CN105720278A - High-efficiency multi-element transition metal phosphide hydrogen-evolution catalyst and preparation method thereof - Google Patents
High-efficiency multi-element transition metal phosphide hydrogen-evolution catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN105720278A CN105720278A CN201610196544.9A CN201610196544A CN105720278A CN 105720278 A CN105720278 A CN 105720278A CN 201610196544 A CN201610196544 A CN 201610196544A CN 105720278 A CN105720278 A CN 105720278A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hydrogen
- precursor
- liberation
- transition metal
- 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.)
- Pending
Links
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
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- 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
-
- 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
Abstract
The invention discloses a high-efficiency multi-element transition metal phosphide hydrogen-evolution catalyst and a preparation method thereof. The catalyst is Co<x>Fe<y>P and is formed by being loaded in carbon cloth by a hydrothermal method. The preparation method of the catalyst comprises the following steps of preparing a precursor by the hydrothermal method, adding a certain amount of a mixture of Co(NO<3>)<2>.6H<2>O and Fe(NO<3>)<3>.9H<2>O into deionized water to form an uniform mixed solution, placing the mixed solution in a reaction kettle, adding carbon cloth (CC) as a carrier, uniformly adding strong ammonia water, hermetically heating the mixed solution to 110-120 DEG C, carrying out heat preservation for 9-10 hours, taking out the CC, and drying the CC to obtain the precursor; and carrying out low-temperature phosphorization on the precursor, separately placing NaH<2>PO<2> and the precursor in an upstream and a downstream of a tube furnace, introducing nitrogen or inert gas, heating the tube furnace to 300-350 DEG C, and carrying out heat preservation for over 2 hours to obtain the hydrogen-evolution catalyst. Compared with the prior art, the hydrogen-evolution catalyst prepared according to the method is endowed with high-efficiency and stable catalytic hydrogen evolution capability in an acidic solution, and the hydrogen production cost through electrolysis of water can be reduced.
Description
Technical field
The present invention relates to a kind of polynary magnesium-yttrium-transition metal phosphide liberation of hydrogen catalyst and preparation method, belong to
In catalysis material technical field.
Background technology
The modernization of World Economics, has benefited from fossil energy, as oil, natural gas extensively should with coal
With.The most exhausted however as fossil energy, and in use pollution to environment, it is desirable to I
Develop cleaning, regenerative resource as early as possible.Hydrogen, may move the energy as one, has higher matter
Energy density, and combustion product is that water receives significant attention.But, up to the present, hydrogen energy source
Mainly also being derived from water, thus water electrolysis hydrogen production has attracted to pay close attention to widely, especially evolving hydrogen reaction
(HER) process 2H++2e-→H2Represent most important process in evolving hydrogen reaction.
For HER process, cathod catalyst effect is particularly significant.So far, the negative electrode that performance is best
Catalyst is noble metal platinum and alloy thereof.This kind of catalyst cost is high, reserves are low, hinders it extensive
Application and commercialized development.Therefore develop cheap, efficient, stable base metal HER catalyst to become
One of focus of reversible hydrogen fuel cell research.Transition metal phosphide (TMP) is low due to its price
Honest and clean, ph stability good, becomes current study hotspot as a kind of novel HER catalyst, as CoP,
Ni2P, FeP, MoP and WP etc. are respectively provided with preferable catalytic hydrogen evolution performance.But, they belong to Dyadic transition
Race's metal phosphide, the avtive spot of only one of which anion state, proton during HER can not be met
The demand of electric discharge, HER process electric current density is the highest, and overpotential is higher, to HER process bring energy consumption high,
The low problem of hydrogen output.
Summary of the invention
The present invention be reduce water electrolysis hydrogen production cost and can the problem of efficient liberation of hydrogen, propose with electric conductivity with
The carbon cloth that corrosion resistance has concurrently, as carrier, is prepared ternary transition race metal phosphide catalyst, is made catalyst
It is coated on carbon cloth surfaces, it is possible to increase effective electro catalytic activity surface area, is that a kind of low-cost height is anti-
Answer active polynary magnesium-yttrium-transition metal phosphide liberation of hydrogen catalyst, can effectively reduce water electrolysis hydrogen producing cost.
The present invention proposes a kind of polynary magnesium-yttrium-transition metal phosphide liberation of hydrogen catalyst, this catalyst be cobalt salt and
Iron salt mixture is supported on carbon cloth by hydrothermal method, forms through low temperature phosphor, wherein cobalt salt and iron salt
Mole is than for 4:1 or 2:1.
Correspondingly, the present invention proposes above-mentioned method for preparing catalyst, comprises the steps:
(1) hydrothermal method prepares precursor: mole mixed than cobalt salt and the iron salt for 4:1 or 2:1
Compound, joins in deionized water, and stirring forms uniform mixed solution；Mixed solution is transferred to instead
Answer in still, add carbon cloth, make carbon cloth be completely immersed in mixed solution；It is uniformly added into strong aqua ammonia；Will reaction
Still seals, and is heated to 110-120 DEG C and keeps constant temperature 9-10h, takes out carbon cloth and be dried, obtaining precursor；
Described strong aqua ammonia is 1ml:1mmol with the ratio of cobalt salt and iron salt mixture.
(2) precursor low temperature phosphor: by NaH2PO2With the upstream that described precursor is individually placed to tube furnace
With dirty, tube furnace is filled with nitrogen or noble gas, is heated to 300-350 DEG C and keeps more than constant temperature 2h,
Obtain described liberation of hydrogen catalyst；Described NaH2PO2It is 3:1 with the mol ratio of cobalt salt and iron salt mixture.
Further, in the preparation method of described catalyst, described hydrothermal temperature is 120 DEG C,
The hydro-thermal reaction time is 10h.
Further, in the preparation method of described catalyst, described low temperature phosphor reaction temperature is 300 DEG C,
Response time is 2h.
Further, in the preparation method of described catalyst, described noble gas is argon.
Further, in the preparation method of described catalyst, dry in described step (1) is in vacuum
In carry out.
Described cobalt salt, including cabaltous nitrate hexahydrate and cobalt chloride hexahydrate；Described iron salt, including nine hydrations
Ferric nitrate and ferric chloride hexahydrate.
Compare with existing preparation method, polynary magnesium-yttrium-transition metal phosphide liberation of hydrogen catalyst prepared by the present invention
There is the highest catalysis activity.The invention by hydrothermal preparing process introduce transition group bimetallic
Hydroxide precursor, overcomes the avtive spot of Dyadic transition group metal phosphide only one of which anion state,
The needs of problems of proton discharge process can not be met.Reacted by low temperature phosphor, the hydrogen around P substituted metal
Oxygen groups forms active center, and active center is mainly made up of two parts: (1) itself is in anion state
P；(2) Fe of the anionic part state that electron rearrangement is formed in course of reaction.Therefore two can be provided
Individual to the ternary transition race metal phosphide in electronically active site can be more beneficial for HER reaction.
Catalyst obtained by the present invention, can be mass, and has abandoned noble metal platinum based catalyst, available
In acidic electrolyte bath, it is electrolysed the reaction of water cathode hydrogen evolution, reduces hydrogen manufacturing cost.Urging obtained by the present invention
The catalysis activity of agent is suitable with Pt, and presents good stability, therefore may be used on reversible hydrogen combustion
In material battery.
Accompanying drawing explanation
Fig. 1 is the polarization curve of the catalyst as prepared by embodiment 1,2,3 and 4；
Fig. 2 is the Tafel curve of the catalyst as prepared by embodiment 1,2；
Fig. 3 is electric current～the timing ampere curve of time of the catalyst as prepared by embodiment 1,2.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and
Embodiment, is further elaborated to the present invention.Should be appreciated that described herein being embodied as
Example only in order to explain the present invention, is not intended to limit the present invention.Additionally, invention described below
Just can mutual group as long as technical characteristic involved in each embodiment does not constitutes conflict each other
Close.
In embodiment, using prepared catalyst as working electrode, area is 1cm2, catalyst is supported on
Quality on carbon cloth is 0.5-1.2mg, in order to the data making electro-chemical test obtain have comparability, below
Example all carries out electrochemistry survey on the CHI 750D electrochemical workstation of Shanghai Chen Hua Instrument Ltd.
Examination.Test condition is as follows: platinum filament is as to electrode, and saturated calomel electrode is as reference electrode, composition
Three electrode test systems, with 0.5M H2SO4Aqueous solution is electrolyte.Wherein, embodiment 2 and 3 is this
Inventive embodiments；Embodiment 1 and 4 is Dyadic transition group metal phosphide liberation of hydrogen prepared by prior art
Catalyst, as reference examples, and is contrasted with liberation of hydrogen ability of the present invention it by electro-chemical test
And evaluation.
Embodiment 1, comprises the steps:
1) hydro-thermal prepares precursor, is joined by 10mmol cabaltous nitrate hexahydrate in 50mL deionized water,
Stirring forms uniform mixed solution；Mixed solution is transferred in 100mL reactor, add carbon cloth
(3×2cm2), make carbon cloth be completely immersed in mixed solution；It is uniformly added into 10mL strong aqua ammonia；Will reaction
Still seals, and is heated to 110 DEG C and keeps constant temperature 9h, takes out carbon cloth and be dried, obtaining precursor；
2) precursor low temperature phosphor: by NaH2PO2With described precursor be individually placed to tube furnace upstream and
Dirty, tube furnace is filled with argon as protective gas, is heated to 300 DEG C and keeps constant temperature 2h, obtains liberation of hydrogen
Catalyst (CoP/CC)；Described NaH2PO2It is 3:1 with the mol ratio of cobalt salt.
Take described catalyst so that it is the area immersing electrolyte in electrochemical property test is 1cm2.With
2mV s-1Sweep speed, measure this catalyst at 0.5M H2SO4Polarization curve in solution.Polarization curve
Test result is as shown in Figure 1.
Embodiment 2, comprises the steps:
1) hydro-thermal prepares precursor, 8mmol cabaltous nitrate hexahydrate and 2mmol Fe(NO3)39H2O is added
Entering in 50mL deionized water, stirring forms uniform mixed solution；Mixed solution is transferred to 100mL
In reactor, add carbon cloth (3 × 2cm2), make carbon cloth be completely immersed in mixed solution；It is uniformly added into 10
ML strong aqua ammonia；Reactor is sealed, is heated to 120 DEG C and keeps constant temperature 10h, take out carbon cloth and be dried,
Obtain precursor；
2) precursor low temperature phosphor: by NaH2PO2With described precursor be individually placed to tube furnace upstream and
Dirty, tube furnace is filled with argon as protective gas, is heated to 300 DEG C and keeps constant temperature 2h, obtains liberation of hydrogen
Catalyst (Co4FeP/CC)；Described NaH2PO2It is 3:1 with the mol ratio of cobalt salt and iron salt mixture.
Take described catalyst so that it is the area immersing electrolyte in electrochemical property test is 1cm2.?
In above-mentioned test system, with 2mV s-1Sweep speed, measure this catalyst at 0.5M H2SO4In solution
Polarization curve, polarization curve test result is as shown in Figure 1.It will be seen from figure 1 that when x:y is 4:1
Time, the catalysis activity of catalyst is the highest, and apparently higher than embodiment 1 gained Dyadic transition group metal phosphorizing
Thing liberation of hydrogen catalyst (CoP/CC).
In above-mentioned test system, with 2mV s-1Sweep speed, measure this catalyst at 0.5M H2SO4Molten
Tafel curve in liquid, test result is as shown in Figure 2.Figure it is seen that embodiment 2 gained
Catalyst (Co4FeP/CC) Tafel slope is sufficiently close to Pt, and apparently higher than embodiment 1 institute
Obtain Dyadic transition group metal phosphide liberation of hydrogen catalyst (CoP/CC).
In above-mentioned test system, under the current potential of-0.4V, measure this catalyst at 0.5M H2SO4Molten
Electric current in liquid～the instant ampere curve of time, test result is as it is shown on figure 3, show embodiment 2 institute
Obtain catalyst (Co4FeP/CC) in an acidic solution can stably catalyzed liberation of hydrogen.
Embodiment 3, comprises the steps:
1) hydro-thermal prepares precursor, and 6.67mmol cabaltous nitrate hexahydrate and 3.33mmol nine are hydrated nitre
Acid ferrum joins in 50mL deionized water, and stirring forms uniform mixed solution；Mixed solution is shifted
In 100mL reactor, add carbon cloth (3 × 2cm2), make carbon cloth be completely immersed in mixed liquor；All
Even addition 10mL strong aqua ammonia；Reactor is sealed, is heated to 110 DEG C and keeps constant temperature 9h, take out carbon
Cloth is also dried, and obtains precursor；
2) precursor low temperature phosphor: by NaH2PO2With described precursor be individually placed to tube furnace upstream and
Dirty, tube furnace is filled with nitrogen or noble gas, is heated to 350 DEG C and keeps more than constant temperature 2h, obtains
Liberation of hydrogen catalyst (Co2FeP/CC)；Described NaH2PO2It is 3 with the mol ratio of cobalt salt and iron salt mixture:
1。
Take described catalyst so that it is the area immersing electrolyte in electrochemical property test is 1cm2.With
2mV s-1Sweep speed, measure this catalyst at 0.5M H2SO4Polarization curve in solution.Polarization curve
Test result is as shown in Figure 1.It will be seen from figure 1 that when x:y is 2:1, the catalysis of catalyst
Activity is only second to embodiment 2 gained catalyst (Co4FeP/CC), and apparently higher than embodiment 1 gained two
Unit's magnesium-yttrium-transition metal phosphide catalyst (CoP/CC).
Embodiment 4, comprises the steps:
1) hydro-thermal prepares precursor, and 10mmol Fe(NO3)39H2O is joined 50mL deionized water
In, stirring forms uniform mixed solution；Mixed solution is transferred in 100mL reactor, add carbon
Cloth (3 × 2cm2), make carbon cloth be completely immersed in mixed liquor；It is uniformly added into 10mL strong aqua ammonia；Will reaction
Still seals, and is heated to 120 DEG C and keeps constant temperature 10h, takes out carbon cloth and be dried, obtaining precursor；
2) precursor low temperature phosphor: by NaH2PO2With described precursor be individually placed to tube furnace upstream and
Dirty, tube furnace is filled with nitrogen or noble gas, is heated to 300 DEG C and keeps more than constant temperature 2h, obtains
Liberation of hydrogen catalyst (FeP/CC)；Described NaH2PO2It is 3:1 with the mol ratio of iron salt.
Take the catalyst of certain area so that it is the area immersing electrolyte in electrochemical property test is 1
cm2.With 2mV s-1Sweep speed, measure this catalyst at 0.5M H2SO4Polarization curve in solution.
Polarization curve test result is as shown in Figure 1.It will be seen from figure 1 that embodiment 4 gained Dyadic transition group
The catalysis activity of metal phosphide liberation of hydrogen catalyst Fe P/CC is significantly lower than the embodiment 2 and 3 polynary mistake of gained
Cross race's metal phosphide liberation of hydrogen catalyst.
Above example is as working electrode at the catalyst prepared using the present invention, platinum filament as to electrode,
Saturated calomel electrode, as reference electrode, forms three electrode test systems, with 0.5M H2SO4Aqueous solution is
Under the test condition of electrolyte, on the CHI 750D electrochemical workstation of Shanghai Chen Hua Instrument Ltd.
Study its catalysis activity, test result indicate that, polynary by prepared by the present invention, i.e. embodiment 2 and 3
Magnesium-yttrium-transition metal phosphide liberation of hydrogen catalyst, compared to existing magnesium-yttrium-transition metal phosphide liberation of hydrogen catalyst,
To H+There is more significant catalytic effect, and liberation of hydrogen is in hgher efficiency, can stably catalyzed analyse in an acidic solution
Hydrogen.
As it will be easily appreciated by one skilled in the art that and the foregoing is only presently preferred embodiments of the present invention,
Not in order to limit the present invention, all made within the spirit and principles in the present invention any amendment, equivalent
Replacement and improvement etc., should be included within the scope of the present invention.
Claims (7)
1. a polynary magnesium-yttrium-transition metal phosphide liberation of hydrogen catalyst, it is characterised in that this catalyst is cobalt salt
It is supported on carbon cloth with iron salt mixture by hydrothermal method, forms through low temperature phosphor, wherein cobalt salt and iron salt
Mole than for 4:1 or 2:1.
2. method for preparing catalyst described in a claim 1, it is characterised in that comprise the steps:
(1) hydrothermal method prepares precursor: mole mixed than cobalt salt and the iron salt for 4:1 or 2:1
Compound, joins in deionized water, and stirring forms uniform mixed solution；Mixed solution is transferred to instead
Answer in still, add carbon cloth, make carbon cloth be completely immersed in mixed solution；It is uniformly added into strong aqua ammonia；Will reaction
Still seals, and is heated to 110-120 DEG C and keeps constant temperature 9-10h, takes out carbon cloth and be dried, obtaining precursor；
Described strong aqua ammonia is 1ml:1mmol with the ratio of cobalt salt and iron salt mixture.
(2) precursor low temperature phosphor: by NaH2PO2With the upstream that described precursor is individually placed to tube furnace
With dirty, tube furnace is filled with nitrogen or noble gas, is heated to 300-350 DEG C and keeps more than constant temperature 2h,
Obtain described liberation of hydrogen catalyst；Described NaH2PO2It is 3:1 with the mol ratio of cobalt salt and iron salt mixture.
The preparation method of polynary magnesium-yttrium-transition metal phosphide liberation of hydrogen catalyst the most according to claim 2,
It is characterized in that, described hydrothermal temperature is 120 DEG C, and the hydro-thermal reaction time is 10h.
4. according to the preparation of the polynary magnesium-yttrium-transition metal phosphide liberation of hydrogen catalyst described in Claims 2 or 3
Method, it is characterised in that described low temperature phosphor reaction temperature is 300 DEG C, the response time is 2h.
5. according to the preparation of the polynary magnesium-yttrium-transition metal phosphide liberation of hydrogen catalyst described in Claims 2 or 3
Method, it is characterised in that described noble gas is argon.
6. according to the preparation of the polynary magnesium-yttrium-transition metal phosphide liberation of hydrogen catalyst described in Claims 2 or 3
Method, it is characterised in that dry in step (1) is carried out in a vacuum.
7. according to the polynary magnesium-yttrium-transition metal phosphide liberation of hydrogen catalyst described in claim 1-6 and preparation side
Method, it is characterised in that described cobalt salt, including cabaltous nitrate hexahydrate and cobalt chloride hexahydrate；Described iron salt,
Including Fe(NO3)39H2O and ferric chloride hexahydrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610196544.9A CN105720278A (en) | 2016-03-31 | 2016-03-31 | High-efficiency multi-element transition metal phosphide hydrogen-evolution catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610196544.9A CN105720278A (en) | 2016-03-31 | 2016-03-31 | High-efficiency multi-element transition metal phosphide hydrogen-evolution catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105720278A true CN105720278A (en) | 2016-06-29 |
Family
ID=56158627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610196544.9A Pending CN105720278A (en) | 2016-03-31 | 2016-03-31 | High-efficiency multi-element transition metal phosphide hydrogen-evolution catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105720278A (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106486680A (en) * | 2016-11-07 | 2017-03-08 | 济南大学 | A kind of preparation method of phosphatization stainless steel electrolytic water catalysis material |
| CN107970960A (en) * | 2017-11-29 | 2018-05-01 | 山东旭晟东阳新材料科技有限公司 | A kind of preparation method of MoP, FeP, redox graphene three-phase composite material |
| CN108160092A (en) * | 2017-10-09 | 2018-06-15 | 江苏大学 | A kind of compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-particle/carbon black and preparation method thereof |
| CN109065901A (en) * | 2018-07-12 | 2018-12-21 | 扬州大学 | Transition metal phosphide-noble metal phosphide composite fuel cell catalyst and its preparation method and application |
| CN109216663A (en) * | 2017-06-30 | 2019-01-15 | 南京理工大学 | A kind of nano particle/carbon cloth combination electrode material and preparation method thereof |
| CN109301267A (en) * | 2018-10-29 | 2019-02-01 | 广东工业大学 | A kind of phosphide nanocatalyst and preparation method thereof |
| CN109759099A (en) * | 2019-03-04 | 2019-05-17 | 河南城建学院 | A kind of photochemical catalyst and preparation method thereof, application |
| CN110172688A (en) * | 2019-06-25 | 2019-08-27 | 青岛大学 | It is a kind of for being electrolysed the preparation method and application of the derivation function hole timber of aquatic products hydrogen |
| CN110180569A (en) * | 2019-05-23 | 2019-08-30 | 武汉科技大学 | Sheet dimolybdenum carbide/transition metal hetero-junctions electro-catalysis composite material and its preparation method |
| CN110404566A (en) * | 2019-08-30 | 2019-11-05 | 安徽理工大学 | It is a kind of to regulate and control the agent of pattern CoFeP Electrocatalytic Activity for Hydrogen Evolution Reaction, preparation method and application by the zinc of substrate of carbon cloth |
| CN110484934A (en) * | 2019-09-02 | 2019-11-22 | 燕山大学 | Nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation method |
| CN110975922A (en) * | 2019-12-31 | 2020-04-10 | 上海应用技术大学 | Co @ FePx-NCs material for hydrogen evolution of alkaline solution and preparation method and application thereof |
| CN111111715A (en) * | 2019-12-31 | 2020-05-08 | 上海应用技术大学 | Fex@Co1-xP-RGO composite material and in-situ synthesis method and application thereof |
| CN111180695A (en) * | 2019-12-31 | 2020-05-19 | 广东工业大学 | MXene/metal phosphide composite material, negative electrode material, preparation and application |
| CN111185206A (en) * | 2020-01-21 | 2020-05-22 | 广东工业大学 | Transition metal-phosphide catalyst and preparation method and application thereof |
| CN111250137A (en) * | 2020-02-20 | 2020-06-09 | 肇庆市华师大光电产业研究院 | Modified g-C for photocatalytic hydrogen production3N4Process for preparing catalyst |
| CN111690945A (en) * | 2019-03-15 | 2020-09-22 | 国家纳米科学中心 | Method for producing hydrogen by electrolyzing waste lignocellulose |
| CN112007671A (en) * | 2020-09-14 | 2020-12-01 | 广西师范大学 | Fe1Co6-P @ CC electrocatalyst and preparation method thereof |
| CN112142000A (en) * | 2019-06-28 | 2020-12-29 | 南京理工大学 | Anion modified nanowire Co3O4Array preparation method |
| CN112774704A (en) * | 2019-11-07 | 2021-05-11 | 天津大学 | Foam nickel self-supporting FeCo phosphide electrocatalyst and preparation method and application thereof |
| CN113249739A (en) * | 2021-06-04 | 2021-08-13 | 中国科学技术大学 | Metal phosphide-loaded monatomic catalyst, preparation method thereof and application of metal phosphide-loaded monatomic catalyst as hydrogen evolution reaction electrocatalyst |
| CN113832494A (en) * | 2021-09-28 | 2021-12-24 | 西安建筑科技大学 | Preparation method and application of transition/rare earth multi-metal co-doped phosphide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100092865A1 (en) * | 2006-12-27 | 2010-04-15 | Tokyo Institute Of Technology | Carbon composite materials and process for production thereof |
| CN104743533A (en) * | 2015-03-23 | 2015-07-01 | 陕西科技大学 | Preparation method for NiCoP nano material |
| CN105214699A (en) * | 2015-09-30 | 2016-01-06 | 南开大学 | A kind of preparation method of porous doping carbon high-dispersion load phosphatization cobalt material and the application in electrocatalytic hydrogen evolution |
-
2016
- 2016-03-31 CN CN201610196544.9A patent/CN105720278A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100092865A1 (en) * | 2006-12-27 | 2010-04-15 | Tokyo Institute Of Technology | Carbon composite materials and process for production thereof |
| CN104743533A (en) * | 2015-03-23 | 2015-07-01 | 陕西科技大学 | Preparation method for NiCoP nano material |
| CN105214699A (en) * | 2015-09-30 | 2016-01-06 | 南开大学 | A kind of preparation method of porous doping carbon high-dispersion load phosphatization cobalt material and the application in electrocatalytic hydrogen evolution |
Non-Patent Citations (6)
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106486680A (en) * | 2016-11-07 | 2017-03-08 | 济南大学 | A kind of preparation method of phosphatization stainless steel electrolytic water catalysis material |
| CN109216663A (en) * | 2017-06-30 | 2019-01-15 | 南京理工大学 | A kind of nano particle/carbon cloth combination electrode material and preparation method thereof |
| CN108160092A (en) * | 2017-10-09 | 2018-06-15 | 江苏大学 | A kind of compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-particle/carbon black and preparation method thereof |
| CN107970960A (en) * | 2017-11-29 | 2018-05-01 | 山东旭晟东阳新材料科技有限公司 | A kind of preparation method of MoP, FeP, redox graphene three-phase composite material |
| CN107970960B (en) * | 2017-11-29 | 2020-11-06 | 山东旭晟东阳新材料科技有限公司 | Preparation method of MoP, FeP and redox graphene three-phase composite material |
| CN109065901A (en) * | 2018-07-12 | 2018-12-21 | 扬州大学 | Transition metal phosphide-noble metal phosphide composite fuel cell catalyst and its preparation method and application |
| CN109065901B (en) * | 2018-07-12 | 2021-09-03 | 扬州大学 | Transition metal phosphide-noble metal phosphide composite fuel cell catalyst and preparation method and application thereof |
| CN109301267A (en) * | 2018-10-29 | 2019-02-01 | 广东工业大学 | A kind of phosphide nanocatalyst and preparation method thereof |
| CN109301267B (en) * | 2018-10-29 | 2021-07-02 | 广东工业大学 | Phosphide nano-catalyst and preparation method thereof |
| CN109759099A (en) * | 2019-03-04 | 2019-05-17 | 河南城建学院 | A kind of photochemical catalyst and preparation method thereof, application |
| CN111690945A (en) * | 2019-03-15 | 2020-09-22 | 国家纳米科学中心 | Method for producing hydrogen by electrolyzing waste lignocellulose |
| CN111690945B (en) * | 2019-03-15 | 2021-05-28 | 国家纳米科学中心 | Method for producing hydrogen by electrolyzing waste lignocellulose |
| CN110180569A (en) * | 2019-05-23 | 2019-08-30 | 武汉科技大学 | Sheet dimolybdenum carbide/transition metal hetero-junctions electro-catalysis composite material and its preparation method |
| CN110172688A (en) * | 2019-06-25 | 2019-08-27 | 青岛大学 | It is a kind of for being electrolysed the preparation method and application of the derivation function hole timber of aquatic products hydrogen |
| CN112142000A (en) * | 2019-06-28 | 2020-12-29 | 南京理工大学 | Anion modified nanowire Co3O4Array preparation method |
| CN112142000B (en) * | 2019-06-28 | 2022-10-28 | 南京理工大学 | Anion modified nanowire Co 3 O 4 Array preparation method |
| CN110404566B (en) * | 2019-08-30 | 2021-12-17 | 安徽理工大学 | Zinc-regulated CoFeP hydrogen evolution electrocatalyst taking carbon cloth as substrate, preparation method and application |
| CN110404566A (en) * | 2019-08-30 | 2019-11-05 | 安徽理工大学 | It is a kind of to regulate and control the agent of pattern CoFeP Electrocatalytic Activity for Hydrogen Evolution Reaction, preparation method and application by the zinc of substrate of carbon cloth |
| CN110484934B (en) * | 2019-09-02 | 2021-06-08 | 燕山大学 | Preparation method of nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material |
| CN110484934A (en) * | 2019-09-02 | 2019-11-22 | 燕山大学 | Nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation method |
| CN112774704A (en) * | 2019-11-07 | 2021-05-11 | 天津大学 | Foam nickel self-supporting FeCo phosphide electrocatalyst and preparation method and application thereof |
| CN111180695A (en) * | 2019-12-31 | 2020-05-19 | 广东工业大学 | MXene/metal phosphide composite material, negative electrode material, preparation and application |
| CN110975922A (en) * | 2019-12-31 | 2020-04-10 | 上海应用技术大学 | Co @ FePx-NCs material for hydrogen evolution of alkaline solution and preparation method and application thereof |
| CN111111715A (en) * | 2019-12-31 | 2020-05-08 | 上海应用技术大学 | Fex@Co1-xP-RGO composite material and in-situ synthesis method and application thereof |
| CN111111715B (en) * | 2019-12-31 | 2023-05-30 | 上海应用技术大学 | Fe (Fe) x @Co 1-x P-RGO composite material and in-situ synthesis method and application thereof |
| CN111185206A (en) * | 2020-01-21 | 2020-05-22 | 广东工业大学 | Transition metal-phosphide catalyst and preparation method and application thereof |
| CN111185206B (en) * | 2020-01-21 | 2023-05-09 | 广东工业大学 | Transition metal-phosphide catalyst and preparation method and application thereof |
| CN111250137A (en) * | 2020-02-20 | 2020-06-09 | 肇庆市华师大光电产业研究院 | Modified g-C for photocatalytic hydrogen production3N4Process for preparing catalyst |
| CN112007671A (en) * | 2020-09-14 | 2020-12-01 | 广西师范大学 | Fe1Co6-P @ CC electrocatalyst and preparation method thereof |
| CN112007671B (en) * | 2020-09-14 | 2022-02-01 | 广西师范大学 | Fe1Co6-P @ CC electrocatalyst and preparation method thereof |
| CN113249739B (en) * | 2021-06-04 | 2022-07-15 | 中国科学技术大学 | Metal phosphide-loaded monatomic catalyst, preparation method thereof and application of metal phosphide-loaded monatomic catalyst as hydrogen evolution reaction electrocatalyst |
| CN113249739A (en) * | 2021-06-04 | 2021-08-13 | 中国科学技术大学 | Metal phosphide-loaded monatomic catalyst, preparation method thereof and application of metal phosphide-loaded monatomic catalyst as hydrogen evolution reaction electrocatalyst |
| CN113832494A (en) * | 2021-09-28 | 2021-12-24 | 西安建筑科技大学 | Preparation method and application of transition/rare earth multi-metal co-doped phosphide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105720278A (en) | High-efficiency multi-element transition metal phosphide hydrogen-evolution catalyst and preparation method thereof | |
| Dutta et al. | Promoting electrocatalytic overall water splitting with nanohybrid of transition metal nitride-oxynitride | |
| CN104174424B (en) | The preparation of the aerogel carried non noble metal oxygen reduction catalyst of a kind of nitrogen-doped graphene | |
| CN110465312A (en) | A kind of self-supporting carbon cloth load cobaltous selenide nickel nanowire preparation method and application | |
| Ribot-Llobet et al. | Assessment of four different cathode materials at different initial pHs using unbuffered catholytes in microbial electrolysis cells | |
| CN109628952A (en) | A kind of Ni-based double-metal hydroxide electrocatalytic hydrogen evolution catalyst of foamed nickel supported Ag doping and preparation method thereof | |
| CN109569683A (en) | A kind of preparation method and application of the porous carbon sheet of nitrogen-phosphor codoping/transition metal phosphide composite material | |
| CN108060411A (en) | A kind of method that one-step method prepares the metal sulfide electrode material of efficient water decomposition | |
| CN104624190B (en) | Cobalt-based transition metal oxygen reduction catalyst, preparation method and application thereof | |
| CN108360030A (en) | The method that electro-deposition prepares self-cradling type nanometer cobalt bimetallic phosphide catalytic hydrogen evolution electrode material in eutectic type ionic liquid | |
| CN110205636A (en) | A kind of preparation method of self-cradling type three-dimensional porous structure double-function catalyzing electrode | |
| CN105304913A (en) | Nitrogen/transition metal-codoped hierarchical-pore carbon oxygen reduction catalyst, and preparation method and application thereof | |
| CN110479320B (en) | High-efficiency bifunctional decomposition water electric catalyst and preparation method thereof | |
| CN106757143A (en) | A kind of water decomposition reaction catalysis electrode and preparation method thereof | |
| CN107188122A (en) | Transition metal phosphide reacts the application of catalyst for preparing hydrogen as borohydride hydrolytic | |
| CN107486233A (en) | A kind of carbonitride adulterates the preparation method and application of carbon-based cobalt/cobalt oxide nanocatalyst | |
| CN109759066B (en) | Preparation method of boron-doped graphene-loaded cobalt-nickel bimetallic oxide oxygen evolution catalyst | |
| WO2020252820A1 (en) | Ferronickel catalytic material, preparation method therefor, and application thereof in preparing hydrogen from electrolyzed water and preparing liquid solar fuel | |
| CN109576730A (en) | A kind of preparation method and application of the cobaltosic oxide nano chip arrays electrode of iron modification | |
| CN109837559A (en) | A kind of FeOOH-nickel-ferric spinel integrated electrode preparation method of hydro-thermal auxiliary | |
| Ma et al. | In situ construction and post-electrolysis structural study of porous Ni 2 P@ C nanosheet arrays for efficient water splitting | |
| CN108611657A (en) | A kind of synthesis and application of the carbon nano-fiber electrochemical catalyst of nitrogenous cobalt molybdenum | |
| CN105977500A (en) | Preparation method of nitrogen-doped carbon/graphene/manganese oxide composite material and application of nitrogen-doped carbon/ graphene/manganese oxide composite material in electrocatalytic reduction of oxygen | |
| CN107974691A (en) | A kind of phosphide/oxidation copper electrode and preparation method thereof | |
| CN105047884B (en) | Three-dimensional oxygen-evolution electrode anode material, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160629 |
|
| RJ01 | Rejection of invention patent application after publication |