CN108923052A - The TiO of N, C doping2Nano-fibre supported Pd@Ni anode catalysts for direct methanol fuel cell - Google Patents

The TiO of N, C doping2Nano-fibre supported Pd@Ni anode catalysts for direct methanol fuel cell Download PDF

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CN108923052A
CN108923052A CN201810735986.5A CN201810735986A CN108923052A CN 108923052 A CN108923052 A CN 108923052A CN 201810735986 A CN201810735986 A CN 201810735986A CN 108923052 A CN108923052 A CN 108923052A
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tio
deionized water
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water solution
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鞠剑峰
吴锦明
石玉军
薛如意
蒋建婷
王蔚
张文静
徐娴
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Nantong 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
    • 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
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    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • 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 kind of N, the TiO of C doping2Nano-fibre supported Pd@Ni anode catalysts for direct methanol fuel cell, catalyst is by the N with high conductivity, the TiO of C doping2Nanofiber is formed with the nano Pd particle@Ni with core-shell structure, the TiO of N, C doping2The mass content of nanofiber is 95 ~ 97%, and the mass content of nano Pd particle@Ni is 3 ~ 5%, n (Pd):N (Ni) is 1:1.Catalyst of the present invention is to methanol catalytic oxidation performance with higher.The intermediate products such as the CO that methanol oxidation generates are adsorbed, are transferred to composite catalyst surface, and are final product CO by direct deep oxidation2.Since the price of Ni, Pd are far below noble metals such as Pt, Ru, and dosage is smaller in the catalyst, therefore the cost of catalyst substantially reduces, and the catalytic performance and resisting CO poison ability of catalyst greatly improve.

Description

The TiO of N, C doping2Nano-fibre supported Pd@Ni direct methanol fuel cell anode is urged Agent
The application is application number：201610206968.9, the applying date：2016.04.06, the title " TiO 2 of N, C doping Nano-fibre supported Pd@Ni direct methanol fuel cell anode is urged
The divisional application of the preparation method of agent ".
Technical field
The present invention relates to a kind of anode catalysts for direct methanol fuel cell and preparation methods.
Background technique
Direct methanol fuel cell（DMFC）With less energy consumption, energy density height, methanol abundance, it is cheap, be System is simple, runs convenient and low noise advantages, it is considered to be future automobile power and other vehicles most promisingization Power supply is learned, the extensive concern of people is caused.The material of DMFC most critical first is that anode catalyst, it directly affects the property of battery Energy, stability, service life and manufacturing cost.Precious metals pt is under cryogenic（Less than 80 DEG C）With excellent catalytic Can, the anode catalyst of DMFC is using Pt as main component at present, and wherein PtRu catalyst has in stronger anti-CO than pure Pt Toxicity can be with higher catalytic activity, it is considered to be the optimal catalyst of DMFC at present, but since it is expensive, in DMFC In utilization rate be less than commercialized requirement.People, which have conducted extensive research, prepares multiplex catalyst to improve its catalysis Activity improves CO and poisons ability, such as has been reported that and be prepared for PtRu-NdOx/C catalyst, it is possible to reduce noble metal in catalyst The dosage of Pt；It is prepared for PtRu-Ni/C composite catalyst according to another report, reduces noble metal dosage, PtRu-Ni/C catalyst ratio PtRu/C catalyst activity is high, and resisting CO poison ability is strong.In addition, due to DMFC anode catalyst mostly with C base such as active carbon, Vulcan XC-72, graphene etc. are carrier, oxidizable, the stable nano-TiO of chemical property in power generation process2It is especially modified Afterwards with the nano-TiO of high electrical conductivity2Composite material is anode-catalyzed even serving as DMFC as DMFC anode catalyst carrier Agent, catalyst activity is high, and resisting CO poison ability is strong, can substantially reduce the manufacturing cost of DMFC anode catalyst.
Summary of the invention
The purpose of the present invention is to provide it is a kind of it is at low cost, catalytic activity is high, the N with mithridatism, the TiO of C doping2It receives The fiber-loaded Pd@Ni anode catalysts for direct methanol fuel cell of rice and preparation method.
The technical solution of the invention is as follows：
A kind of TiO of N, C doping2Nano-fibre supported Pd@Ni anode catalysts for direct methanol fuel cell, it is characterized in that：By The TiO of the N of high conductivity, C doping2Nanofiber is formed with the nano Pd particle@Ni with core-shell structure, the TiO of N, C doping2Nanometer The mass content of fiber is 95 ~ 97%, and the mass content of nano Pd particle@Ni is 3 ~ 5%, n (Pd):N (Ni) is 1:1.
A kind of TiO of N, C doping2The preparation side of nano-fibre supported Pd@Ni anode catalysts for direct methanol fuel cell Method, it is characterized in that：Include the following steps：
（1）The TiO of N, C doping2The preparation of nanofiber：Using sol-gel method and method of electrostatic spinning：By butyl titanate and gather Vinylpyrrolidone（PVP) be dissolved in dehydrated alcohol, be then added dropwise under stiring dehydrated alcohol, glacial acetic acid, deionized water it is mixed Object is closed, carries out electrostatic spinning after forming the colloidal sol of homogeneous transparent；When electrostatic spinning, electrostatic spinning apparatus is added in the colloidal sol, Adjusting voltage is 25 KV, and the distance of spinning head to tinfoil paper is 15 cm, sprays colloidal sol 2ml per hour, obtains PVP/TiO2Fiber.It will PVP/TiO2Fiber is placed in tubular heater, and 300 DEG C of air atmospheres roast 2 h, N2Under protection, N, C is made in 700 DEG C of 1 h of roasting The TiO of doping2Nanofiber.
The dosage molar ratio of above-mentioned each component when preparing colloidal sol is：n（Butyl titanate）:n（Dehydrated alcohol）:n（Glacial acetic acid）: n（Deionized water）:n（Polyvinylpyrrolidone）=1:20~40:1~2.5:2~6:0.1~0.2；
（2）By N, the TiO of C doping2Nanofiber is add to deionized water in the ratio of 20 ~ 50 mg/ml, and ultrasonic disperse is equal It is even, obtain N, the TiO of C doping2Nanofiber dispersion liquid；
（3）By PdCl2It is dissolved into deionized water, forms the PdCl of 5 ~ 10mg Pd/ml2/ deionized water solution；
（4）By NiSO4It is dissolved into deionized water, forms the NiSO of 2 ~ 4mg Ni/ml4 / deionized water solution；
（5）It is 3 ~ 5%, molar ratio n by the mass content of Pd@Ni in the catalyst being finally synthesizing（Pd）:n（Ni）=1:2 ratio PdCl is measured respectively2/ deionized water solution and Ni SO4/ deionized water solution；
（6）By step（5）Measured Ni SO4/ deionized water solution is added drop-wise to the uniform N of ultrasonic disperse, the TiO of C doping2It receives In rice fiber dispersion, dispersion liquid is obtained；
（7）NaOH is dissolved into deionized water, the NaOH deionized water solution that NaOH concentration is 2mol/L is configured to；
（8）Above-mentioned NaOH deionized water solution is added drop-wise to step（6）In dispersion liquid obtained, adjusting pH value is 8.5 ~ 12, is obtained Suspension；
（9）By KBH4It is dissolved into deionized water and is configured to KBH4Concentration is the KBH of 0.2 ~ 0.5 mol/L4/ deionized water solution；
（10）At stirring, inert gas shielding, 80 ~ 90 DEG C, to step（8）KBH is added dropwise in obtained suspension4/ deionization Aqueous solution reacts 2 ~ 6 hours；
（11）It filters after completion of the reaction, deionized water washs into filter liquor sulfate radical-free ion, and 80 ~ 120 DEG C of vacuum drying obtain Load the N of Ni, the TiO of C doping2Nanofiber；
（12）By step（11）The N of load Ni obtained, the TiO of C doping2Nanofiber is added in the ratio of 20 ~ 50 mg/ml Into deionized water, ultrasonic disperse is uniform, must load the N of Ni, the TiO of C doping2Nanofiber dispersion liquid；
（13）Stirring, inert gas shielding, at room temperature by step（5）Measured PdCl2/ deionized water solution is added drop-wise to ultrasound point Dissipate the N of uniform load Ni, the TiO of C doping2In nanofiber dispersion liquid, react 2 ~ 6 hours；
（14）It filters after completion of the reaction, deionized water is washed into filter liquor without chloride ion, and 80 ~ 120 DEG C of vacuum drying must be catalyzed Agent.
The present invention is with the N with high conductivity and high-ratio surface, the TiO of C doping2Nanofiber is carrier and has nucleocapsid The nano Pd particle@Ni of structure is compounded to form multicomponent catalyst；The Pd@Ni catalytic performance with higher of core-shell structure itself, and Pd@ The compound raising TiO of Ni2Electric conductivity and TiO2Catalytic performance, N, C doping improve TiO2Catalytic performance, due to its collaboration Effect, catalyst is to methanol catalytic oxidation performance with higher.The intermediate products such as the CO that methanol oxidation generates are adsorbed, shift It is final product CO to composite catalyst surface, and by direct deep oxidation2.Since the price of Ni, Pd are expensive far below Pt, Ru etc. Metal, and dosage is smaller in the catalyst, therefore can substantially reduce the cost of catalyst, improves the resisting CO poison energy of catalyst Power.
Below with reference to embodiment, the invention will be further described.
Specific embodiment
Embodiment 1：
A kind of TiO of N, C doping2The preparation method of nano-fibre supported Pd@Ni anode catalysts for direct methanol fuel cell, packet Include the following steps：
（1）The TiO of N, C doping2The preparation of nanofiber：Using sol-gel method and method of electrostatic spinning：By 2.2ml metatitanic acid fourth Ester and 4 grams of polyvinylpyrrolidones（PVP）Be dissolved in 22ml dehydrated alcohol, then under stiring be added dropwise 22ml dehydrated alcohol, The mixture of 3.6ml glacial acetic acid, 1.8ml deionized water carries out electrostatic spinning after forming the colloidal sol of homogeneous transparent；Electrostatic spinning When, electrostatic spinning apparatus is added in the colloidal sol, adjusting voltage is 25 KV, and the distance of spinning head to tinfoil paper is 15 cm, per small When spray colloidal sol 2ml, obtain PVP/TiO2Fiber.By PVP/TiO2Fiber is placed in tubular heater, and 300 DEG C of air atmospheres roast 2 h, N2 Under protection, N, the TiO of C doping is made in 700 DEG C of 1 h of roasting2Nanofiber；
（2）By N, the TiO of C doping2Nanofiber is add to deionized water in the ratio of 20 ~ 50 mg/ml, and ultrasonic disperse is equal It is even, obtain N, the TiO of C doping2Nanofiber dispersion liquid；
（3）By PdCl2It is dissolved into deionized water, forms the PdCl of 5 ~ 10mg Pd/ml2/ deionized water solution；
（4）By NiSO4It is dissolved into deionized water, forms the Ni SO of 2 ~ 4mg Ni/ml4/ deionized water solution；
（5）It is 3 %, molar ratio n by the mass content of Pd@Ni in the catalyst being finally synthesizing（Pd）:n（Ni）=1:2 ratio point It Liang Qu not PdCl2/ deionized water solution and Ni SO4/ deionized water solution；
（6）By step（5）Measured NiSO4/ deionized water solution is added drop-wise to the uniform N of ultrasonic disperse, the TiO of C doping2Nanometer In fiber dispersion, dispersion liquid is obtained；
（7）NaOH is dissolved into deionized water, the NaOH deionized water solution that NaOH concentration is 2mol/L is configured to；
（8）Above-mentioned NaOH deionized water solution is added drop-wise to step（6）In dispersion liquid obtained, adjusting pH value is 8.5 ~ 12, is obtained Suspension；
（9）By KBH4It is dissolved into deionized water and is configured to KBH4Concentration is 0.2 ~ 0.5 mol/L（0.2 mol/L of example, 0.4 mol/L,0.5 mol/L）KBH4/ deionized water solution；
（10）In stirring, inert gas shielding, 80 ~ 90 DEG C（80 DEG C, 85 DEG C, 90 DEG C of example）Under, to step（8）Obtained suspension Middle dropwise addition KBH4/ deionized water solution reacts 2 ~ 6 hours（Example 2 hours, 4 hours, 6 hours）；
（11）It filtering after completion of the reaction, deionized water washs into filter liquor sulfate radical-free ion, and 80 ~ 120 DEG C（80 DEG C of example, 100 ℃,120℃）Vacuum drying must load the N of Ni, the TiO of C doping2Nanofiber；
（12）By step（11）The N of load Ni obtained, the TiO of C doping2Nanofiber is added in the ratio of 20 ~ 50 mg/ml Into deionized water, ultrasonic disperse is uniform, must load the N of Ni, the TiO of C doping2Nanofiber dispersion liquid；
（13）Stirring, inert gas shielding, at room temperature by step（5）Measured PdCl2/ deionized water solution is added drop-wise to ultrasound point Dissipate the N of uniform load Ni, the TiO of C doping2In nanofiber dispersion liquid, react 2 ~ 6 hours（Example 2 hours, 4 hours, it is 6 small When）；
（14）It filtering after completion of the reaction, deionized water is washed into filter liquor without chloride ion, and 80 ~ 120 DEG C（80 DEG C of example, 100 DEG C, 120℃）Vacuum drying, obtains catalyst.
Gained catalyst is by the N with high conductivity, the TiO of C doping2Nanofiber and the nanometer with core-shell structure Pd@Ni composition, the TiO of N, C doping2The mass content of nanofiber is 97%, and the mass content of nano Pd particle@Ni is 3 %, n (Pd):N (Ni) is 1:1.
Embodiment 2：
Step（1）When preparing colloidal sol：By 2.2ml butyl titanate and 4 grams of polyvinylpyrrolidones（PVP）It is dissolved in 22ml dehydrated alcohol In, then under stiring be added dropwise 22ml dehydrated alcohol, 4.8ml glacial acetic acid, 3.6ml deionized water mixture, formed uniformly it is saturating Electrostatic spinning is carried out after bright colloidal sol；Step（5）By the catalyst W being finally synthesizing（Pd@Ni）=4%, molar ratio n（Pd）:n（Ni） =1:2 ratio measures PdCl2/ deionized water solution and NiSO4/ deionized water solution；Remaining is the same as embodiment 1.Gained catalyst By the N with high conductivity, the TiO of C doping2Nanofiber is formed with the nano Pd particle@Ni with core-shell structure, N, C doping TiO2The mass content of nanofiber is 96 %, and the mass content of nano Pd particle@Ni is 4 %, n (Pd):N (Ni) is 1:1.
Embodiment 3：
Step（1）When preparing colloidal sol：By 2.2ml butyl titanate and 4 grams of polyvinylpyrrolidones（PVP）It is dissolved in 22ml dehydrated alcohol In, then under stiring be added dropwise 22ml dehydrated alcohol, 7.2ml glacial acetic acid, 4.8ml deionized water mixture, formed uniformly it is saturating Electrostatic spinning is carried out after bright colloidal sol；Step（5）By the catalyst W being finally synthesizing（Pd@Ni）=5%, molar ratio n（Pd）:n（Ni） =1:2 ratio measures PdCl2/ deionized water solution and NiSO4/ deionized water solution；Remaining is the same as embodiment 1.Gained catalyst By the N with high conductivity, the TiO of C doping2Nanofiber is formed with the nano Pd particle@Ni with core-shell structure, N, C doping TiO2The mass content of nanofiber is 95 %, and the mass content of nano Pd particle@Ni is 5 %, n (Pd):N (Ni) is 1:1.
Other embodiments：
The dosage molar ratio of above-mentioned each component when preparing colloidal sol is：n（Butyl titanate）:n（Dehydrated alcohol）:n（Glacial acetic acid）:n（It goes Ionized water）:n（Polyvinylpyrrolidone）=1:20~40:1~2.5:2~6:0.1~0.2；Remaining is the same as embodiment 1.

Claims (1)

1. the TiO of a kind of N, C doping2Nano-fibre supported Pd@Ni anode catalysts for direct methanol fuel cell, it is characterized in that：By The TiO of N with high conductivity, C doping2Nanofiber is formed with the nano Pd particle@Ni with core-shell structure, the TiO of N, C doping2 The mass content of nanofiber is 97%, and the mass content of nano Pd particle@Ni is 3 %, n (Pd):N (Ni) is 1:1；By following method It is prepared：
（1）The TiO of N, C doping2The preparation of nanofiber：Using sol-gel method and method of electrostatic spinning：By 2.2ml butyl titanate With 4 grams of polyvinylpyrrolidones（PVP）It is dissolved in 22ml dehydrated alcohol, 22ml dehydrated alcohol, 3.6ml is then added dropwise under stiring The mixture of glacial acetic acid, 1.8ml deionized water carries out electrostatic spinning after forming the colloidal sol of homogeneous transparent；When electrostatic spinning, by institute It states colloidal sol and electrostatic spinning apparatus is added, adjusting voltage is 25 KV, and the distance of spinning head to tinfoil paper is 15 cm, sprays colloidal sol per hour 2ml obtains PVP/TiO2Fiber；By PVP/TiO2Fiber is placed in tubular heater, and 300 DEG C of air atmospheres roast 2 h, N2Under protection, N, the TiO of C doping is made in 700 DEG C of 1 h of roasting2Nanofiber；
（2）By N, the TiO of C doping2Nanofiber is add to deionized water in the ratio of 20 ~ 50 mg/ml, and ultrasonic disperse is equal It is even, obtain N, the TiO of C doping2Nanofiber dispersion liquid；
（3）By PdCl2It is dissolved into deionized water, forms the PdCl of 5 ~ 10mg Pd/ml2/ deionized water solution；
（4）By NiSO4It is dissolved into deionized water, forms the Ni SO of 2 ~ 4mg Ni/ml4/ deionized water solution；
（5）It is 3 %, molar ratio n by the mass content of Pd@Ni in the catalyst being finally synthesizing（Pd）:n（Ni）=1:2 ratio point It Liang Qu not PdCl2/ deionized water solution and Ni SO4/ deionized water solution；
（6）By step（5）Measured NiSO4/ deionized water solution is added drop-wise to the uniform N of ultrasonic disperse, the TiO of C doping2Nanometer In fiber dispersion, dispersion liquid is obtained；
（7）NaOH is dissolved into deionized water, the NaOH deionized water solution that NaOH concentration is 2mol/L is configured to；
（8）Above-mentioned NaOH deionized water solution is added drop-wise to step（6）In dispersion liquid obtained, adjusting pH value is 8.5 ~ 12, is obtained Suspension；
（9）By KBH4It is dissolved into deionized water and is configured to KBH4Concentration is the KBH of 0.2 ~ 0.5 mol/L4/ deionized water solution；
（10）At stirring, inert gas shielding, 80 ~ 90 DEG C, to step（8）KBH is added dropwise in obtained suspension4/ deionized water Solution reacts 2 ~ 6 hours；
（11）It filters after completion of the reaction, deionized water washs into filter liquor sulfate radical-free ion, and 80 ~ 120 DEG C of vacuum drying obtain Load the N of Ni, the TiO of C doping2Nanofiber；
（12）By step（11）The N of load Ni obtained, the TiO of C doping2Nanofiber is added in the ratio of 20 ~ 50 mg/ml In deionized water, ultrasonic disperse is uniform, must load the N of Ni, the TiO of C doping2Nanofiber dispersion liquid；
（13）Stirring, inert gas shielding, at room temperature by step（5）Measured PdCl2/ deionized water solution is added drop-wise to ultrasound point Dissipate the N of uniform load Ni, the TiO of C doping2In nanofiber dispersion liquid, react 2 ~ 6 hours；
（14）It filters after completion of the reaction, deionized water is washed into filter liquor without chloride ion, and 80 ~ 120 DEG C of vacuum drying must be catalyzed Agent.
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CN108963283B (en) * 2018-07-17 2021-07-02 大连理工大学 High-dispersion load type core-shell structure Pd @ Ni/WC direct alcohol fuel cell catalyst and preparation method thereof
CN109023558B (en) * 2018-09-26 2021-01-12 南通大学 Electrostatic spinning device and electrostatic spinning method for realizing nitrogen doping of carbon material
CN109244485B (en) * 2018-10-16 2021-12-31 南通大学 NiCo/TiO2Battery anode catalyst and preparation method thereof
CN109860641A (en) * 2018-12-26 2019-06-07 武汉喜玛拉雅光电科技股份有限公司 A kind of fuel cell PtRh-C alloy catalyst and its production method and application

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102361089A (en) * 2011-09-09 2012-02-22 南通大学 PdNi / TiO2 nanofiber anode catalyst for direct methanol fuel cell and preparation method thereof
CN102836708A (en) * 2012-09-06 2012-12-26 南通大学 Preparation method of PdAg/TiO2 nanotube direct methanol fuel cell anode catalyst
CN105316797A (en) * 2014-08-05 2016-02-10 无锡华臻新能源科技有限公司 Preparation of titanium dioxide nanofiber modified with nitrogen-doped mesoporous carbon

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100411731C (en) * 2006-09-22 2008-08-20 中国海洋大学 Method for preparing nano powder photocatalyst
CN102945970A (en) * 2012-11-09 2013-02-27 天津工业大学 Method for strengthening stability and conductivity of direct alcohol fuel battery catalyst
CN103769073B (en) * 2014-01-15 2016-04-13 南通大学 A kind of preparation method of potassium doped nanometer titanium dioxide photocatalyst
CN104998676A (en) * 2015-06-30 2015-10-28 宁波工程学院 High-purity N-doped TiO2 full-mesoporous nanofiber

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102361089A (en) * 2011-09-09 2012-02-22 南通大学 PdNi / TiO2 nanofiber anode catalyst for direct methanol fuel cell and preparation method thereof
CN102836708A (en) * 2012-09-06 2012-12-26 南通大学 Preparation method of PdAg/TiO2 nanotube direct methanol fuel cell anode catalyst
CN105316797A (en) * 2014-08-05 2016-02-10 无锡华臻新能源科技有限公司 Preparation of titanium dioxide nanofiber modified with nitrogen-doped mesoporous carbon

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