CN109012704A - A kind of two cobaltous selenide of nanometer load carbon nano-fiber composite material and its preparation method and application - Google Patents
A kind of two cobaltous selenide of nanometer load carbon nano-fiber composite material and its preparation method and application Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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Abstract
The invention belongs to field of nano material preparation, a kind of two cobaltous selenide of nanometer load carbon nano-fiber composite material and its preparation method and application is disclosed.Preparation method includes the following steps: (1) preparation of carbon nano-fiber；(2) four hydration cobalt acetates are added in carbon nano-fiber, stirring dissolves four hydration cobalt acetates, obtains dispersion liquid；(3) selenium powder is added in hydrazine hydrate solution, stirring makes selenium powder be completely dissolved to obtain selenium solution, selenium solution is taken to be added dropwise in dispersion liquid made from step (2), obtained mixed solution, which is transferred in reaction kettle, to react, be centrifuged, wash after reaction, dry after obtain two cobaltous selenide of nanometer load carbon nano-fiber composite material.The preparation method is simple, and hydrogen precipitation in acid condition is had excellent performance, and can be applied to catalytic electrolysis water electrode material, relative to precious metals platinum catalyst, the material cost is lower, has good stability.
Description
Technical field
The invention belongs to field of nano material preparation, and in particular to a kind of two cobaltous selenide of nanometer load carbon nano-fiber is compound
Material and its preparation method and application.
Background technique
The world today is faced with two acid tests the most, first is that environmental pollution, second is that energy crisis.Environment and the energy
The economic development of problem and countries in the world is closely related, therefore the development and utilization of sustainable development new energy are by many countries
Pay attention to.Product after combustion of hydrogen only has water, is " no pollution " fuel truly, thus is considered as 21st century
The optimal energy.Water reserve is abundant on the earth, and there are about 71% to be covered with water for earth surface, and water electrolysis hydrogen production is that comparison is clean
Hydrogen manufacturing mode, and selection relatively good at present.So far, the most effective catalyst of water electrolysis hydrogen production is that platinum and its platinum close
Gold.But the factors such as expensive, scarcity of resources limit extensive use and the commercialized development of platinum.Therefore, it finds a kind of high
The hot spot for becoming Recent study is precipitated for hydrogen for the non-precious metal catalyst of performance.
It includes two classes that catalyst, which is precipitated, in base metal hydrogen: (1) nonmetalloid is used to construct the precipitation of inorganic non-metallic hydrogen and urges
Agent mainly includes boron, carbon, nitrogen phosphate and sulfur and selenium；(2) transition metal is used to construct base metal hydrogen precipitation catalyst, mainly
Including iron, cobalt, nickel, copper, molybdenum and tungsten.Wherein, due to unique physicochemical properties, the first row transition metal selenides (selenizing
Iron, cobaltous selenide, nickelous selenide) it has received widespread attention.Iron, cobalt, nickel selenides belong to cube, rhombic system, metallic atom
In the form of octahedral in conjunction with selenium atom, it can be partially filled with Eg energy band band gap, more excellent hydrogen is accordingly regarded as and catalysis is precipitated
Agent.But transition metal selenides is easy to reunite, and the electric conductivity of itself is not strong enough.Therefore develop a kind of good conductivity,
It is extremely urgent that catalyst material is precipitated in the hydrogen of stability and high efficiency.
Summary of the invention
In order to solve the disadvantage that the prior art and shortcoming, primary and foremost purpose of the present invention are to provide a kind of two cobaltous selenide of nanometer
Load carbon nano-fiber composite material.
Another object of the present invention is to provide the preparation side of above-mentioned two cobaltous selenide of nanometer load carbon nano-fiber composite material
Method.
Another object of the present invention is to provide the application of above-mentioned two cobaltous selenide of nanometer load carbon nano-fiber composite material.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of two cobaltous selenide of nanometer load carbon nano-fiber composite material, comprising the following steps:
(1) bacteria cellulose is dipped into water to neutrality first, is then freeze-dried, finally in protective gas gas
It is calcined under atmosphere, carbon nano-fiber is obtained after cooling down to room temperature；
(2) carbon nano-fiber made from step (1) is taken to be dispersed in water, ultrasonic disperse at uniform mixed liquor, then plus
Enter four hydration cobalt acetates, stirring dissolves four hydration cobalt acetates, obtains dispersion liquid；
(3) selenium powder is added in hydrazine hydrate solution, stirring makes selenium powder be dissolved completely in hydrazine hydrate solution, and it is molten to obtain selenium
Liquid takes selenium solution to be added dropwise in dispersion liquid made from step (2), and obtained mixed solution, which is transferred in reaction kettle, to react, instead
Be centrifuged, wash after answering, dry after obtain two cobaltous selenide of nanometer load carbon nano-fiber composite material.
Preferably, the dispersion concentration of step (2) described carbon nano-fiber in water is 0.3~1mg/mL, four hydration
Concentration of the cobalt acetate in dispersion liquid is 0.01~0.04mol/L.
Preferably, additional amount of the selenium powder in hydrazine hydrate solution described in step (3) is 0.03~0.06mol/L.
Preferably, the mass fraction of step (3) described hydrazine hydrate solution is 40%~80%, the additional amount of the selenium solution
Volume ratio with reaction system is 1~3:21, and reaction system dispersion liquid made from selenium solution and step (2) forms.
Preferably, the temperature of step (3) described stirring is 80 DEG C~100 DEG C, it is furthermore preferred that the temperature of the stirring is 80
℃。
Preferably, the reaction temperature of step (3) described reaction kettle is 180~220 DEG C, and the reaction time is 10h~12h.
Preferably, the revolving speed of step (3) described centrifuge separation is 6000~9000r/min, it is furthermore preferred that the centrifugation point
From revolving speed be 8000r/min.
Preferably, the temperature of step (3) described drying is 60 DEG C~100 DEG C, and the dry time is 8h~12h, more preferably
, the temperature of the drying is 60 DEG C, and the dry time is 8h.
Preferably, the temperature of step (1) described calcining is 600~900 DEG C, and the time of the calcining is 1h~2h.
Preferably, the heating rate of step (1) described calcining is 2 DEG C of min-1, the rate of the cooling is 5 DEG C of min-1。
Preferably, protective gas described in step (1) is inert gas or nitrogen.
Two cobaltous selenide of nanometer of the preparation method preparation of above-mentioned two cobaltous selenide of nanometer load carbon nano-fiber composite material
Load carbon nano-fiber composite material.
Above-mentioned two cobaltous selenide of nanometer load carbon nano-fiber composite material is precipitated in electrode material in preparation catalysis hydrogen
Using.
Reaction mechanism of the invention are as follows: two cobaltous selenides are easy to reunite during the preparation process, and the electric conductivity of itself is inadequate
By force.Bacteria cellulose is a kind of environmentally friendly nano meter biomaterial haveing excellent performance, and is synthesized by the fermentation of part bacterium living beings
A kind of high-molecular compound.Carbon nano-fiber derived from bacteria cellulose has tridimensional nano net structure, with carbon Nanowire
Dimension is used as substrate, is capable of increasing specific surface area, provides more active sites to catalysis reaction to improve performance.Using bacterium
Carbon nano-fiber derived from cellulose is template, with the method for a step hydro-thermal, the two cobaltous selenide nanometers that can will be prepared
Grain is evenly distributed on carbon nano-fiber surface；Meanwhile the good electric conductivity of carbon nano-fiber can promote material to be precipitated instead in hydrogen
Answer the transmission of process intermediate ion/electronics.
Compared with prior art, the invention has the advantages that and the utility model has the advantages that
(1) raw material sources are extensive, at low cost, and preparation process is simple, and experimental period is short, reproducible；
(2) bacteria cellulose of porous structure is capable of providing biggish specific surface area and enhances the electric conductivity of catalyst, this
Be conducive to the transmission of hydrogen precipitation process ion/electronics；
(3) two selenizing cobalt nano-particles are supported on the carbon nano-fiber of three-dimensional reticular structure, avoid two cobaltous selenides
The reunion of nano particle improves hydrogen and performance is precipitated so as to the more active sites of exposure.
Detailed description of the invention
Fig. 1 is CoSe made from comparative example 12The scanning electron microscope diagram of NPs.
Fig. 2 is CNFs/CoSe made from embodiment 12(1) scanning electron microscope (SEM) photograph.
Fig. 3 is CNFs/CoSe made from embodiment 12(1) transmission electron microscope picture.
Fig. 4 is CNFs/CoSe made from embodiment 12(1) N2Adsorption desorption curve graph.
Fig. 5 is CNFs/CoSe made from embodiment 12(1), CoSe made from comparative example 12NPs, 50wt.%Pt/C and carbon
Nanofiber (CNFs) is in 1.0mol L-1H2SO4Linear sweep voltammetry curve graph under electrolyte.
Fig. 6 is CNFs/CoSe made from embodiment 12(1) electrocatalytic hydrogen evolution catalytic stability test chart.
Fig. 7 is CNFs/CoSe made from embodiment 12(1) XRD diagram.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
The bacteria cellulose used in the following example is purchased from Hainan Yeguo Food Co., Ltd.
Embodiment 1
A kind of preparation method of two cobaltous selenide of nanometer load carbon nano-fiber composite material, comprises the steps that
(1) bacteria cellulose is dipped to neutrality with deionized water, and cut into pieces, specification is 2cm × 2cm；
(2) bacteria cellulose after step (1) slice obtained is freeze-dried, then puts it into temperature programming tubular type
In N in furnace2Protection under after 600 DEG C of calcining 2h cooling down, three-dimensional netted carbon nano-fiber (CNFs) is obtained, wherein rising
Warm rate is 2 DEG C of min-1, and with 5 DEG C of min-1Rate of temperature fall be cooled to room temperature；
(3) carbon nano-fiber made from 50mg step (2) is taken to be scattered in 100mL deionized water, ultrasonic disperse 1h is at equal
Then four hydration cobalt acetates are added in even mixed liquor, stirring 15min dissolves four hydration cobalt acetates, obtain dispersion liquid, four hydrations
Concentration of the cobalt acetate in dispersion liquid is 0.01mol/L；
(4) 1mmol selenium powder being added in the hydrazine hydrate solution of 30mL 40wt%, 30min is stirred in 80 DEG C of waters bath with thermostatic control,
It is dissolved completely in selenium powder in hydrazine hydrate solution, obtains selenium solution, 5mL selenium solution is taken to be added dropwise to obtained point of step (3)
In dispersion liquid, obtained mixed solution is transferred in the reaction kettle of polytetrafluoroethyllining lining, keeps 10h under the conditions of 180 DEG C, then
It is cooled to room temperature, 8000r/min centrifuge separation is washed with deionized three times, 60 DEG C of dry 8h obtain two selenizing of nanometer
Cobalt loads carbon nano-fiber composite material, is named as CNFs/CoSe2(1)。
Embodiment 2
A kind of preparation method of two cobaltous selenide of nanometer load carbon nano-fiber composite material, comprises the steps that
(1) bacteria cellulose is dipped to neutrality with deionized water, and cut into pieces, specification is 2cm × 2cm；
(2) bacteria cellulose after step (1) slice obtained is freeze-dried, then puts it into temperature programming tubular type
In N in furnace2Protection under after 700 DEG C of calcining 2h cooling down, obtain three-dimensional netted carbon nano-fiber, wherein heating rate
For 2 DEG C of min-1, and with 5 DEG C of min-1Rate of temperature fall be cooled to room temperature；
(3) carbon nano-fiber made from 30mg step (2) is taken to be scattered in 100mL deionized water, ultrasonic disperse 1h is at equal
Then four hydration cobalt acetates are added in even mixed liquor, stirring 15min dissolves four hydration cobalt acetates, obtain dispersion liquid, four hydrations
Concentration of the cobalt acetate in dispersion liquid is 0.02mol/L；
(4) 1mmol selenium powder being added in the hydrazine hydrate solution of 30mL 40wt%, 30min is stirred in 80 DEG C of waters bath with thermostatic control,
It is dissolved completely in selenium powder in hydrazine hydrate solution, obtains selenium solution, 10mL selenium solution is taken to be added dropwise to obtained point of step (3)
In dispersion liquid, obtained mixed solution is transferred in the reaction kettle of polytetrafluoroethyllining lining, keeps 12h under the conditions of 180 DEG C, then
It is cooled to room temperature, 8000r/min centrifuge separation is washed with deionized three times, 60 DEG C of dry 8h obtain two selenizing of nanometer
Cobalt loads carbon nano-fiber composite material, is named as CNFs/CoSe2(2)。
Embodiment 3
A kind of preparation method of two cobaltous selenide of nanometer load carbon nano-fiber composite material, comprises the steps that
(1) bacteria cellulose is dipped to neutrality with deionized water, and cut into pieces, specification is 2cm × 2cm；
(2) bacteria cellulose after step (1) slice obtained is freeze-dried, then puts it into temperature programming tubular type
In N in furnace2Protection under after 800 DEG C of calcining 2h cooling down, obtain three-dimensional netted carbon nano-fiber, wherein heating rate
For 2 DEG C of min-1, and with 5 DEG C of min-1Rate of temperature fall be cooled to room temperature；
(3) carbon nano-fiber made from 80mg step (2) is taken to be scattered in 100mL deionized water, ultrasonic disperse 1h is at equal
Then four hydration cobalt acetates are added in even mixed liquor, stirring 15min dissolves four hydration cobalt acetates, obtain dispersion liquid, four hydrations
Concentration of the cobalt acetate in dispersion liquid is 0.03mol/L；
(4) 1.5mmol selenium powder is added in the hydrazine hydrate solution of 30mL 40wt%, 80 DEG C of water bath with thermostatic control stirrings
30min is dissolved completely in selenium powder in hydrazine hydrate solution, obtains selenium solution, and 15mL selenium solution is taken to be added dropwise to step (3) system
In the dispersion liquid obtained, obtained mixed solution is transferred in the reaction kettle of polytetrafluoroethyllining lining, is kept under the conditions of 200 DEG C
10h is then cooled to room temperature, and 8000r/min centrifuge separation is washed with deionized three times, and 60 DEG C of dry 8h obtain described receive
Two cobaltous selenides of rice load carbon nano-fiber composite material, are named as CNFs/CoSe2(3)。
Embodiment 4
A kind of preparation method of two cobaltous selenide of nanometer load carbon nano-fiber composite material, comprises the steps that
(1) bacteria cellulose is dipped to neutrality with deionized water, and cut into pieces, specification is 2cm × 2cm；
(2) bacteria cellulose after step (1) slice obtained is freeze-dried, then puts it into temperature programming tubular type
In N in furnace2Protection under after 900 DEG C of calcining 2h cooling down, obtain three-dimensional netted carbon nano-fiber, wherein heating rate
For 2 DEG C of min-1, and with 5 DEG C of min-1Rate of temperature fall be cooled to room temperature；
(3) carbon nano-fiber made from 100mg step (2) is taken to be scattered in 100mL deionized water, ultrasonic disperse 1h is at equal
Then four hydration cobalt acetates are added in even mixed liquor, stirring 15min dissolves four hydration cobalt acetates, obtain dispersion liquid, four hydrations
Concentration of the cobalt acetate in dispersion liquid is 0.04mol/L；
(4) 1.5mmol selenium powder is added in the hydrazine hydrate solution of 30mL 40wt%, 80 DEG C of water bath with thermostatic control stirrings
30min is dissolved completely in selenium powder in hydrazine hydrate solution, obtains selenium solution, and 15mL selenium solution is taken to be added dropwise to step (3 systems
In the dispersion liquid obtained, obtained mixed solution is transferred in the reaction kettle of polytetrafluoroethyllining lining, is kept under the conditions of 200 DEG C
12h is then cooled to room temperature, and 8000r/min centrifuge separation is washed with deionized three times, and 60 DEG C of dry 8h obtain described receive
Two cobaltous selenides of rice load carbon nano-fiber composite material, are named as CNFs/CoSe2(4)。
Comparative example 1
The preparation of two selenizing cobalt nano-particles
(1) in 50mL deionized water, 1mmol tetra- is added and is hydrated cobalt acetate, stirring 15min keeps four hydration cobalt acetates molten
Solution, obtains solution 1
(2) 1mmol selenium powder is added in 30mL 40wt% hydrazine hydrate solution, 30min is stirred in 80 DEG C of waters bath with thermostatic control, is made
Selenium powder is dissolved completely in hydrazine hydrate solution, obtains selenium solution, and 10mL selenium solution is taken to be added dropwise to solution 1 made from rapid (1),
The mixed solution finally obtained is transferred in the reaction kettle of polytetrafluoroethyllining lining, is kept 12h in 180 DEG C of conditions, is then cooled to
Room temperature, 8000r/min centrifuge separation, is washed with deionized three times, and 60 DEG C of dry 8h obtain two selenizing cobalt nano-particles, name
For CoSe2NPs。
Fig. 1 is two selenizing cobalt nano-particle (CoSe made from comparative example 12NPs scanning electron microscope diagram), from figure
It can be seen that particle agglomeration is more serious.Fig. 2 is CNFs/CoSe made from embodiment 12(1) scanning electron microscope (SEM) photograph, Fig. 3 are real
Apply CNFs/CoSe made from example 12(1) transmission electron microscope picture.It can be observed from fig. 2 that three-dimensional netted carbon nano-fiber is as network
Skeleton, two selenizing cobalt nano-particle uniform loads are on carbon nano-fiber surface；It can be seen in figure 3 that CNFs/CoSe2(1) it is in
Reticular structure, the diameter of carbon nano-fiber is about 50nm, while two cobaltous selenide nanometer little particles are supported on carbon nano-fiber table
Face.
By the test of specific surface area, CNFs/CoSe made from embodiment 1 is obtained2(1) N2Adsorption desorption curve graph, such as
Shown in Fig. 4, CNFs/CoSe can be calculated2(1) specific surface area is 401cm2g-1。
By CNFs/CoSe made from embodiment 12(1) for load glass-carbon electrode as working electrode, carbon-point is auxiliary electrode,
Hg/Hg2Cl2For reference electrode, with 0.5mol L-1H2SO4For electrolyte, forms three-electrode system and carry out hydrogen precipitation performance test.
Linear scan test is carried out first, and sweep speed is 2mV s-1, sweep interval is 0V~-0.4V vs standard hydrogen electrode.In order into
Performance is precipitated in the catalysis hydrogen that one step assesses it, by itself and CoSe made from 50wt.%Pt/C, comparative example 12NPs and embodiment 1 are made
Standby carbon nano-fiber (CNFs) compares, and obtains linear sweep voltammetry curve graph as shown in figure 5,50wt.% as seen from Figure 5
The hydrogen precipitation performance of Pt/C is best, take-off potential 0V, and the hydrogen of carbon nano-fiber (CNFs) is precipitated performance and can almost neglect
Slightly, CNFs/CoSe2It (1) is that -0.085V starts that hydrogen is precipitated in take-off potential, hydrogen is precipitated performance and is relatively inferior to 50wt.%Pt/
C, but two far superior to simple selenizing cobalt nano-particle CoSe2NPs (take-off potential is -0.145V).It is comprehensive these, can be with
Carbon nano-fiber is obtained as three-dimensional network skeleton, can succeed evenly dispersed two selenizings cobalt nano-particle, and exposure is more living
Property site, thus improve hydrogen be precipitated performance.
By CNFs/CoSe made from embodiment 12(1) in 0.5mol L-1H2SO4Stability test is carried out in electrolyte, is surveyed
Test result is as shown in Figure 6.It can be found that CNFs/CoSe from Fig. 62(1) after lasting catalysis hydrogen is precipitated 10 hours, current strength
It does not significantly decrease, shows that it is with good stability.
To CNFs/CoSe made from embodiment 12(1) X-ray diffraction measure is carried out, test results are shown in figure 7, in 2 θ
=28.97 °, 30.77 °, 34.52 °, 47.72 ° correspond respectively to orthohormbic structure CoSe2(011), (101), (111), (211)
(JCPDS No.53-0449) diffraction crystal face；In 2 θ=30.42 °, 46.39 °, 51.75 °, 56.41 °, 63.45 ° are corresponded respectively to
Cubic structure CoSe2(220) (221), (311), (400) (JCPDS No.09-0234) diffraction crystal face；In the position of 2 θ=26 °
It is equipped with a peak, is the typical characteristic peak of carbon material (002) crystal face.
Two cobaltous selenide of nanometer made from Examples 1 to 4 loads the specific surface area and starting electricity of carbon nano-fiber composite material
The test result of position is as shown in table 1, wherein the test condition of embodiment 2,3 and 4 is the same as embodiment 1.
1 specific surface area of table and take-off potential test result
| Material | Specific surface area (cm2g-1) | Take-off potential (V) |
| Embodiment 1 | 401 | -0.085 |
| Embodiment 2 | 396 | -0.089 |
| Embodiment 3 | 398 | -0.092 |
| Embodiment 4 | 400 | -0.095 |
| Comparative example 1 | 68 | -0.145 |
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of two cobaltous selenide of nanometer load carbon nano-fiber composite material, which is characterized in that including following step
It is rapid:
(1) bacteria cellulose is dipped into water to neutrality first, is then freeze-dried, finally under protective gas atmosphere
It is calcined, carbon nano-fiber is obtained after cooling down to room temperature；
(2) carbon nano-fiber made from step (1) is taken to be dispersed in water, then ultrasonic disperse is added four at uniform mixed liquor
It is hydrated cobalt acetate, stirring dissolves four hydration cobalt acetates, obtains dispersion liquid；
(3) selenium powder is added in hydrazine hydrate solution, stirring makes selenium powder be dissolved completely in hydrazine hydrate solution, obtains selenium solution, takes
Selenium solution is added dropwise in dispersion liquid made from step (2), and obtained mixed solution, which is transferred in reaction kettle, to react, and reaction terminates
Carbon nano-fiber composite material is loaded by two cobaltous selenide of nanometer is obtained after centrifuge separation, washing, drying.
2. the preparation method of two cobaltous selenide of nanometer load carbon nano-fiber composite material according to claim 1, feature
It is, the dispersion concentration of step (2) described carbon nano-fiber in water is 0.3~1mg/mL, and the four hydration cobalt acetate is dividing
Concentration in dispersion liquid is 0.01~0.04mol/L.
3. the preparation method of two cobaltous selenide of nanometer load carbon nano-fiber composite material according to claim 2, feature
It is, additional amount of step (3) the described selenium powder in hydrazine hydrate solution is 0.03~0.06mol/L.
4. the preparation side of described in any item two cobaltous selenide of nanometer load carbon nano-fiber composite materials according to claim 1~3
Method, which is characterized in that the mass fraction of step (3) described hydrazine hydrate solution is 40%~80%, the additional amount of the selenium solution
Volume ratio with reaction system is 1~3:21.
5. the preparation side of described in any item two cobaltous selenide of nanometer load carbon nano-fiber composite materials according to claim 1~3
Method, which is characterized in that the temperature of step (1) described calcining is 600~900 DEG C, and the time of the calcining is 1h~2h.
6. the preparation side of described in any item two cobaltous selenide of nanometer load carbon nano-fiber composite materials according to claim 1~3
Method, which is characterized in that the temperature of step (3) described stirring is 80 DEG C~100 DEG C, the reaction temperature of the reaction kettle is 180~
220 DEG C, the reaction time is 10h~12h.
7. the preparation side of described in any item two cobaltous selenide of nanometer load carbon nano-fiber composite materials according to claim 1~3
Method, which is characterized in that the revolving speed of step (3) described centrifuge separation is 6000~9000r/min, and the temperature of the drying is 60 DEG C
~100 DEG C, the dry time is 8h~12h.
8. the preparation side of described in any item two cobaltous selenide of nanometer load carbon nano-fiber composite materials according to claim 1~3
Method, which is characterized in that protective gas described in step (1) is inert gas or nitrogen.
9. the preparation method system of two cobaltous selenide of nanometer load carbon nano-fiber composite material according to any one of claims 1 to 8
Standby two cobaltous selenide of nanometer loads carbon nano-fiber composite material.
10. electrode is precipitated in preparation catalysis hydrogen in two cobaltous selenide of nanometer load carbon nano-fiber composite material as claimed in claim 9
Application in material.
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| CN112952060A (en) * | 2021-02-26 | 2021-06-11 | 广东工业大学 | Vanadium diselenide/carbon cellulose composite material and preparation method and application thereof |
| CN113101949A (en) * | 2021-04-08 | 2021-07-13 | 深圳大学 | Transition metal selenide heterostructure material and preparation method thereof |
| CN113774402A (en) * | 2021-09-13 | 2021-12-10 | 辽宁大学 | Cobalt-nickel bimetallic selenide loaded cellulose-based graphene composite material and application thereof in electrocatalysis |
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