a speed of 5 ℃/min, keeping for 2 hours, and then performing temperature programming to 25 ℃ at a speed of 5 ℃/min to obtain a biomass-derived carbon-based catalyst material;
the tetrabromophenyl porphyrin cobalt compound is a 5,10,15, 20-tetra (4-bromophenyl) porphyrin cobalt compound;
the mass percentage of the tetrabromophenyl porphyrin compound and the mushroom powder required by the self-assembly precursor is 5-20%, and the pyrolysis temperature is 700-900 ℃ under the protection of inert gas.
2. Use of a biomass-derived oxygen reduction and hydrogen evolution catalyst prepared according to the method of claim 1 in a metal-air battery.
3. The use according to claim 2, the metal-air battery being a zinc-air battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910931573.9A CN110707332B (en) | 2019-09-29 | 2019-09-29 | Preparation method and application of bromine-regulated biomass-derived oxygen reduction and hydrogen evolution catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910931573.9A CN110707332B (en) | 2019-09-29 | 2019-09-29 | Preparation method and application of bromine-regulated biomass-derived oxygen reduction and hydrogen evolution catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110707332A CN110707332A (en) | 2020-01-17 |
| CN110707332B true CN110707332B (en) | 2022-06-21 |
Family
ID=69197883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910931573.9A Active CN110707332B (en) | 2019-09-29 | 2019-09-29 | Preparation method and application of bromine-regulated biomass-derived oxygen reduction and hydrogen evolution catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110707332B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113571719B (en) * | 2021-07-29 | 2022-09-30 | 云南大学 | Biomass carbon material derived transition metal-based catalyst, preparation method and application thereof, and solid zinc-air battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107051386A (en) * | 2017-05-18 | 2017-08-18 | 王煜桐 | The carbon material of chromium ion and its preparation in a kind of energy adsorption aqueous solution |
| CN109346730A (en) * | 2017-11-21 | 2019-02-15 | 中国石油大学(华东) | A kind of preparation method of the oxygen reduction catalyst material based on modified peanut |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101894920B1 (en) * | 2016-12-21 | 2018-09-04 | 현대자동차주식회사 | Non-noble metal based catalyst and method of manufacturing the same |
-
2019
- 2019-09-29 CN CN201910931573.9A patent/CN110707332B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107051386A (en) * | 2017-05-18 | 2017-08-18 | 王煜桐 | The carbon material of chromium ion and its preparation in a kind of energy adsorption aqueous solution |
| CN109346730A (en) * | 2017-11-21 | 2019-02-15 | 中国石油大学(华东) | A kind of preparation method of the oxygen reduction catalyst material based on modified peanut |
Non-Patent Citations (1)
| Title |
|---|
| A facile Self-activated Strategy to Obtain Co,N-contaning Mesoporous Biomass-Derived Carbons as Robust Bifunctional Electrocatalysts for ORR/HER at All pH Values;Xuehui Lv et al;《Abstract of the First Asian Conference on Porphyrins, Phthalocyanines, and Related Materials (ACPP-1) & The Sixth National Conference on Porphyrins, Phthalocyanines, and Related Materials (NCPP-6)》;20190826;第181页摘要 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110707332A (en) | 2020-01-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | From bimetallic metal-organic framework to porous carbon: high surface area and multicomponent active dopants for excellent electrocatalysis | |
| CN110380062B (en) | Preparation method of sulfur-doped bifunctional oxygen catalyst based on ZIF-67 and conductive graphene | |
| CN110739463B (en) | Preparation method and application of bimetal organic framework composite material | |
| Yue et al. | Surface engineering of hierarchical Ni (OH) 2 nanosheet@ nanowire configuration toward superior urea electrolysis | |
| CN109065897B (en) | Phosphorus-doped porous carbon-coated cobaltosic oxide oxygen reduction catalyst and preparation method and application thereof | |
| JP2019157265A (en) | Bismuth nanosheet of which thickness can be controlled, and manufacturing method and use of alloy thereof | |
| CN113270595B (en) | Nitrogen-doped carbon-supported non-noble metal nano catalyst prepared based on MOF | |
| CN111001428B (en) | Metal-free carbon-based electrocatalyst, preparation method and application | |
| Chang et al. | Fabrication of bimetallic Co/Zn leaf blade structure template derived Co3O4-ZIF/Zn and its ORR catalytic performance for MFC | |
| CN113699554B (en) | Preparation method and application of rare earth metal and transition metal co-doped carbon-based material | |
| CN110707337B (en) | Preparation method and application of carbon-based non-noble metal oxygen reduction catalyst | |
| CN113061929A (en) | Nickel phosphide-doped iron-based three-dimensional ultrathin nanosheet material and preparation method and application thereof | |
| Xu et al. | In situ exsolved Co components on wood ear-derived porous carbon for catalyzing oxygen reduction over a wide pH range | |
| CN113373471A (en) | For electrocatalytic reduction of CO2Preparation method and application of indium-based catalyst for preparing low-carbon alcohol | |
| Zou et al. | CoSe 2/Co nanoheteroparticles embedded in Co, N co-doped carbon nanopolyhedra/nanotubes as an efficient oxygen bifunctional electrocatalyst for Zn–air batteries | |
| Zhuang et al. | Enhancing oxygen reduction reaction in air-cathode microbial fuel cells treating wastewater with cobalt and nitrogen co-doped ordered mesoporous carbon as cathode catalysts | |
| CN113410480B (en) | Nickel polyphenol network modified composite triazine-based copolymer carbon nano electro-catalyst material and preparation method and application thereof | |
| Lian et al. | ZIF-derived porous carbon supported cobalt and selenium dual sites enhanced oxygen reduction reaction | |
| CN110707332B (en) | Preparation method and application of bromine-regulated biomass-derived oxygen reduction and hydrogen evolution catalyst | |
| CN111151281B (en) | C 3 N 4 Modified Co 3 O 4 Self-supported ultrathin porous nanosheet and preparation method and application thereof | |
| Wang et al. | Enhancement of electricity generation in single chamber microbial fuel cell using binuclear-cobalt-phthalocyanine and cerium oxide Co-supported on ordered mesoporous carbon as cathode catalyst | |
| CN108963283B (en) | High-dispersion load type core-shell structure Pd @ Ni/WC direct alcohol fuel cell catalyst and preparation method thereof | |
| CN114744220A (en) | In-situ S-doped Fe-NxPreparation method and application of modified mesoporous carbon-oxygen reduction catalyst | |
| Li et al. | Catalytic performance of hybrid Pt@ ZnO NRs on carbon fibers for methanol electro-oxidation | |
| Huang et al. | Development of supported bifunctional oxygen electrocatalysts with high performance for unitized regenerative fuel cell applications |
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 |