CN108452817A - A kind of carrier-borne transition metal phosphide and preparation method thereof and its application on catalyzing manufacturing of hydrogen - Google Patents
A kind of carrier-borne transition metal phosphide and preparation method thereof and its application on catalyzing manufacturing of hydrogen Download PDFInfo
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Abstract
The invention discloses a kind of carrier-borne transition metal phosphides and preparation method thereof, the carrier-borne transition metal phosphide in preparation process without introduce other chemical substances as phosphorus source, without preparing template, but it is phosphorus source, in-situ preparation transition metal phosphide to utilize the P elements contained by biological material itself.Contain the elements such as a large amount of carbon, hydrogen, oxygen, nitrogen, phosphorus in the source of the biological material --- biological material；By simple hydro-thermal method, the biomaterial can form the carbon material with a large amount of holes and more highly conductive ability after carbonization；And biological material surface has abundant surface functional group, there is the ability of very strong absorption and reduction high-valence state metal to many heavy metal ion.The preparation method reaction step is few, chemical reagent consumption amount is low, easy to operate, reaction time is short and raw material sources are extensive, simple and easy to get, energy conservation and environmental protection, cost-effective, with large-scale industrial production foreground.
Description
Technical field
The invention belongs to catalyst for preparing hydrogen technical fields, and in particular to a kind of carrier-borne transition metal phosphide, its preparation
Method and its application on catalyzing manufacturing of hydrogen.
Background technology
Realize that the clean manufacturing of fuel is a difficult and important task, wherein the research department of mostly important catalyst
Point it is the hot subject of experts and scholars' concern always.Hydrogen Energy is a kind of energy of non-polluting renewable, storage high with fuel value
The advantages that amount is abundant is the clean type energy that a new generation is widely adopted after the non-renewable energy resources such as coal, oil and natural gas
Source.Hydrogen is considered as a carrier of future source of energy, can be widely used in the fields such as automobile-used, household and electron electric power equipment.
Traditional hydrogen gas production essentially from natural gas or coal, the preparation method of industrial hydrogen be mainly vapor pass through it is scorching hot
Coke extracts hydrogen from water-gas, and the hydrogen purity that these methods are prepared is relatively low；Moreover, hydrogen is being prepared
During gas, can also cause fossil fuel consume excessively and the discharge of carbon dioxide；If working out a kind of green ring
The hydrogen production process of guarantor then can largely reduce the consumption of fossil fuel and the discharge of carbon dioxide.Existing hydrogen manufacturing
Technology includes mainly solar photoelectric oxygen, water electrolysis hydrogen production, reforming biomass hydrogen preparation, light biological hydrogen producing and photocatalysis hydrogen production
Deng；Wherein utilize water electrolysis hydrogen production it is efficient, easily form industrialization, be research history at most, achievement hydrogen manufacturing mode most outstanding
One of.One of link as most critical in water electrolysis hydrogen production system, water electrolysis hydrogen production catalyst are always the weight of people's research
Point object.Common catalyst includes mainly noble metal (brill, ruthenium, silver etc.) and alloy (nickel alloy etc.) in electrolysis water.Wherein, expensive
Metal is most wide one of the water electrolysis hydrogen production catalyst of application range, but the rare and high cost of these materials makes their nothings
Method obtains large-scale application.Nickel alloy shows high activity in the alkaline electrolyte, but its activity can drop in an acidic solution
It is low.Therefore, a kind of environmental-friendly method is worked out to synthesize cheap, high-performance and the electricity being stabilized in an acidic solution
Solution water catalyst for preparing hydrogen remains a challenge.
In recent years, as a kind of new catalyst, molybdenum disulfide gradually enters into the visual field of people, and chemism is higher,
Possess the features such as dissolubility is low, catalytic activity is high, chemical property is stablized simultaneously, first in hydrodesulfurization
It is used widely in the field (Hydrodesulfiirization, HDS)；Then it is found that it is in water electrolysis hydrogen production
Excellent catalytic performance is shown in the field (Hydrogen Evolution Reaction, HER), by its internal mechanism
Research finds that molybdenum disulfide has similar reaction mechanism and activated centre in HER and HDS, to find the catalysis of other HER types
Agent provides guide, transition metal phosphide such as phosphating sludge (MoP) and nickel phosphide (Ni2P) as a kind of efficient HDS types catalysis
Agent has the potential quality as HER type catalyst.Loaded catalyst and the most important difference of unsupported catalyst are：Support type
Catalyst has the specific surface area of bigger, more Adsorptions, thus has better catalytic performance.
Currently, the preparation method of carrier-borne transition metal phosphide, has been reported very much.But not all method is all
Highly desirable, the shortcomings that being primarily present, has：It is stringent equipment, higher reaction condition (high temperature and pressure, vacuum condition), complicated cumbersome
The step of, dangerous property or expensive reaction raw materials, the by-product etc. for having pollution.Therefore, a kind of operation letter is found
Single, pollution-free and cost-effective preparation method is extremely significant.
Invention content
In order to solve the deficiencies in the prior art, the purpose of the present invention is to provide a kind of carrier-borne transition metal phosphide and
Preparation method and its application in catalyzing manufacturing of hydrogen.
Purpose of the present invention is to what is be achieved through the following technical solutions：
A kind of preparation method of carrier-borne transition metal phosphide, described method includes following steps：
1) using biological material, source metal, coupler as raw material, hydro-thermal reaction is carried out, intermediate product a is prepared；
2) the intermediate product a that will be prepared in step 1), is placed in tube furnace, after calcining, that is, is prepared described
Carrier-borne transition metal phosphide, the carrier-borne transition metal phosphide include biomass carbon and are carried on the biomass carbon
In transition metal phosphide, wherein the biomass carbon is that hydro-thermal of the biological material through step 1) and step 2) is anti-
It should be with carbon material obtained by calcination processing (i.e. carbonisation).
According to the present invention, the step 1) is specially：Biological material, source metal, coupler are dispersed in water, formed
Reaction system；And the pH value (preferably 3~6) of reaction system is adjusted, it then continues in ptfe autoclave, carries out hydro-thermal
Reaction, after reaction, the intermediate product a is prepared in separation, washing, drying.
According to the present invention, the biological material is before use, be first washed with deionized clean.
According to the present invention, the hydrothermal temperature is 100~280 DEG C, preferably 180~200 DEG C；The hydro-thermal reaction
Time is 6~12h, preferably 7~9h.
According to the present invention, the cleaning solution can be at least one of deionized water, ethyl alcohol.
According to the present invention, the drying condition is dry 4~16h at 60~100 DEG C.
According to the present invention, it is described adjust reaction system pH value be using selected from formic acid, acetic acid, hydrochloric acid, nitric acid, sulfuric acid,
At least one of perchloric acid, ammonium hydroxide, sodium hydroxide, potassium hydroxide adjust the pH value of reaction system.
In the present invention, under the hydrothermal temperature, the source metal introduced can be made uniformly to divide in biological material
It dissipates, so that the carrier-borne transition metal phosphide being evenly distributed can be prepared.
According to the present invention, in step 1), the biological material contains the elements such as C, H, O, N, P；Preferably, the life
Material is selected from the pollen or spore, microalgae, green alga, soybean, agaric, peanut, watermelon seeds, dried mushroom, soya-bean milk, saccharomycete of plant
In one or more, preferably saccharomycete.It hydro-thermal reaction of the biological material through step (1) and step (2) and forges
The carbon material obtained after burning processing (i.e. carbonisation) is biomass carbon.The concentration of the biological material in the reaction system exists
0.01~1000g/L, preferably 0.1~100g/L.
According to the present invention, in step 1), the coupler is selected from least one of sodium chloride or glutaraldehyde；It is described
Tie a concentration of 1 × 10 of agent in the reaction system-6~10mol/L, preferably 1 × 10-5~1mol/L.It is described in the present invention
The effect of knot agent is the protoplast removed in biological material body.
According to the present invention, in step 1), the source metal is selected from chlorate, sulfate, the nitric acid of transition metal element
At least one of salt and acetate；The transition metal element include one kind in Mn, Co, Ni, Fe, Ce, Cu, Zn, Sn or
It is a variety of；The source metal in the reaction system a concentration of 1 × 10-6~0.1mol/L, preferably 1 × 10-5~0.01mol/L.
According to the present invention, in step 2), the calcining the specific steps are：Under inert gas protection, with 0.1~50
DEG C/heating rate of min is warming up to 500~1500 DEG C, constant temperature 1~for 24 hours；Preferably, under inert gas protection, with 1~50
DEG C/heating rate of min is warming up to 700~1200 DEG C, 1~10h of constant temperature.
According to the present invention, the inert gas can be one or more in nitrogen, argon gas, helium.
According to the present invention, the transition metal phosphide can be phosphatization manganese, phosphatization cobalt, nickel phosphide, iron phosphide, phosphatization
It is one or more in cerium, phosphorized copper, zinc phosphide and phosphorization tin.
According to the present invention, the method specifically comprises the following steps：
1) biological material, source metal, coupler are dispersed in water, form reaction system；And adjust reaction system
PH value is then continued to 3~6 in ptfe autoclave, and 6~12h of hydro-thermal reaction, reaction knot are carried out at 100~280 DEG C
Solid product is collected by centrifugation in Shu Hou, and washed respectively with deionized water and/or ethyl alcohol, after in 60~100 DEG C of dry 4~16h,
The intermediate product a is prepared；
2) the intermediate product a that will be prepared in step 1), is placed in tube furnace, under nitrogen protection, with 0.1~50
DEG C/heating rate of min is warming up to 500~1500 DEG C, after constant temperature 1~for 24 hours, that is, the carrier-borne transition metal phosphorus is prepared
Compound.
The present invention also provides a kind of loads that the preparation method using above-mentioned carrier-borne transition metal phosphide is prepared
Type transition metal phosphide containing biomass carbon and is carried in the biomass carbon in the carrier-borne transition metal phosphide
Transition metal phosphide, the biomass carbon obtains by biological material through hydro-thermal reaction and calcination processing.
According to the present invention, the pattern of the carrier-borne transition metal phosphide has spherical, class spider net form or piece shape.For ball
When shape, grain size is 0.5~5 μm；Preferably 1.0~3 μm；Also preferably 1.5~2 μm.
According to the present invention, the pattern of the biomass carbon in the carrier-borne transition metal phosphide has spherical, class cobweb
Shape or piece shape.Preferably, specific surface area is 400~2000m2/g；Preferably 500~1500m2/g；Also preferably 550~
1300m2/g。
According to the present invention, the pattern of the transition metal phosphide being carried in the biomass carbon is in granular form, institute
The grain size for stating transition metal phosphide is 10~50nm；Preferably 15~20nm or 10~20nm.
According to the present invention, the transition metal phosphide even particulate dispersion is simultaneously carried in the biomass carbon.
The present invention also provides the application of above-mentioned carrier-borne transition metal phosphide, the carrier-borne transition metal phosphide can
For in the fields such as catalyzing manufacturing of hydrogen and energy storage.
The present invention also provides a kind of methods of catalyzing manufacturing of hydrogen, wherein using above-mentioned carrier-borne transition metal phosphide conduct
Catalyst carries out the reaction of catalyzing manufacturing of hydrogen.
According to the present invention, the carrier-borne transition metal phosphide is used as catalyst in the method in use, it is filled
Carrying capacity is 50~100 μ g/cm2, preferably 68~75 μ g/cm2。
Beneficial effects of the present invention：
1. a kind of carrier-borne transition metal phosphide of present invention offer and preparation method thereof, the carrier-borne transition metal phosphorus
Compound in preparation process without introduce other chemical substances as phosphorus source, without preparing template, but utilize biological material
P elements contained by itself are phosphorus source, and in-situ preparation transition metal phosphide prepares support type mistake by simple hydro-thermal method
Cross metal phosphide material.The preparation method reaction step is few, chemical reagent consumption amount is low, easy to operate, reaction time is short,
And raw material sources are extensive, simple and easy to get, energy conservation and environmental protection, cost-effective, with large-scale industrial production foreground.
2. carrier-borne transition metal phosphide prepared by the present invention has very high in catalyzing manufacturing of hydrogen and energy storage field
Practicability application prospect.Catalyzing manufacturing of hydrogen method by the carrier-borne transition metal phosphide as catalyst, material due to
The particle of the transition metal phosphide of generation is smaller (10~50nm), and biomass carbon (spherical, class spider net form or piece shape) also has
There is very high specific surface area (400~2000m2/ g), therefore the Supported transition that its active site is synthesized relative to other methods
Metal phosphide is more, so it is with higher hydrogen production activity, the transition metal phosphide catalyst synthesized with other methods
Compared to also having a clear superiority.
Description of the drawings
Fig. 1 is the transmission electron microscope photo for two cobalt of carrier-borne transition metal phosphatization that embodiment 1 is prepared.
Fig. 2 is the electron scanning micrograph for two cobalt of carrier-borne transition metal phosphatization that embodiment 1 is prepared
Fig. 3 is the XRD test results for two cobalt of carrier-borne transition metal phosphatization that embodiment 1 is prepared.
Fig. 4 is the EDS test results for two cobalt of carrier-borne transition metal phosphatization that embodiment 1 is prepared.
Fig. 5 is the test result of the catalytic performance for two cobalt of carrier-borne transition metal phosphatization that embodiment 1 is prepared.
Specific implementation mode
In the present invention, the preparation method is using biological material as phosphorus source, and the biological material is selected from：The flower of plant
A series of phosphorus element-containings such as powder or spore, microalgae, green alga, soybean, agaric, peanut, watermelon seeds, dried mushroom, soya-bean milk, saccharomycete are more
Biological material in it is one or more.Contain the elements such as a large amount of carbon, hydrogen, oxygen, nitrogen, phosphorus in these biological materials,
It is the supplier of micro Nano material natural carbon source and nitrogen source and phosphorus source；The biological material can be formed after carbonization to be had
The carbon material (i.e. biomass carbon of the invention) of a large amount of holes and more highly conductive ability；And biological material surface is with abundant
Surface functional group, to many heavy metal ion have it is very strong absorption and reduction high-valence state metal ability.Therefore, it adsorbs
The biological material of metal ion by high temperature anaerobic carbonization (hydro-thermal) processing after, so that it may with obtain metal, metal oxide or
The composite material of metal phosphide and carbon；Again after further carbonization (roasting) processing, that is, the support type of the present invention is prepared
Transition metal phosphide, such composite material have good permeability, higher conductivity and porosity, are to prepare electrode material
The ideal chose of material, catalyst etc..The preparation method of the present invention is namely based on what such thinking was developed.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read recorded content of the invention, this field skill
Art personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within limited range of the present invention.
Embodiment 1
1. the preparation of two cobalt of carrier-borne transition metal phosphatization (saccharomycete is carbon source and phosphorus source)
1g biological material saccharomycete is washed with deionized totally, is dispersed in 30mL deionized waters, 0.75g is added
The glutaraldehyde and 0.1g transition metals cobalt salt precursor body cobalt acetates of sodium chloride and 50 μ L, are put into 100mL beakers and stir evenly.
Above-mentioned mixed solution is transferred in the autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction 8h at 190 DEG C.Reaction terminates
Afterwards, it is collected by centrifugation, and washes with water 3 times, ethyl alcohol cleans 3 times, and the precipitation of collection is put into baking oven, and dry 8h, that is, make at 80 DEG C
It is standby to obtain intermediate product a；It after being cooled to room temperature, is put into tube furnace, under an inert atmosphere with the heating rate of 5 DEG C/min
700 DEG C are warming up to, 6h is kept the temperature, obtains two cobalt of carrier-borne transition metal phosphatization.
Fig. 1 is the transmission electron microscope photo for two cobalt of carrier-borne transition metal phosphatization that embodiment 1 is prepared.By scheming
As can be seen that evenly dispersed two cobalt granule of transition metal phosphatization in carbon ball.
Fig. 2 is the electron scanning micrograph for two cobalt of carrier-borne transition metal phosphatization that embodiment 1 is prepared.By scheming
As can be seen that the pattern of two cobalt of carrier-borne transition metal phosphatization is the sphere of 1.5~2 μm and stable homogeneous.
Fig. 3 is the XRD test results for two cobalt of carrier-borne transition metal phosphatization that embodiment 1 is prepared.Fig. 4 is embodiment
The EDS test results of 1 two cobalt of carrier-borne transition metal phosphatization being prepared.It can be seen that inside carbon ball by Fig. 3 and Fig. 4
Grain is two cobalt of transition metal phosphatization really.
The specific surface area of biomass carbon in two cobalt of carrier-borne transition metal phosphatization that the present embodiment is prepared is
576m2/g；The grain size of two cobalt of transition metal phosphatization in two cobalt of carrier-borne transition metal phosphatization is 15~20nm.
2. performance test of two cobalt of carrier-borne transition metal phosphatization as the catalyzing manufacturing of hydrogen of catalyst
The preparation of 2-1. electrodes
Two cobalt of carrier-borne transition metal phosphatization that 1.00mg above-described embodiments are prepared is weighed with accurate electronic balance
As catalyst, the perfluorosulfonic acid type polymer solution (Nafion solution) that 80 μ L mass fractions are 5wt% is then added, and molten
(volume ratio of second alcohol and water is 1 in the mixed solution of the second alcohol and water of 600 μ L:4, i.e. 120 μ L ethyl alcohol and 480 μ L distill
Water), after ultrasonic disperse 0.5h, take 5 μ L (about 5 μ g) drops in (electrode uses polishing powder before use on the glass-carbon electrode of a diameter of 3mm
Polished and cleaned), it carries out air-drying processing, the about 71 μ g/ of useful load of two Co catalysts of carrier-borne transition metal phosphatization at room temperature
cm2。
2-2. catalytic performance test
Catalytic performance test is carried out on IM6ex electrochemical workstations, is assessed its catalytic performance, is recycled
Voltammetric scan (CV), linear voltammetric scan (LSV), stability test and testing impedance, whole system is with 0.5M H2SO4Solution
(100mL) is used as electrolyte, and using saturated calomel electrode as reference electrode, carbon-point is as auxiliary electrode, glass-carbon electrode conduct
Working electrode；Obtain working electrode potential by comparing saturated calomel electrode, and by reversible hydrogen electrode (Reversible and
Hydrogen electrode, RHE) it is corrected.
Fig. 5 is the test result of the catalytic performance for two cobalt of carrier-borne transition metal phosphatization that embodiment 1 is prepared.By scheming
As can be seen that the material has the performance of good catalyzing manufacturing of hydrogen, in 10mAcm-2Under, overpotential 145mV.
Embodiment 2
1. the preparation of two cobalt of carrier-borne transition metal phosphatization (agaric is carbon source and phosphorus source)
It is washed with deionized totally, is dispersed in 30mL deionized waters after 1g biological material agarics are impregnated, is added
The glutaraldehyde and 0.1g transition metals cobalt salt precursor body cobalt acetates of 0.75g sodium chloride and 50 μ L, are put into 100mL beakers and stir
Uniformly.Above-mentioned mixed solution is transferred in the autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction 8h at 190 DEG C.Reaction
After, it being collected by centrifugation, and wash with water 3 times, ethyl alcohol cleans 3 times, and the precipitation of collection is put into baking oven, the dry 8h at 80 DEG C,
Intermediate product a is prepared；It after being cooled to room temperature, is put into tube furnace, under an inert atmosphere with the heating of 5 DEG C/min
Rate is warming up to 700 DEG C, keeps the temperature 6h, obtains two cobalt of carrier-borne transition metal phosphatization.
The appearance structure for two cobalt of carrier-borne transition metal phosphatization that the present embodiment is prepared is class spider net form；It is described negative
The specific surface area of biomass carbon in two cobalt of load type transition metal phosphatization is 1239m2/g；The carrier-borne transition metal phosphatization two
The grain size of two cobalt of transition metal phosphatization in cobalt is 10~20nm.
2. the performance test of two cobalt catalyzing manufacturing of hydrogen of carrier-borne transition metal phosphatization
The preparation of 2-1. electrodes
Two cobalt of carrier-borne transition metal phosphatization that 1.00mg above-described embodiments are prepared is weighed with accurate electronic balance
Then catalyst is added 80 μ L mass fractions and is the perfluorosulfonic acid type polymer solution (Nafion solution) of 5wt%, and is dissolved in
(volume ratio of second alcohol and water is 1 in the mixed solution of the second alcohol and water of 600 μ L:4, i.e. 120 μ L ethyl alcohol and 480 μ L distilled water),
After ultrasonic disperse 0.5h, take 5 μ L (about 5 μ g) drops in (electrode is polished using preceding with polishing powder on the glass-carbon electrode of a diameter of 3mm
Cleaning), it carries out air-drying processing, the about 71 μ g/cm of useful load of two Co catalysts of carrier-borne transition metal phosphatization at room temperature2。
2-2. catalytic performance test
Catalytic performance test is the same as the catalytic performance test described in 2-2 in embodiment 1.
It is that embodiment 2 is prepared the result shows that two cobalt of carrier-borne transition metal phosphatization catalytic performance test result table
It is bright：The material has the performance of good catalyzing manufacturing of hydrogen, in 10mAcm-2Under, overpotential 146mV.
Embodiment 3
1. the preparation of two cobalt of carrier-borne transition metal phosphatization (dried mushroom is carbon source and phosphorus source)
It is placed in 1g biological material dried mushroom deionized water washes cleans in 30mL deionized waters, 0.75g chlorinations are added
The glutaraldehyde and 0.1g transition metals cobalt salt precursor body cobalt acetates of sodium and 50 μ L, are put into 100mL beakers and stir evenly.It will be upper
It states mixed solution to be transferred in the autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction 8h at 190 DEG C.After reaction, from
The heart is collected, and is washed with water 3 times, and ethyl alcohol cleans 3 times, and the precipitation of collection is put into baking oven, and dry 8h, that is, be prepared at 80 DEG C
Intermediate product a；It after being cooled to room temperature, is put into tube furnace, is warming up under an inert atmosphere with the heating rate of 5 DEG C/min
900 DEG C, 6h is kept the temperature, two cobalt of carrier-borne transition metal phosphatization is obtained.
The appearance structure for two cobalt of carrier-borne transition metal phosphatization that the present embodiment is prepared is sheet；The support type mistake
The specific surface area for crossing the biomass carbon in two cobalt of metal phosphorizing is 638m2/g；In two cobalt of carrier-borne transition metal phosphatization
The grain size of two cobalt of transition metal phosphatization is 10~20nm.
2. the performance test of two cobalt catalyzing manufacturing of hydrogen of carrier-borne transition metal phosphatization
The preparation of 2-1. electrodes
Two cobalt of carrier-borne transition metal phosphatization that 1.00mg above-described embodiments are prepared is weighed with accurate electronic balance
Then catalyst is added 80 μ L mass fractions and is the perfluorosulfonic acid type polymer solution (Nafion solution) of 5wt%, and is dissolved in
(volume ratio of second alcohol and water is 1 in the mixed solution of the second alcohol and water of 600 μ L:4, i.e. 120 μ L ethyl alcohol and 480 μ L distilled water),
After ultrasonic disperse 0.5h, take 5 μ L (about 5 μ g) drops in (electrode is polished using preceding with polishing powder on the glass-carbon electrode of a diameter of 3mm
Cleaning), it carries out air-drying processing, the about 71 μ g/cm of useful load of two Co catalysts of carrier-borne transition metal phosphatization at room temperature2。
2-2. catalytic performance test
Catalytic performance test is the same as the catalytic performance test described in 2-2 in embodiment 1.
It is that embodiment 3 is prepared the result shows that two cobalt of carrier-borne transition metal phosphatization catalytic performance test result table
It is bright：The material has the performance of good catalyzing manufacturing of hydrogen, in 10mAcm-2Under, overpotential 160mV.
Embodiment 4
1. the preparation of two cobalt of carrier-borne transition metal phosphatization (peanut is carbon source and phosphorus source)
1g biological material peanut powder is washed with deionized totally, is dispersed in 30mL deionized waters, is added
The glutaraldehyde and 0.1g transition metals cobalt salt precursor body cobalt acetates of 0.75g sodium chloride and 50 μ L, are put into 100mL beakers and stir
Uniformly.Above-mentioned mixed solution is transferred in the autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction 8h at 190 DEG C.Reaction
After, it being collected by centrifugation, and wash with water 3 times, ethyl alcohol cleans 3 times, and the precipitation of collection is put into baking oven, the dry 8h at 80 DEG C,
Intermediate product a is prepared；It after being cooled to room temperature, is put into tube furnace, under an inert atmosphere with the heating of 5 DEG C/min
Rate is warming up to 900 DEG C, keeps the temperature 6h, obtains two cobalt of carrier-borne transition metal phosphatization.
The appearance structure for two cobalt of carrier-borne transition metal phosphatization that the present embodiment is prepared is sheet；The support type mistake
The specific surface area for crossing the biomass carbon in two cobalt of metal phosphorizing is 689m2/g；In two cobalt of carrier-borne transition metal phosphatization
The grain size of two cobalt of transition metal phosphatization is 15~20nm.
2. the performance test of two cobalt catalyzing manufacturing of hydrogen of carrier-borne transition metal phosphatization
The preparation of 2-1. electrodes
Two cobalt of carrier-borne transition metal phosphatization that 1.00mg above-described embodiments are prepared is weighed with accurate electronic balance
Then catalyst is added 80 μ L mass fractions and is the perfluorosulfonic acid type polymer solution (Nafion solution) of 5wt%, and is dissolved in
(volume ratio of second alcohol and water is 1 in the mixed solution of the second alcohol and water of 600 μ L:4, i.e. 120 μ L ethyl alcohol and 480 μ L distilled water),
After ultrasonic disperse 0.5h, take 5 μ L (about 5 μ g) drops in (electrode is polished using preceding with polishing powder on the glass-carbon electrode of a diameter of 3mm
Cleaning), it carries out air-drying processing, the about 71 μ g/cm of useful load of two Co catalysts of carrier-borne transition metal phosphatization at room temperature2。
2-2. catalytic performance test
Catalytic performance test is the same as the catalytic performance test described in 2-2 in embodiment 1.
It is that embodiment 4 is prepared the result shows that two cobalt of carrier-borne transition metal phosphatization catalytic performance test result table
It is bright：The material has the performance of good catalyzing manufacturing of hydrogen, in 10mAcm-2Under, overpotential 155mV.
Embodiment 5
1. the preparation of two cobalt of carrier-borne transition metal phosphatization (soya-bean milk is carbon source and phosphorus source)
1g will be weighed after biological material soya-bean milk filtration drying, be dispersed in 30mL deionized waters, 0.75g sodium chloride is added
With the glutaraldehyde and 0.1g Cobalt salts presoma cobalt acetates of 50 μ L, it is put into 100mL beakers and stirs evenly.By above-mentioned mixing
Solution is transferred in the autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction 8h at 190 DEG C.After reaction, it is collected by centrifugation,
And wash with water 3 times, ethyl alcohol cleans 3 times, and the precipitation of collection is put into baking oven, and dry 8h, that is, be prepared intermediate production at 80 DEG C
Object a；It after being cooled to room temperature, is put into tube furnace, is warming up to 900 DEG C under an inert atmosphere with the heating rate of 5 DEG C/min,
6h is kept the temperature, two cobalt of carrier-borne transition metal phosphatization is obtained.
The appearance structure for two cobalt of carrier-borne transition metal phosphatization that the present embodiment is prepared is sheet；The support type mistake
The specific surface area for crossing the biomass carbon in two cobalt of metal phosphorizing is 1030m2/g；Mistake in the carrier-borne transition metal phosphide
The grain size for crossing two cobalt of metal phosphorizing is 10~20nm.
2. performance test of two cobalt of carrier-borne transition metal phosphatization as the catalyzing manufacturing of hydrogen of catalyst
The preparation of 2-1. electrodes
Two cobalt of carrier-borne transition metal phosphatization that 1.00mg above-described embodiments are prepared is weighed with accurate electronic balance
As catalyst, the perfluorosulfonic acid type polymer solution (Nafion solution) that 80 μ L mass fractions are 5wt% is then added, and molten
(volume ratio of second alcohol and water is 1 in the mixed solution of the second alcohol and water of 600 μ L:4, i.e. 120 μ L ethyl alcohol and 480 μ L distill
Water), after ultrasonic disperse 0.5h, take 5 μ L (about 5 μ g) drops in (electrode uses polishing powder before use on the glass-carbon electrode of a diameter of 3mm
Polished and cleaned), it carries out air-drying processing, the about 71 μ g/ of useful load of two Co catalysts of carrier-borne transition metal phosphatization at room temperature
cm2。
2-2. catalytic performance test
Catalytic performance test is the same as the catalytic performance test described in 2-2 in embodiment 1.
It is that embodiment 5 is prepared the result shows that two cobalt of carrier-borne transition metal phosphatization catalytic performance test result table
It is bright：The material has the performance of good catalyzing manufacturing of hydrogen, in 10mAcm-2Under, overpotential 154mV.
Embodiment 6
1. the preparation of carrier-borne transition metal phosphatization nickel phosphide (saccharomycete is carbon source and phosphorus source)
1g biological material saccharomycete is washed with deionized totally, is dispersed in 30mL deionized waters, 0.75g is added
The glutaraldehyde and 0.1g transiting metal nickel salt precursor body nickel sulfates of sodium chloride and 50 μ L, are put into 100mL beakers and stir evenly.
Above-mentioned mixed solution is transferred in the autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction 8h at 190 DEG C.Reaction terminates
Afterwards, it is collected by centrifugation, and washes with water 3 times, ethyl alcohol cleans 3 times, and the precipitation of collection is put into baking oven, and dry 8h, that is, make at 80 DEG C
It is standby to obtain intermediate product a；It after being cooled to room temperature, is put into tube furnace, under an inert atmosphere with the heating rate of 5 DEG C/min
700 DEG C are warming up to, 6h is kept the temperature, obtains carrier-borne transition metal nickel phosphide.
The appearance structure for the carrier-borne transition metal nickel phosphide that the present embodiment is prepared is spherical shape, and grain size is 1.5~2
μm；The specific surface area of biomass carbon in the carrier-borne transition metal nickel phosphide is 645m2/g；Carrier-borne transition metal phosphatization
The grain size of transition metal nickel phosphide in nickel is 15~25nm.
2. performance test of the carrier-borne transition metal nickel phosphide as the catalyzing manufacturing of hydrogen of catalyst
The preparation of 2-1. electrodes
The carrier-borne transition metal nickel phosphide that 1.00mg above-described embodiments are prepared is weighed with accurate electronic balance to make
For catalyst, 80 μ L mass fractions are then added and are the perfluorosulfonic acid type polymer solution (Nafion solution) of 5wt%, and are dissolved in
(volume ratio of second alcohol and water is 1 in the mixed solution of the second alcohol and water of 600 μ L:4, i.e. 120 μ L ethyl alcohol and 480 μ L distilled water),
After ultrasonic disperse 0.5h, take 5 μ L (about 5 μ g) drops in (electrode is polished using preceding with polishing powder on the glass-carbon electrode of a diameter of 3mm
Cleaning), it carries out air-drying processing, the about 71 μ g/cm of useful load of the carrier-borne transition metal catalyst of phosphatizing nickel at room temperature2。
2-2. catalytic performance test
Catalytic performance test is carried out on IM6ex electrochemical workstations, is assessed its catalytic performance, is recycled
Voltammetric scan (CV), linear voltammetric scan (LSV), stability test and testing impedance, whole system is with 0.5M H2SO4Solution
(100mL) is used as electrolyte, and using saturated calomel electrode as reference electrode, carbon-point is as auxiliary electrode, glass-carbon electrode conduct
Working electrode；Obtain working electrode potential by comparing saturated calomel electrode, and by reversible hydrogen electrode (Reversible and
Hydrogen electrode, RHE) it is corrected.
The test result of the catalytic performance for the carrier-borne transition metal nickel phosphide that embodiment 6 is prepared can be seen that this
Material has the performance of good catalyzing manufacturing of hydrogen, in 10mAcm-2Under, overpotential 139mV.
Embodiment 7
1. the preparation of carrier-borne transition metal phosphatization iron phosphide (saccharomycete is carbon source and phosphorus source)
1g biological material saccharomycete is washed with deionized totally, is dispersed in 30mL deionized waters, 0.75g is added
The glutaraldehyde and 0.1g transition metal iron salt precursor body ferric nitrates of sodium chloride and 50 μ L, are put into 100mL beakers and stir evenly.
Above-mentioned mixed solution is transferred in the autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction 8h at 190 DEG C.Reaction terminates
Afterwards, it is collected by centrifugation, and washes with water 3 times, ethyl alcohol cleans 3 times, and the precipitation of collection is put into baking oven, and dry 8h, that is, make at 80 DEG C
It is standby to obtain intermediate product a；It after being cooled to room temperature, is put into tube furnace, under an inert atmosphere with the heating rate of 5 DEG C/min
700 DEG C are warming up to, 6h is kept the temperature, obtains carrier-borne transition metal iron phosphide.
The appearance structure for the carrier-borne transition metal iron phosphide that the present embodiment is prepared is spherical shape, and grain size is 1.5~2
μm；The specific surface area of biomass carbon in the carrier-borne transition metal iron phosphide is 667m2/g；Carrier-borne transition metal phosphatization
The grain size of transition metal iron phosphide in iron is 15~25nm.
2. performance test of the carrier-borne transition metal iron phosphide as the catalyzing manufacturing of hydrogen of catalyst
The preparation of 2-1. electrodes
The carrier-borne transition metal iron phosphide that 1.00mg above-described embodiments are prepared is weighed with accurate electronic balance to make
For catalyst, 80 μ L mass fractions are then added and are the perfluorosulfonic acid type polymer solution (Nafion solution) of 5wt%, and are dissolved in
(volume ratio of second alcohol and water is 1 in the mixed solution of the second alcohol and water of 600 μ L:4, i.e. 120 μ L ethyl alcohol and 480 μ L distilled water),
After ultrasonic disperse 0.5h, take 5 μ L (about 5 μ g) drops in (electrode is polished using preceding with polishing powder on the glass-carbon electrode of a diameter of 3mm
Cleaning), it carries out air-drying processing, the about 71 μ g/cm of useful load of the carrier-borne transition metal phosphatization iron catalyst at room temperature2。
2-2. catalytic performance test
Catalytic performance test is carried out on IM6ex electrochemical workstations, is assessed its catalytic performance, is recycled
Voltammetric scan (CV), linear voltammetric scan (LSV), stability test and testing impedance, whole system is with 0.5M H2SO4Solution
(100mL) is used as electrolyte, and using saturated calomel electrode as reference electrode, carbon-point is as auxiliary electrode, glass-carbon electrode conduct
Working electrode；Obtain working electrode potential by comparing saturated calomel electrode, and by reversible hydrogen electrode (Reversible and
Hydrogen electrode, RHE) it is corrected.
The test result of the catalytic performance for the carrier-borne transition metal iron phosphide that embodiment 7 is prepared can be seen that this
Material has the performance of good catalyzing manufacturing of hydrogen, in 10mAcm-2Under, overpotential 142mV.
From, as can be seen that in the present invention, the preparation method is a kind of synthesis hand with universality in above-described embodiment
Section, using biological material as phosphorus source, such as：Pollen or spore, microalgae, green alga, soybean, agaric, peanut, watermelon seeds, the mouth of plant
A series of more biological material of phosphorus element-containings such as mushroom, soya-bean milk, saccharomycete；Using different transition metal salts as source metal,
Such as acetate, nitrate, sulfate, successfully prepare carrier-borne transition metal phosphatization cobalt, nickel phosphide, phosphatization manganese, phosphorized copper,
Iron phosphide, zinc phosphide etc..
More than, embodiments of the present invention are illustrated.But the present invention is not limited to the above embodiments.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. a kind of preparation method of carrier-borne transition metal phosphide, which is characterized in that described method includes following steps：
1) using biological material, source metal, coupler as raw material, hydro-thermal reaction is carried out, intermediate product a is prepared；
2) the intermediate product a that will be prepared in step 1), is placed in tube furnace, after calcining, that is, the load is prepared
Type transition metal phosphide, the carrier-borne transition metal phosphide include biomass carbon and are carried in the biomass carbon
Transition metal phosphide, wherein hydro-thermal reaction that the biomass carbon is the biological material through step 1) and step 2) and
Carbon material obtained by calcination processing (i.e. carbonisation).
2. preparation method according to claim 1, which is characterized in that the step 1) is specially：By biological material, gold
Category source, coupler are dispersed in water, and form reaction system；And the pH value (preferably 3~6) of reaction system is adjusted, it then continues at
In ptfe autoclave, hydro-thermal reaction is carried out, after reaction, the intermediate production is prepared in separation, washing, drying
Object a.
3. preparation method according to claim 1 or 2, which is characterized in that the biological material is before use, first spend
Ionized water washes clean.
Preferably, the hydrothermal temperature is 100~280 DEG C, preferably 180~200 DEG C；The hydro-thermal reaction time is 6
~12h, preferably 7~9h.
Preferably, the cleaning solution can be at least one of deionized water, ethyl alcohol.
Preferably, the drying condition is dry 4~16h at 60~100 DEG C.
Preferably, the pH value for adjusting reaction system is using selected from formic acid, acetic acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, ammonia
At least one of water, sodium hydroxide, potassium hydroxide adjust the pH value of reaction system.
4. according to claim 1-3 any one of them preparation methods, which is characterized in that in step 1), the biology material
Material contains the elements such as C, H, O, N, P；Preferably, the biological material be selected from the biological material be selected from plant pollen or
It is one or more in spore, microalgae, green alga, soybean, agaric, peanut, watermelon seeds, dried mushroom, soya-bean milk, saccharomycete, preferably ferment
Female bacterium.The biological material obtains after the hydro-thermal reaction and calcination processing (i.e. carbonisation) of step (1) and step (2)
Carbon material be biomass carbon.The concentration of the biological material in the reaction system is in 0.01~1000g/L, preferably 0.1
~100g/L.
5. according to claim 1-4 any one of them preparation methods, which is characterized in that in step 1), the coupler choosing
From at least one of sodium chloride or glutaraldehyde；The coupler in the reaction system a concentration of 1 × 10-6~10mol/L, it is excellent
It is selected as 1 × 10-5~1mol/L.
Preferably, in step 1), the source metal is selected from chlorate, sulfate, nitrate and the acetic acid of transition metal element
At least one of salt；The transition metal element includes one or more in Mn, Co, Ni, Fe, Ce, Cu, Zn, Sn；It is described
Source metal in the reaction system a concentration of 1 × 10-6~0.1mol/L, preferably 1 × 10-5~0.01mol/L.
Preferably, in step 2), the calcining the specific steps are：Under inert gas protection, with 0.1~50 DEG C/min's
Heating rate is warming up to 500~1500 DEG C, and constant temperature 1~for 24 hours；Preferably, under inert gas protection, with 1~50 DEG C/min's
Heating rate is warming up to 700~1200 DEG C, 1~10h of constant temperature.
Preferably, the inert gas can be one or more in nitrogen, argon gas, helium.
6. according to the preparation method described in any one of claim 1-5 claims, which is characterized in that the transition metal
Phosphide can be one kind in phosphatization manganese, phosphatization cobalt, nickel phosphide, iron phosphide, phosphatization cerium, phosphorized copper, zinc phosphide and phosphorization tin
Or it is a variety of.
7. according to the preparation method described in any one of claim 1-6 claims, which is characterized in that the method is specifically wrapped
Include following steps：
1) biological material, source metal, coupler are dispersed in water, form reaction system；And adjust the pH value of reaction system
It to 3~6, then continues in ptfe autoclave, 6~12h of hydro-thermal reaction is carried out at 100~280 DEG C, reaction terminates
Afterwards, solid product is collected by centrifugation, and washed respectively with deionized water and/or ethyl alcohol, after in 60~100 DEG C of dry 4~16h, system
It is standby to obtain the intermediate product a；
2) the intermediate product a that will be prepared in step 1), is placed in tube furnace, under nitrogen protection, with 0.1~50 DEG C/min
Heating rate be warming up to 500~1500 DEG C, after constant temperature 1~for 24 hours, that is, the carrier-borne transition metal phosphide is prepared.
8. a kind of preparation method using the carrier-borne transition metal phosphide described in any one of claim 1-7 claims
The carrier-borne transition metal phosphide being prepared, which is characterized in that contain biology in the carrier-borne transition metal phosphide
Matter carbon and the transition metal phosphide being carried in the biomass carbon, the biomass carbon is by biological material through hydro-thermal reaction
It is obtained with calcination processing.
Preferably, the pattern of the carrier-borne transition metal phosphide has spherical, class spider net form or piece shape.For spherical shape when,
Grain size is 0.5~5 μm；Preferably 1.0~3 μm；Also preferably 1.5~2 μm.
Preferably, the pattern of the biomass carbon in the carrier-borne transition metal phosphide has spherical, class spider net form or piece shape.
Preferably, specific surface area is 400~2000m2/g；Preferably 500~1500m2/g；Also preferably 550~1300m2/g。
Preferably, the pattern of the transition metal phosphide being carried in the biomass carbon is in granular form, the transition gold
The grain size for belonging to phosphide is 10~50nm；Preferably 15~20nm or 10~20nm.
Preferably, it the transition metal phosphide even particulate dispersion and is carried in the biomass carbon spheric granules.
9. the application of carrier-borne transition metal phosphide according to any one of claims 8, which is characterized in that the carrier-borne transition metal
Phosphide can be used in the fields such as catalyzing manufacturing of hydrogen and energy storage.
10. a kind of method of catalyzing manufacturing of hydrogen, which is characterized in that the method is using Supported transition according to any one of claims 8 gold
Belong to the reaction that phosphide carries out catalyzing manufacturing of hydrogen as catalyst.
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| CN113881965A (en) * | 2021-09-10 | 2022-01-04 | 哈尔滨工业大学 | Metal nanoparticle-loaded catalyst taking biomass carbon source as template and preparation method and application thereof |
| CN113881965B (en) * | 2021-09-10 | 2023-03-14 | 哈尔滨工业大学 | Metal nanoparticle supported catalyst with biomass carbon source as template and preparation method and application thereof |
| CN116078413A (en) * | 2022-12-13 | 2023-05-09 | 青岛科技大学 | Low-noble metal phosphide electrocatalyst based on microbial template derivatization and preparation method and application thereof |
| CN116873886A (en) * | 2023-05-15 | 2023-10-13 | 同济大学 | Yeast-derived metal phosphide electrode material and preparation method and application thereof |
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