CN101337188A - Aquatherm preparation method of high effective catalyst (MIn)xCd2(1-x)S2 for the solar water analysing hydrogen production - Google Patents
Aquatherm preparation method of high effective catalyst (MIn)xCd2(1-x)S2 for the solar water analysing hydrogen production Download PDFInfo
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- CN101337188A CN101337188A CNA2008100488221A CN200810048822A CN101337188A CN 101337188 A CN101337188 A CN 101337188A CN A2008100488221 A CNA2008100488221 A CN A2008100488221A CN 200810048822 A CN200810048822 A CN 200810048822A CN 101337188 A CN101337188 A CN 101337188A
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Abstract
The invention provides a hydrothermal preparation method of a high efficient catalyst (MIn)xCd2(1-X)S2 which is used in the system of hydrogen photoproduction by water splitting. The simple hydrothermal preparation method of the invention comprises the following steps: through controlling the proportion of reactants, the reaction temperature, the reaction time, etc., CdS is doped with a semiconductor material MInS (M is a univalent transition metal), thereby enabling the band structure of the CdS to have the best hydrogen producing effect; under simulated sunlight and no precious metal loading, the highest hydrogen yield of the prepared visible-light photocatalyst (MIn)xCd2(1-x)S2 with nanostructure can be 650 mu molh<-1>g<-1>, and the quantum yield is almost 10 percent, thereby the hydrogen producing effect is a dozen times of that of the pure CdS loaded by the precious metal.
Description
Technical field
The present invention relates to sunshine hydrogen production by water decomposition Preparation of catalysts method, particularly Hydrothermal Preparation sunshine hydrogen production by water decomposition Preparation of catalysts method.Belong to the energy and material technical field.
Background technology
Because energy crisis is serious day by day, makes clean energy resource with regenerative resource--Hydrogen Energy just becomes the focus of various countries' research.Since Honda in 1972 and Fujishima have reported semi-conducting material Optical Electro-Chemistry hydrogen production by water decomposition (Nature, 1972,238,37), the conductor photocatalysis hydrogen production by water decomposition just becomes the focus that people pay close attention to.Though the research in this field has up to the present obtained some progress, catalyst that is developed such as TiO
2(Renew.Sustain.Energy Rew., 2007,11,401) can only produce effect under ultraviolet light, not responding to visible light.Though the so visible light-responded semiconductor hydrogen manufacturing material of CdS (Langmuir 1990,6,565) is also arranged, and this material require carried noble metal such as Pt, Ru etc. just have very strong activity, also easy photoetch, instability have also limited its practical application.Therefore be necessary to design efficient, the non precious metal appendix semiconductor catalyst that accounts for the visible light of sunshine 43% energy with development utilization.
Multicomponent catalyst became a new direction in the solar hydrogen making catalysis material in recent years, because by forming the band structure that solid solution can be regulated catalyst between broad-band gap and the narrow gap semiconductor.Japan Kudo group has reported (AgIn)
xZn
2 (1-x)S
2 ((J.Am.Chem.Soc.2004,126,13406) and (CuIn)
xZn
2 (1-x)S
2(J.Phys.Chem.B 2005,109,7323) quaternary photocatalyst finds that the adjusting of passing ratio composition can realize moving of catalyst band gap, and this catalyst can be in the visible light wave range range response, wherein, and (AgIn) after the annealing in process
xZn
2 (1-x)S
2Under the non precious metal load, just has 1mmol h
-1g
-1Hydrogen-producing speed, this has caused that people are for the great interest of quaternary hydrogen manufacturing photochemical catalyst.In the research of quaternary photocatalysis system, the generally good nanostructured effective catalyst of people, replacing conventional catalyst with the catalyst of nanostructured has many advantages, and the one, quantum efficiency improves, and the productive rate of hydrogen manufacturing in theory can the increase of exponentially level multiple.The 2nd, can realize regulation and control by the hetero nano structure catalyst design to energy gap, standard electronics and hole transport passage, improve the efficient of photocatalysis hydrogen production.The Japan scientist also pays close attention to this field in recent years always, existing PRELIMINARY RESULTS report in the research of nano-structured calalyst, Japan Domen research group just prepares porous nanometer structure CdS (Chem.Mater.2008,20,110), its supporting Pt hydrogen manufacturing speed is the best report of present CdS hydrogen manufacturing effect up to 16mmol/hg.But its very big defective be the catalyst instability easily by photoetch, it is nearly 20% just to have descended in the activity that recycles 12 hours rear catalysts, and this CdS material require carried noble metal.Therefore study efficient, stability and the cost problem that nanostructured quaternary composite catalyst is expected comprehensively to solve photocatalysis hydrogen production.
The solid phase solwution method is a synthetic polynary hydrogen manufacturing photochemical catalyst method commonly used, but this method needs the high temperature of more than 1,000 degree to prepare material, and equipment is had very high requirement, is not suitable for extensive, the low-cost use.Hydro-thermal method is a kind of straightforward procedure that people are commonly used to nano materials, this method need temperature lower, through being everlasting below 200 ℃, this method has been successfully used to synthetic polynary catalyst for preparing hydrogen (Adv.Funct.Mater to the sunshine response, 2006,16,1349).
Summary of the invention
The objective of the invention is to utilize simple hydro-thermal method to prepare MInS
2The CdS sunshine hydrogen production by water decomposition catalyst that mixes, and make the conduction band of quaternary composite nanostructure catalysis material more negative is beneficial to that hydrogen is easier separates out.
Principle of the present invention is: MInS
2Be that energy gap is the semiconductor of 1.4～2.5eV, the forbidden band of CdS is 2.3eV, MInS
2The conduction band current potential than CdS for negative, the electronics that its optical excitation produces down can be transferred on the conduction band of CdS and participates in hydrionic reduction, and the CdS hole that produces that is stimulated just can be transferred to the less MInS of valence band current potential
2On the valence band with solution in the reaction of hole sacrifice agent, participate in the hydrionic hydrogen that is reduced into and stayed more electronics.Like this, two kinds of semi-conducting material electronics, hole-recombination reduce on the one hand, are beneficial to quantum yield and improve, and make composite itself just have high hydrogen production activity; Photoetch is taken place by hole oxidation in the valence band in CdS itself easily on the other hand, when CdS transfers to the lower MInS of valence band current potential with the hole in the valence band
2On the valence band and with solution in the reaction of hole sacrifice agent, just significantly reduced among the CdS hole content in the valence band, just suppressed the generation of CdS photoetch naturally, can improve stability greatly.Therefore, (MIn)
xCd
2 (1-x)S
2Nanostructured composites is at MInS
2" robbing " hole and CdS " robs " under the synergy of electronics, not only itself show well directly using visible light to decompose water and make hydrogen activity (need not the noble metal load) and stability preferably, and the catalyst hydrogen production activity is further increased substantially by technology of preparing optimization, have the prospect of large-scale application.
The scheme that realizes the object of the invention is:
Direct sunshine hydrogen production by water decomposition catalyst (MIn)
xCd
2 (1-x)S
2The preparation method, M is the monovalence transition metal, it is characterized in that, hydrothermal method, this method with thiocarbamide as the sulphur source, the compound that contains cadmium is the cadmium source, the compound that contains indium is the indium source, the compound that contains transition metal is the source of monovalence transition metal in the product, with above-mentioned sulphur source, the cadmium source, four kinds of compounds of indium source and monovalence transition metal are at pure water, the ultrasonic back of mixing imports water heating kettle in the mixed solvent of straight alcohol or ethanol and water, after the sealing, hydro-thermal reaction is carried out in heating, after the cooling, the deposit in the water heating kettle is removed accessory substance with ethanol and water washing, promptly obtain catalyst product after the vacuum drying.
Prepare above-mentioned nanostructured, efficient, direct sunshine hydrogen production by water decomposition catalyst (MIn)
xCd
2 (1-x)S
2Method, it is characterized in that described monovalence transition metal M is copper (Cu), silver (Ag) or gold (Au),, the x scope is from 0.01～0.3.Best x scope is 0.01～0.1.
Prepare above-mentioned nanostructured, efficient, direct sunshine hydrogen production by water decomposition catalyst (MIn)
xCd
2 (1-x)S
2Method, it is characterized in that the described compound that contains cadmium is selected from water-containing acetic acid cadmium, acetic anhydride cadmium, caddy, cadmium sulfate or cadmium nitrate, the initial concentration that contains the compound of cadmium during hydro-thermal reaction is 1 * 10
-5～1 mol.
Prepare above-mentioned nanostructured, efficient, direct sunshine hydrogen production by water decomposition catalyst (MIn)
xCd
2 (1-x)S
2Method, it is characterized in that the concentration range of described reactant thiocarbamide is 2 * 10
-4～2 mol.
Prepare above-mentioned nanostructured, efficient, direct sunshine hydrogen production by water decomposition catalyst (MIn)
xCd
2 (1-x)S
2Method, it is characterized in that the described compound that contains indium is selected from inidum chloride, indium sulfate, indium nitrate or indium acetate, the initial concentration that contains indium compound during hydro-thermal reaction is 1 * 10
-6～0.1 mol.
Prepare above-mentioned nanostructured, efficient, direct sunshine hydrogen production by water decomposition catalyst (MIn)
xCd
2 (1-x)S
2Method, it is characterized in that if M monovalence transition metal Cu in the product, then its corresponding reactant source is selected from Schweinfurt green, copper chloride, copper nitrate or copper sulphate; If M monovalence Transition Metal Ag, then its corresponding reactant source is silver nitrate; If M monovalence transition metal Au, then its corresponding reactant source is gold trichloride or gold monochloride; The initial concentration of these reactants is 1 * 10
-6～0.1 mol.
Prepare above-mentioned nanostructured, efficient, direct sunshine hydrogen production by water decomposition catalyst (MIn)
xCd
2 (1-x)S
2Method, it is characterized in that the solvent of hydro-thermal reaction is pure water, straight alcohol or water and ethanol mixed solvent, water is any ratio with the ratio of ethanol.
Prepare above-mentioned nanostructured, efficient, direct sunshine hydrogen production by water decomposition catalyst (MIn)
xCd
2 (1-x)S
2Method, it is characterized in that the temperature of hydro-thermal reaction is 140～200 ℃.
Prepare above-mentioned nanostructured, efficient, direct sunshine hydrogen production by water decomposition catalyst (MIn)
xCd
2 (1-x)S
2Method, it is characterized in that the time of hydro-thermal reaction was controlled at 12～80 hours.
Description of drawings
Fig. 1 (AgIn)
xCd
2 (1-x)S
2The SEM photo of catalyst series
B is the sample of x=0.01; B ' is the amplification SEM photo of the sample of x=0.01; C is the sample of x=0.05; E is the sample of x=0.3.
Fig. 2 (AgIn)
xCd
2 (1-x)S
2The XRD figure spectrum of catalyst series
A is the sample of x=0; B is the sample of x=0.01; C is the sample of x=0.05; D is the sample of x=0.1; E is the sample of x=0.3; F is the sample of x=0.5.
Fig. 3 (CuIn)
xCd
2 (1-x)S
2The SEM photo of catalyst series
b
1Sample for x=0.01; b
1' be the amplification SEM photo of the sample of x=0.01; c
1Sample for x=0.05; e
1Sample for x=0.3.
Fig. 4 (CuIn)
xCd
2 (1-x)S
2The XRD figure spectrum of catalyst series
a
1Sample for x=0; b
1Sample for x=0.01; c
1Sample for x=0.05; d
1Sample for x=0.1; e
1Sample for x=0.3.
Fig. 5 catalyst (AgIn)
0.05Cd
1.9S
2(a) and (CuIn)
0.05Cd
1.9S
2(b1) hydrogen manufacturing stability curve.
The specific embodiment
Embodiment 1:(AgIn)
xCd
2 (1-x)S
2The preparation of catalyst series
Come the Cd (Ac) of the corresponding molal quantity of weighing respectively in product molecular formula ratio x=0,0.01,0.05,0.1,0.3 and 0.5
2H
2O, In
2(SO
4) 3, AgNO
3, allow the excessive twice of thiocarbamide simultaneously, for example if x=0.1, then with 6.25 * 10
-4The Cd (Ac) of mole
2H
2O, 3.47 * 10
-5The AgNO of mole
3, 1.74 * 10
-5The In of mole
2(SO
4)
3With 8 * 10
-4The thiocarbamide of mole mixes the water heating kettle inner bag of putting into 100ml, ultrasonic mixing back sealing in 80ml straight alcohol solvent, and reaction is 36 hours in 180 ℃ Muffle furnace.Treat that product cooling back takes out, to remove accessory substance, in 60 ℃ of vacuum drying ovens, promptly obtain needed product after dry 4 hours with straight alcohol and water washing 3～5 times.Along with the increase of x value, the color of product by the orange loess look that becomes, arrives brick-red gradually again.
(SEM) observes this catalyst series with ESEM, and Fig. 1 is the photo of gained, and b is the sample of x=0.01; B ' is the amplification SEM photo of the sample of x=0.01; C is the sample of x=0.05; E is the sample of x=0.3.As seen along with x increases, the catalyst pattern that is assembled into by granule becomes irregular bulk by the ball of rule gradually by photo, and low particle size is less than below the 100nm.
Fig. 2 is (AgIn)
xCd
2 (1-x)S
2The XRD figure spectrum of catalyst series, a is the sample of x=0 among the figure; B is the sample of x=0.01; C is the sample of x=0.05; D is the sample of x=0.1; E is the sample of x=0.3; F is the sample of x=0.5.When x was 0, the sample that obtains was pure CdS as seen from the figure, and this CdS is a hexagonal crystal structure.According to the literature, the crystal structure of this hexagonal has higher hydrogen production activity than other configurations CdS.Along with the increase of x, the spectrogram complexity that becomes gradually, but be increased to more than 0.3 as x, and obviously see AgInS
2The appearance at XRD peak, therefore, this tetraplex can be regarded CdS and AgInS as
2Compound.
What table 1 showed is the comparison of the hydrogen production activity of catalyst under the different composition situations, visible (AgIn)
xCd
2 (1-x)S
2Catalyst series is to have best hydrogen production activity at 0.05 o'clock at x, and the hydrogen manufacturing effect during no Pt load reaches 274.5 μ mol h
-1g
-1, than active taller nearly 6 times of the CdS of supporting Pt.Undoubtedly, the catalyst activity behind the plating Pt has improved several times especially.Simultaneously, the minor variations of x also causes the composite catalyst energy gap that variation has taken place, and the energy gap that reduces makes catalyst can absorb more visible light even ultraviolet light.
Table 1 (AgIn)
xCd
2 (1-x)S
2The comparison of catalyst series sunshine hydrogen production by water decomposition effect, material energy gap
Catalyst: 0.1g. reaction solution: 80mL (0.25 mol K
2SO
3+ 0.35 mol Na
2S). light source: 300W halogen tungsten lamp.
Embodiment 2:(CuIn)
xCd
2 (1-x)S
2The preparation of catalyst series
Come the Cd (NO of the corresponding molal quantity of weighing respectively in product molecular formula ratio x=0,0.01,0.05,0.1,0.3 and 0.5
3)
2, In (NO
3)
3, Cu (CH
3COO)
2, allow the excessive twice of thiocarbamide simultaneously, for example if x=0.1, then with 1.35 * 10
-3Cd (the NO of mole
3)
2, 6.94 * 10
-5Cu (the CH of mole
3COO) 2,6.94 * 10
-5In (the NO of mole
3)
3With 1.6 * 10
-3The thiocarbamide of mole mixes the water heating kettle inner bag of putting into 100ml, ultrasonic mixing back sealing in 80ml second alcohol and water (volume ratio 1: 1) solvent, and reaction is 30 hours in 200 ℃ Muffle furnace.Treat that product cooling back takes out, to remove accessory substance, in 60 ℃ of vacuum drying ovens, promptly obtain (CuIn) after dry 4 hours with straight alcohol and water washing 3～5 times
xCd
2 (1-x)S
2The catalyst series product.Along with the increase of x value, the color of product is gradually by the orange loess look that becomes.
With this catalyst series of scanning electron microscopic observation, Fig. 3 is the photo of gained, b among the figure
1Sample for x=0.01; b
1' be the amplification SEM photo of the sample of x=0.01; c
1Sample for x=0.05; e
1Sample for x=0.3.Increase along with x as seen from the figure, the catalyst pattern that is assembled into by granule is become irregularly shaped gradually by the ball of rule, and short grained size is less than below the 100nm.
Fig. 4 is (CuIn)
xCd
2 (1-x)S
2The XRD figure spectrum of catalyst series, a among the figure
1Sample for x=0; b
1Sample for x=0.01; c
1Sample for x=0.05; d
1Sample for x=0.1; e
1Sample for x=0.3.When x was 0, the sample that obtains was pure CdS as seen from the figure, and this CdS is a hexagonal crystal structure.Along with the increase of x, the spectrogram complexity that becomes gradually, but be increased to 0.3 as x, and obviously see CuInS
2The appearance at XRD peak, therefore, this tetraplex can be regarded CdS and CuInS as
2Compound.The size of this catalyst series that calculates by the Scherrer formula is respectively 18.2nm (x=0), 17.6nm (x=0.01), and 17.5nm (x=0.05), 16.6nm (x=0.1) is with the observed basically identical as a result of SEM.
What table 2 showed is under the different composition situations (CuIn)
xCd
2 (1-x)S
2The comparison of the hydrogen production activity of catalyst series, visible (CuIn)
xCd
2 (1-x)S
2Catalyst series is to have best hydrogen production activity at 0.05 o'clock at x also, and the hydrogen manufacturing effect during no Pt load reaches 645 μ mol h
-1g
-1, than active taller nearly tens times of the CdS of supporting Pt.The catalyst activity that crosses behind the Pt has improved several times especially.The minor variations of x also causes the composite catalyst energy gap that faint variation has taken place simultaneously, and the energy gap that reduces makes catalyst can absorb more visible light even ultraviolet light.
Table 2 (CuIn)
xCd
2 (1-x)S
2The comparison of catalyst series sunshine hydrogen production by water decomposition effect, material energy gap
Catalyst: 0.1g. reaction solution: 80mL (0.25 mol K
2SO
3+ 0.35 mol Na
2S). light source: 300W halogen tungsten lamp.
When Fig. 5 is x=0.05, (CuIn)
0.05Cd
1.9S
2With (AgIn)
0.05Cd
1.9S
2The efficient of two kinds of catalyst hydrogen manufacturing under different time compares, and as seen in 20 hours, activity of such catalysts does not have very big variation substantially, it is apparent that (CuIn)
0.05Cd
1.9S
2The hydrogen manufacturing effect than (AgIn)
0.05Cd
1.9S
2It is many to double.This may to influence the situation difference of CdS band structure relevant with different semi-conducting materials.
Embodiment 3:(AuIn)
xCd
2 (1-x)S
2The preparation of catalyst series
Come the Cd (Ac) of the corresponding molal quantity of weighing respectively in product molecular formula ratio x=0,0.01,0.05,0.1 and 0.3
2H
2O, InCl
3, AuCl, allow the excessive twice of thiocarbamide simultaneously, for example if x=0.1, then with 2.70 * 10
-3The Cd (Ac) of mole
2, 1.39 * 10
-4The AuCl, 1.39 * 10 of mole
-4The InCl of mole
3With 3.2 * 10
-3The thiocarbamide of mole mixes the water heating kettle inner bag of putting into 100ml, ultrasonic mixing back sealing in 80ml pure water solvent, and reaction is 60 hours in 160 ℃ Muffle furnace.Treat that product cooling back takes out, to remove accessory substance, in 60 ℃ of vacuum drying ovens, promptly obtain needed (AuIn) after dry 4 hours with straight alcohol and water washing 3～5 times
xCd
2 (1-x)S
2The catalyst series product.
With this catalyst series of scanning electron microscopic observation, along with x increases, the catalyst pattern that is assembled into by granule is become irregularly shaped gradually by rule spherical, and low particle size is less than below the 100nm.(AuIn)
xCd
2 (1-x)S
2The XRD figure of catalyst series spectrum shows: along with the increase of x, spectrogram is by the characteristic peak of the CdS complexity that becomes gradually, but is increased to 0.3 as x, and obviously sees AuInS
2The appearance at XRD peak, therefore, this tetraplex can be regarded CdS and AuInS as
2Compound.This catalyst series that calculates by the Scherrer formula between 10～30nm, with the observed basically identical as a result of SEM.Under the different composition situations (AuIn)
xCd
2 (1-x)S
2The relatively discovery of catalyst series sunshine hydrogen production by water decomposition activity, (AuIn)
xCd
2 (1-x)S
2Catalyst series is to have best hydrogen production activity at 0.05 o'clock at x also, and the hydrogen manufacturing effect during no Pt load reaches 530 μ mol h
-1g
-1, active taller a lot of than the CdS of supporting Pt.The catalyst activity that crosses behind the Pt has improved several times especially.
Claims (10)
1. sunshine hydrogen production by water decomposition catalyst (MIn)
xCd
2 (1-x)S
2The preparation method, M is the monovalence transition metal, it is characterized in that, hydrothermal method, this method with thiocarbamide as the sulphur source, the compound that contains cadmium is the cadmium source, the compound that contains indium is the indium source, the compound that contains transition metal is the source of monovalence transition metal in the product, with above-mentioned sulphur source, the cadmium source, four kinds of compounds of indium source and monovalence transition metal are at pure water, the ultrasonic back of mixing imports water heating kettle in the mixed solvent of straight alcohol or ethanol and water, after the sealing, hydro-thermal reaction is carried out in heating, after the cooling, the deposit in the water heating kettle is removed accessory substance with ethanol and water washing, promptly obtain catalyst product after the vacuum drying.
2. sunshine hydrogen production by water decomposition catalyst as claimed in claim 1 (MIn)
xCd
2 (1-x)S
2The preparation method, it is characterized in that described monovalence transition metal M is copper, silver or golden, the x scope is from 0.01～0.3.
3. sunshine hydrogen production by water decomposition catalyst as claimed in claim 2 (MIn)
xCd
2 (1-x)S
2The preparation method, it is characterized in that described x scope is 0.01～0.1.
4. sunshine hydrogen production by water decomposition catalyst as claimed in claim 1 (MIn)
xCd
2 (1-x)S
2The preparation method, it is characterized in that the described compound that contains cadmium is selected from water-containing acetic acid cadmium, acetic anhydride cadmium, caddy, cadmium sulfate or cadmium nitrate, the initial concentration that contains the compound of cadmium during hydro-thermal reaction is 1 * 10
-5～1 mol.
5. sunshine hydrogen production by water decomposition catalyst as claimed in claim 1 (MIn)
xCd
2 (1-x)S
2The preparation method, it is characterized in that the concentration range of described reactant thiocarbamide is 2 * 10
-4～2 mol.
6. sunshine hydrogen production by water decomposition catalyst as claimed in claim 1 (MIn)
xCd
2 (1-x)S
2The preparation method, it is characterized in that the described compound that contains indium is selected from inidum chloride, indium sulfate, indium nitrate or indium acetate, the initial concentration that contains indium compound during hydro-thermal reaction is 1 * 10
-6～0.1 mol.
7. sunshine hydrogen production by water decomposition catalyst as claimed in claim 1 (MIn)
xCd
2 (1-x)S
2The preparation method, it is characterized in that if M monovalence transition metal Cu in the product, then its corresponding reactant source is selected from Schweinfurt green, copper chloride, copper nitrate or copper sulphate; If M monovalence Transition Metal Ag, then its corresponding reactant source is silver nitrate; If M monovalence transition metal Au, then its corresponding reactant source is gold trichloride or gold monochloride; The initial concentration of these reactants is 1 * 10
-6～0.1 mol.
8. sunshine hydrogen production by water decomposition catalyst as claimed in claim 1 (MIn)
xCd
2 (1-x)S
2The preparation method, it is characterized in that, described water and ethanol mixed solvent, its water and ethanol are than being any ratio.
9. sunshine hydrogen production by water decomposition catalyst as claimed in claim 1 (MIn)
xCd
2 (1-x)S
2The preparation method, it is characterized in that the temperature of hydro-thermal reaction is 140～200 ℃.
10. sunshine hydrogen production by water decomposition catalyst as claimed in claim 1 (MIn)
xCd
2 (1-x)S
2The preparation method, it is characterized in that the time of hydro-thermal reaction was controlled at 12～80 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190442A (en) * | 2014-09-03 | 2014-12-10 | 上海电力学院 | Cadmium sulfide visible light photocatalyst and preparation method thereof |
| CN104324733A (en) * | 2014-09-26 | 2015-02-04 | 上海交通大学 | Preparation method of precious-metal-free high-activity photocatalytic-water-splitting hydrogen-producing catalyst |
| CN105797752A (en) * | 2016-04-01 | 2016-07-27 | 上海师范大学 | Fullerene modified graphene/cadmium sulfide catalyst as well as preparation method and application thereof |
| CN110354867A (en) * | 2019-07-18 | 2019-10-22 | 陕西科技大学 | A kind of Zn0.2Cd0.8The preparation method of S/rGO catalysis material |
-
2008
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190442A (en) * | 2014-09-03 | 2014-12-10 | 上海电力学院 | Cadmium sulfide visible light photocatalyst and preparation method thereof |
| CN104324733A (en) * | 2014-09-26 | 2015-02-04 | 上海交通大学 | Preparation method of precious-metal-free high-activity photocatalytic-water-splitting hydrogen-producing catalyst |
| CN104324733B (en) * | 2014-09-26 | 2017-09-08 | 上海交通大学 | The preparation method of non precious metal high activity photolytic hydrogen production catalyst |
| CN105797752A (en) * | 2016-04-01 | 2016-07-27 | 上海师范大学 | Fullerene modified graphene/cadmium sulfide catalyst as well as preparation method and application thereof |
| CN110354867A (en) * | 2019-07-18 | 2019-10-22 | 陕西科技大学 | A kind of Zn0.2Cd0.8The preparation method of S/rGO catalysis material |
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