CN111916772A - Pd/HNC catalytic material, preparation method thereof and application of Pd/HNC catalytic material as fuel cell catalyst - Google Patents

Pd/HNC catalytic material, preparation method thereof and application of Pd/HNC catalytic material as fuel cell catalyst Download PDF

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CN111916772A
CN111916772A CN202010597624.1A CN202010597624A CN111916772A CN 111916772 A CN111916772 A CN 111916772A CN 202010597624 A CN202010597624 A CN 202010597624A CN 111916772 A CN111916772 A CN 111916772A
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hnc
catalytic material
shewanella
palladium
fuel cell
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梁伊丽
张绍辉
谢志勇
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Central South University
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    • 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
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • Y02E60/50—Fuel cells

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Abstract

The invention discloses a Pd/HNC catalytic material, a preparation method thereof and application of the Pd/HNC catalytic material as a fuel cell catalyst. The Pd/HNC catalytic material is formed by uniformly dispersing nano-palladium particles on Shewanella carbide, and the preparation method comprises the steps of stirring a palladium source solution and a Shewanella solution to enable the Shewanella to fully adsorb a palladium source, and carrying out carbonization treatment and reduction treatment on the Shewanella adsorbed with the palladium source to obtain the Pd/HNC catalytic material; the prepared Pd/HNC catalytic material has high oxygen reduction catalytic activity and high stability in both acidic and alkaline environments, and can be applied as a catalytic material of a fuel cell.

Description

Pd/HNC catalytic material, preparation method thereof and application of Pd/HNC catalytic material as fuel cell catalyst
Technical Field
The invention relates to a fuel cell catalyst material, in particular to a Pd/HNC material, a method for adsorbing a palladium source by using Shewanella bacteria and preparing the Pd/HNC material by carbonization and reduction, and application of the Pd/HNC material as a fuel cell catalyst, belonging to the field of fuel cell catalysts.
Background
In recent years, pem fuel cells have attracted considerable attention as green and clean energy conversion devices for use in vehicles and mobile electronic devices. At present, platinum and its alloy are commonly used as electrode catalyst of proton exchange membrane fuel cell, but two important problems in proton exchange fuel cell are not solved yet: on the one hand, the stability of the catalyst is reduced due to corrosion of the carbon support; on the other hand, the catalyst uses noble metals and is expensive, thereby limiting the industrial development thereof. Therefore, it is urgent to improve the stability of the catalyst in catalyzing oxygen reduction and to reduce the production cost.
At present, platinum is generally used as a catalyst for a fuel cell, 20 percent of platinum nanoparticles of the current commercialized fuel cell catalyst are directly loaded on Carbon XC-72, but the shortage of platinum resources and high cost directly restrict the popularization of the fuel cell technology and hinder the commercialization process of the fuel cell catalyst, Pd and Pt belong to the same main group, compared with platinum, the source of palladium is wider, the storage amount in platinum group metals is the highest, the property is similar to that of Pt, and the Pd catalyst has stronger resistance to poisoning, so Pd is often selected as the catalyst, and in addition, the Carbon XC-72 carrier is easy to corrode under an acidic medium.
Disclosure of Invention
Aiming at the defects of poor stability and the like of the existing fuel cell catalyst and carrier thereof, the invention aims to provide a Pd/HNC catalytic material which is obtained by stably loading Pd catalytic active substances on a Shewanella carbide bacterial carrier with high corrosion resistance, good stability and high catalytic activity.
Another object of the present invention is to provide a simple and low-cost method for preparing the Pd/HNC catalytic material.
The third purpose of the invention is to provide an application of the Pd/HNC catalytic material in a fuel cell, which has the characteristics of good catalytic performance, high stability and the like.
In order to achieve the technical purpose, the invention provides a Pd/HNC catalytic material which is formed by uniformly dispersing nano palladium particles on Shewanella carbide.
In the technical scheme of the invention, the Shewanella carbonum has a nitrogen doping effect, and is used for loading nano palladium particles, so that the loading stability of palladium can be improved, and the catalytic activity of palladium can be synergistically improved. The shewanella can well adsorb palladium ions, the palladium ions can be uniformly and stably loaded in the shewanella carbide after carbonization, and particularly, a carbon material formed by the shewanella carbonization has good corrosion resistance.
As a preferable technical scheme, the load capacity of the nano palladium particles on Shewanella carbontea is 5-10%.
As a preferable technical scheme, the Shewanella carbonum is rod-shaped, and the diameter of the Shewanella carbonum is distributed in the range of 40-100 nm.
As a preferable technical scheme, the particle size of the nano palladium particles is distributed between 3 nm and 6 nm.
The invention also provides a preparation method of the Pd/HNC catalytic material, which comprises the steps of stirring the palladium source solution and the Shewanella solution to enable the Shewanella to fully adsorb the palladium source, and carbonizing and reducing the Shewanella adsorbing the palladium source.
Shewanella (Shewanella) selected by the technical scheme of the invention is widely distributed in natural environments of fresh water, ocean, sediments and the like, more than 50 Shewanella are found at present, and a large number of researches show that Shewanella oneidensis MR-1 contains rich hydrogenase, has high tolerance to noble metals and Pd and has high tolerance to Pd2+Has excellent adsorption capacity and certain reduction capacity on metal ions under certain conditions, so that the aim of well depositing metal nano particles can be fulfilled by using Shewanella, and the Shewanella is selected to Pd2+The adsorption characteristic and the subsequent carbonization process can synthesize the carbonized bacteria supported noble metal catalyst with good stability and high catalytic activity. The Shewanella is most preferably Shewanella oneidensis MR-1.
As a preferred technical scheme, the palladium source solution is a sodium chloropalladate solution.
As a preferred technical solution, the carbonization treatment process is: firstly, heating to 180-220 ℃ from room temperature within 0.5-1.5 h under the air atmosphere, preserving heat for 1.5-2.5 h, and further heating to 600-900 ℃ within 1-2 h under the argon atmosphere, preserving heat for 1.5-2.5 h.
As a preferred technical solution, the reduction treatment process is: and (3) preserving the heat for 2-4 hours at 180-220 ℃ in a hydrogen reducing atmosphere.
The invention also provides an application of the Pd/HNC catalytic material, which is characterized in that: as a fuel cell catalyst.
The preparation method of the Pd/HNC catalytic material comprises the following process steps:
firstly, Shewanella culture:
the harboring strain was streaked, and Shewanella oneidedensis MR-1 single colonies (purchased directly) were selected and inoculated into 50mL of sterilized Luria-Bertani medium (5 g yeast extract, 5g NaCl, 10g tryptone per liter of medium) for culture. Shaking the mixture for 12-20 h at 30 ℃ by a shaking table with the rotating speed of 170rpm, and taking 1-2 mL to measure OD 600;
secondly, adsorbing palladium ions by Shewanella:
taking 4L of LB culture solution after sterilization treatment, adding 0.08L of activated bacteria (the inoculum size is 2-3%), shaking by a shaking table at 170rpm for 20-30 h at 30 ℃ (OD600 is about 1.5); then rotating and centrifuging for 7min at 12000rmp for collecting bacteria, pouring out supernatant, respectively cleaning the precipitate for 2-3 times by using phosphate buffer and sterile water, weighing the precipitate (about 47.5g), re-dissolving the cleaned Shewanella cells (performing ultrasonic treatment for 0.5h) in a proper amount of deionized water, and adding a proper amount of dilute hydrochloric acid to adjust the pH value to 4 for later use; 150mL of 1000-1500 mg/L Pd2+Slowly dripping the solution into 300-500 mL of 3.34g/L bacterial solution (pH is 4) by using a syringe needle, stirring by using magnetic force in the whole process, and stirring for 20-24 hours after the solution is dripped and mixed so as to ensure the dispersibility of the subsequent Pd; after stirring, shaking at 170rpm for 60min at 30 deg.C to ensure bacterial pairing to Pd2+The adsorption amount of (c); finally, collecting the sample by rotating and centrifuging at 12000rmp for 7min, taking the supernatant, and measuring Pd by an absorbance method2+Content (estimated palladium content), and placing residual liquid into a waste liquid tank; weighing the precipitate, adding sterile water (about 0.1L), sucking, uniformly mixing, pouring into a cell culture dish (with the thickness of 1-3 mm), horizontally placing in a refrigerator at-80 ℃ for freezing for 24h, performing vacuum freeze drying, weighing and grinding.
Thirdly, heat treatment:
pd is contained in the solution obtained in the second step2+The Shewanella is placed in a tube furnace, and air is firstly introduced to rise from room temperature to 200 ℃ over 1 hour; preserving heat at 200 ℃ for 2h to partially carbonize and activate the bacterial cells; introducing Ar to the mixture, and raising the temperature from 200 ℃ to 600 ℃ after 1-2 h-900 ℃; keeping the temperature of 600-900 ℃ for 2h to completely carbonize the bacteria.
IV, H2Reduction:
putting the sample obtained in the third step in Ar: H2Keeping the temperature at 200 ℃ for 3h under the atmosphere with the flow ratio of 3:1 to ensure that Pd is2+Are sufficiently reduced.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) the Pd/HNC catalytic material has the characteristics of good stability and high catalytic activity in acidic and alkaline systems, and can be widely applied as an oxygen reduction catalyst of a fuel cell.
2) The Pd/HNC catalytic material contains more nitrogen elements, wherein pyridine nitrogen can improve the performance of the catalyst.
3) The technical scheme of the invention adopts Shewanella (Shewanella) to Pd for the first time2+The tolerance and strong adsorption of the metal ions and the reduction capability of the metal ions to realize the catalytic activity Pd2+The deposition is beneficial to obtaining the Pd/HNC catalytic material with good stability and high catalytic activity.
4) The Pd/HNC catalytic material has the advantages of convenient preparation, simple operation and batch production.
Drawings
FIG. 1 is a transmission electron micrograph of the Pd/HNC fuel cell catalyst prepared in example 1.
Fig. 2 is a CV comparison graph of the Pd/HNC fuel cell catalyst prepared in example 1 before and after 5000 ADT cycles in an acid system.
FIG. 3 is a CV comparison graph of 10% Pd/C before and after 5000 ADT cycles in an acidic system.
FIG. 4 is a CV comparison graph of the Pd/HNC fuel cell catalyst prepared in example 1 with pure carbo-bacteria and 10% Pd/C in an alkaline system.
Fig. 5 is a N1S XPS plot of the Pd/HNC fuel cell catalyst prepared in example 1 versus pure carbonfiguration bacteria.
Detailed Description
The following non-limiting specific examples are intended to further illustrate the present disclosure in detail, but are not intended to further limit the scope of the invention as claimed.
The reagents used in the examples of the present invention are commercially available without specific indication.
Example 1
Shewanella culture
A single colony of Shewanella oneidensis MR-1 was selected and inoculated into 50mL of sterilized Luria-Bertani medium (5 g yeast extract, 5g NaCl, 10g tryptone per liter of medium) for culture. Shaking the shaker at a speed of 170rpm at 30 ℃ for 12 h.
Adsorption of palladium ions by Shewanella
Adding 0.08L of activated bacteria (inoculum size is 2%) into sterilized 4L LB culture solution, shaking at 30 deg.C and 170rpm for 20 hr (OD600 is about 1.5); centrifuging at 12000rmp for 7min to collect bacteria, pouring out supernatant, washing the precipitate with phosphate buffer and sterile water for 2 times, respectively, weighing the precipitate (47.5 g), dissolving the washed Shewanella cells in deionized water, and adding dilute hydrochloric acid to adjust pH to 4; 150mL of 1000mg/L Pd2+Slowly dripping the solution into 300mL of 3.34g/L bacterial solution (pH is 4) by using a syringe needle, stirring by using a magnetic force in the whole process, and stirring for 24 hours after the solution is dripped and mixed so as to ensure the dispersibility of the subsequent Pd; after stirring, shaking at 170rpm for 60min at 30 deg.C to ensure bacterial pairing to Pd2+The adsorption amount of (c); finally, collecting the sample by rotating and centrifuging at 12000rmp for 7min, taking the supernatant, and measuring Pd by an absorbance method2+The content (estimating the palladium content, putting the residual liquid into a waste liquid tank, weighing the precipitate by wet weight, adding sterilized water (about 0.1L), sucking, pumping, mixing uniformly, pouring into a cell culture dish (the thickness is 1-3 mm), horizontally placing in a refrigerator at-80 ℃ for freezing for 24h, carrying out vacuum freeze drying, weighing and grinding.
Third, heat treatment
Pd is contained in the solution obtained in the second step2+The Shewanella is placed in a tube furnace, and air is firstly introduced to rise from room temperature to 200 ℃ over 1 hour; preserving heat at 200 ℃ for 2h to partially carbonize and activate the bacterial cells; introducing Ar to rise from 200 ℃ to 600 ℃ over 1 h; keeping the temperature at 600 ℃ for 2h to completely carbonize the bacteria.
IV, H2Reduction of
Putting the sample obtained in the third step in Ar: H2Keeping the temperature at 200 ℃ for 3h under the atmosphere with the flow ratio of 3:1 to ensure that Pd is2+Are sufficiently reduced.
Fifth, electrochemical detection
Dispersing 4mg of prepared Pd/HNC catalytic material in a mixed solution of 500 mu L of ethanol, 400 mu L of distilled water and 100 mu L of 5 wt% nafion solution, performing ultrasonic treatment for half an hour, dripping 15 mu L of the mixed solution on a glassy carbon electrode, naturally drying, and measuring the electrochemical performance of the Pd/HNC catalyst by using an electrochemical workstation, wherein the acidic system uses a saturated calomel electrode as a reference electrode, a platinum sheet as a counter electrode and 0.1M HClO4The sweeping speed is 0.01V/S; in the alkaline system, a silver chloride electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, 0.1M KOH is used as electrolyte, and the sweeping speed is 0.02V/S.
Fig. 1 is a transmission electron microscope image of the Pd/HNC fuel cell catalyst prepared in example 1, from which it can be seen that Pd catalyst nanoparticles are uniformly dispersed on the carbonized bacteria carrier without agglomeration, which indicates that carbonized bacteria can highly disperse the catalyst nanoparticles.
Fig. 2 is a CV comparison graph of the Pd/HNC fuel cell catalyst prepared in example 1 before and after 5000 rounds of ADT in an acidic system, and fig. 3 is a CV comparison graph of 10% Pd/C before and after 5000 rounds of ADT in an acidic system. Comparing fig. 2 and fig. 3, it can be seen that the prepared Pd/HNC catalyst has a higher palladium oxide reduction potential (0.729V) than the commercial Pd/C catalyst in the acidic medium, i.e. the activity of catalyzing oxygen reduction reaction is higher, and in addition, according to 5000-cycle accelerated aging test, the CV curve of the Pd/HNC catalyst is very small in change, while the CV curve of the commercial Pd/C is significantly reduced, which indicates that the prepared Pd/HNC catalyst has higher stability. The mass specific activity of the Pd/HNC catalyst obtained by carbonizing at 600 ℃ in an acidic medium is calculated to be 0.261 mA/mu g; through 5000-turn circulation stability test, the quality specific activity is reduced by 11.8 percent,
FIG. 4 is a graph comparing CV of the Pd/HNC fuel cell catalyst prepared in example 1 with pure carbo-bacteria and 10% Pd/C in an alkaline system. The results show that the prepared Pd/HNC has higher oxygen reduction catalytic activity than the commercial Pd/C catalyst under alkaline medium. The mass specific activity of the Pd/HNC catalyst obtained by carbonizing at 600 ℃ in an alkaline medium is calculated to be 0.381 mA/mu g; through 5000 cycles of circulation stability test, the quality specific activity is reduced by 9.5 percent,
figure 5 is a N1S XPS plot of the Pd/HNC fuel cell catalyst prepared in example 1 versus pure carbonfiguration bacteria. From the figure, it can be known that the prepared Pd/HNC catalyst contains 5 nitrogen types, wherein the existence of pyridine nitrogen and Pd-N can improve the performance of the catalyst.
Example 2
The heat treatment is changed into the following steps: first, the temperature is raised to 200 ℃ from room temperature over 1h by introducing air; preserving heat at 200 ℃ for 2h to partially carbonize and activate the bacterial cells; introducing Ar to rise from 200 ℃ to 700 ℃ over 1 h; keeping the temperature at 700 ℃ for 2h to completely carbonize the bacteria. Other treatment conditions were the same as in example 1.
After 700 ℃ carbonization treatment, the particle size range of the catalyst particles is 3-8 nm, the electrical conductivity of bacterial carbon is improved, and the specific activity of the carbonized bacterial supported palladium catalyst obtained at the carbonization temperature in an acidic medium is 0.276 mA/mu g, which is 1.06 times that of the carbonized bacterial supported palladium catalyst obtained at 600 ℃; through 5000-circle circulation stability test, the quality specific activity is reduced by 10.2%, and the stability is higher than that obtained through 600 ℃ carbonization. Namely the activity and the stability of the carbonized bacteria supported palladium catalyst obtained by carbonization at 700 ℃ are higher than those of carbonized bacteria supported palladium catalyst obtained by carbonization at 600 ℃.
Example 3
The heat treatment is changed into the following steps: first, the temperature is raised to 200 ℃ from room temperature over 1h by introducing air; preserving heat at 200 ℃ for 2h to partially carbonize and activate the bacterial cells; introducing Ar to rise from 200 ℃ to 800 ℃ over 1.5 h; keeping the temperature at 800 ℃ for 2h to completely carbonize the bacteria. Other treatment conditions were the same as in example 1.
After carbonization treatment at 800 ℃, the particle size range of catalyst particles is 3-10 nm, the bacterial carbon conductivity is further improved, and the specific mass activity of the carbonized bacterial supported palladium catalyst obtained at the carbonization temperature in an acidic medium is 0.339 mA/mu g, which is 1.3 times that of the carbonized bacterial supported palladium catalyst obtained at 600 ℃; through 5000-circle circulation stability test, the quality specific activity is reduced by 8.1%, and the stability is higher than that obtained through 600 ℃ carbonization. Namely, the activity and the stability of the carbonized bacteria supported palladium catalyst obtained by carbonization at 800 ℃ are higher than those of carbonized bacteria supported palladium catalyst obtained by carbonization at 600 ℃ and 700 ℃.
Example 4
The heat treatment is changed into the following steps: first, the temperature is raised to 200 ℃ from room temperature over 1h by introducing air; preserving heat at 200 ℃ for 2h to partially carbonize and activate the bacterial cells; introducing Ar to rise from 200 ℃ to 900 ℃ over 2 h; keeping the temperature at 900 ℃ for 2h to completely carbonize the bacteria. Other treatment conditions were the same as in example 1.
After carbonization treatment at 900 ℃, the particle size of the catalyst particles is in the range of 6-15 nm, the electrical conductivity of the bacterial carbon is further improved, but the catalyst is seriously agglomerated at the high temperature, so that the catalyst nanoparticles become coarse, and the performance of the catalyst is seriously reduced. The specific activity of the carbonized bacterial supported palladium catalyst obtained at the carbonization temperature in the acidic medium is 0.197 mA/mu g, which is 0.75 time of that obtained by carbonization treatment at 600 ℃; through 5000-circle circulation stability test, the quality specific activity is reduced by 10.8%, and the stability is slightly higher than that obtained through 600 ℃ carbonization. Namely, the activity of the carbonized bacteria supported palladium catalyst obtained by carbonization at 900 ℃ is far lower than that obtained by treatment at 600 ℃, and the stability is slightly higher than that obtained by treatment at 600 ℃.
From this, it is found that the oxygen reduction catalytic performance of the palladium catalyst supported on the bacteria for carbonization can be improved by appropriately raising the carbonization temperature, but the carbonization temperature is strictly controlled because the palladium catalyst nanoparticles are coarsened and the catalytic performance is deteriorated.

Claims (8)

1. A Pd/HNC catalytic material, characterized in that: is formed by dispersing nano palladium particles on Shewanella carbofrax uniformly.
2. A Pd/HNC catalytic material according to claim 1, characterized in that: the load capacity of the nano palladium particles on the Shewanella carbide is 5-10%.
3. A Pd/HNC catalytic material according to claim 1, characterized in that:
the Shewanella carbonum is rod-shaped, the diameter is distributed in the range of 40-100 nm,
the particle size distribution of the nano palladium particles is between 3 and 6 nm.
4. The method for preparing the Pd/HNC catalytic material as claimed in any one of claims 1 to 3, wherein the Pd/HNC catalytic material comprises the following steps: stirring the palladium source solution and the Shewanella solution to enable the Shewanella to fully adsorb the palladium source, and carbonizing and reducing the Shewanella adsorbing the palladium source to obtain the palladium-enriched palladium.
5. The method for preparing Pd/HNC catalytic material according to claim 4, wherein the Pd/HNC catalytic material is prepared by the following steps:
the palladium source solution is a sodium chloropalladate solution;
the Shewanella is Shewanella oneidensis MR-1.
6. The method for preparing Pd/HNC catalytic material according to claim 4, wherein the Pd/HNC catalytic material is prepared by the following steps: the carbonization treatment process comprises the following steps: firstly, heating to 180-220 ℃ from room temperature within 0.5-1.5 h under the air atmosphere, preserving heat for 1.5-2.5 h, and further heating to 600-900 ℃ within 1-2 h under the argon atmosphere, preserving heat for 1.5-2.5 h.
7. The method for preparing Pd/HNC catalytic material according to claim 4, wherein the Pd/HNC catalytic material is prepared by the following steps: the reduction treatment process comprises the following steps: and (3) preserving the heat for 2-4 hours at 180-220 ℃ in a hydrogen reducing atmosphere.
8. Use of a Pd/HNC catalytic material according to any one of claims 1 to 3, wherein: as a fuel cell catalyst.
CN202010597624.1A 2020-06-28 2020-06-28 Pd/HNC catalytic material, preparation method thereof and application of Pd/HNC catalytic material as fuel cell catalyst Pending CN111916772A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104588677A (en) * 2014-12-04 2015-05-06 华南理工大学 Method for synthesizing shewanella halitios into god nanoparticles and application of gold nanoparticles
CN109019868A (en) * 2018-07-16 2018-12-18 中南大学 A kind of application of load of microorganisms type platinum-nickel alloys nanocatalyst in p-nitrophenol or azo dyes catalytic degradation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104588677A (en) * 2014-12-04 2015-05-06 华南理工大学 Method for synthesizing shewanella halitios into god nanoparticles and application of gold nanoparticles
CN109019868A (en) * 2018-07-16 2018-12-18 中南大学 A kind of application of load of microorganisms type platinum-nickel alloys nanocatalyst in p-nitrophenol or azo dyes catalytic degradation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHAOHUI ZHANG: "Facile synthesis of Pd supported on Shewanella as an efficient catalyst for oxygen reduction reaction", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 *

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