CN101176846B - Non precious metal loaded cuprum doped with sulfureous, zincium and vestalium as well as preparation method thereof - Google Patents
Non precious metal loaded cuprum doped with sulfureous, zincium and vestalium as well as preparation method thereof Download PDFInfo
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- CN101176846B CN101176846B CN2007100187041A CN200710018704A CN101176846B CN 101176846 B CN101176846 B CN 101176846B CN 2007100187041 A CN2007100187041 A CN 2007100187041A CN 200710018704 A CN200710018704 A CN 200710018704A CN 101176846 B CN101176846 B CN 101176846B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a high-hydrogen-producing-activity photocatalyst of copper doped sulfur, zinc and cadmium without precious metals load. The chemical expression of the photocatalyst of copper doped sulfur, zinc and cadmium is CdxCuyZn1-x-yS, wherein 0<x+y>1 and the proportion of Cd:Cu:Zn is free. The new photocatalyst of copper doped sulfur, zinc and cadmium has the advantages of good absorption property of visible light, a higher position of the conduction band, a property of large specific surface area and great improvement of hydrogen producing activity compared with the traditional catalysts such as sulfur, zinc and cadmium. The rate of hydrogen production of the photocatalyst of copper doped sulfur, zinc and cadmium without load under visible light reaches 84 [mu]mol/h with a quantum efficiency of 9.6% at 420 nm. The invention has the advantages of easy operation, low energy consumption; the product prepared by the invention has no need of the precious metal load but high activity, low cost and facilitated popularization.
Description
Technical field
The invention belongs to clean hydrogen producing technology field, be to be the photocatalytic hydrogen production by water decomposition technology of raw material with water under the visible light condition of simulated solar irradiation, relate to a kind of photochemical catalyst and preparation method thereof, cuprum doped with sulfureous, zincium cadmium photochemical catalyst of particularly a kind of non precious metal load and preparation method thereof, the cuprum doped with sulfureous, zincium cadmium photochemical catalyst of the present invention's preparation has very high visible light catalysis activity under immunization with gD DNA vaccine.
Background technology
Natural energy source such as coal, oil is about to face exhausted danger.Simultaneously, environmental pollution and greenhouse effects that the fossil energy burning causes impel people to have to seek new alternative energy source.This wherein, hydrogen becomes the best substitute of non-renewable energy resources such as oil, coal and natural gas as unique pollution-free reproducible energy.Scholarly forecast is arranged, will form " hydrogen economy "-center on the economy that forms for daily life fuel with hydrogen future.The key factor that Hydrogen Energy economy forms is to obtain cheap hydrogen energy source.At present, all prepare to have only in the method for hydrogen and utilize solar energy photocatalytic hydrogen production by water decomposition technology to be hopeful most to obtain cheap hydrogen and accomplish scale production.
The principle of photocatalysis hydrogen production is: under the irradiation of certain energy light, catalyst be subjected to exciting produce electronics and the hole right.Electron transfer is reduced to hydrogen to catalyst surface with water, and the hole is consumed by the sacrifice agent of the suitable cheapness that is added in the system.The key that realizes the solar energy photocatalytic decomposition water is to seek the visible light-responded photochemical catalyst with appropriate bandgap.Although the report of visible light-responded in a large number photochemical catalyst is arranged at present in the world, most activity is on the low side and need carried noble metal as co-catalyst.Cadmium sulfide is a kind of generally acknowledged photochemical catalyst that has under visible light than the high yield hydrogen activity, but because its conduction band position is lower, realizes that highly effective hydrogen yield must be to its carried noble metal.The cost problem of being brought by carried noble metal will seriously restrict its actual use in the future.And zinc sulphide still have very high product hydrogen activity under the situation of noble metals such as not load platinum, but its photoresponse scope only is confined to the ultra-violet (UV) band because it has high conduction band position.In view of zinc sulphide conduction band position advantage of higher, the researcher has launched comparatively extensive studies to the modification of zinc sulphide photochemical catalyst both at home and abroad, and main method has mixes and synthetic solid solution:
1) copper, nickel doped zinc sulphide photochemical catalyst
Near the zinc sulphide valence band, form new energy level by bivalent cupric ion or nickel ion, make catalyst have visible light and produce hydrogen activity, and need not carried noble metal.But the catalyst energy gap after mixing is broad still, can not utilize energy (Catalysis Letters, 1999,58,241 of visible light wave range efficiently; Chemical Communications, 2000,1371).
2) sulphur zinc cadmium solid solution catalyst
Preparation sulphur zinc cadmium solid solution can solve the deficiency of cadmium sulfide and zinc sulphide to a certain extent, makes catalyst still have higher visible light activity under non-loaded situation.It is exactly to work as cadmium content more after a little while that but sulphur zinc cadmium solid solution has a defective, and the forbidden band broad can not effectively utilize visible light; And cadmium content is when too high, and catalyst conduction band position is not high enough, and the light induced electron reducing power dies down, and needs carried noble metal could obtain to produce preferably hydrogen activity (Journal of Physical Chemistry, 1986,90,824).
Summary of the invention
The objective of the invention is to, cuprum doped with sulfureous, zincium cadmium photochemical catalyst of a kind of non precious metal load and preparation method thereof is provided, adopt doping and the two method that combines of solid solution that zinc sulphide is carried out modification, and by coprecipitation preparation, obtained the high visible activity, need not the photochemical catalyst cuprum doped with sulfureous, zincium cadmium (Cd of load
xCu
yZn
1-x-yS).
For achieving the above object, the present invention adopts following technical solution:
A kind of preparation method of cuprum doped with sulfureous, zincium cadmium photochemical catalyst of non precious metal load, carry out according to the following steps:
The chemical expression that makes this cuprum doped with sulfureous, zincium cadmium photochemical catalyst is Cd
0.1Cu
0.01Zn
0.89S;
Cadmium nitrate, copper nitrate and zinc nitrate are pressed stoichiometric proportion Cd: Cu: Zn=0.1 in the described step 1: 0.01: 0.89.
A kind of cuprum doped with sulfureous, zincium cadmium photochemical catalyst of preparation method's preparation of cuprum doped with sulfureous, zincium cadmium photochemical catalyst of non precious metal load, described cuprum doped with sulfureous, zincium cadmium photochemical catalyst is Cd
0.1Cu
0.01Zn
0.89S, described Cd
0.1Cu
0.01Zn
0.89The hydrogen-producing speed of S has reached 84 μ mol/h.
Cd of the present invention
xCu
yZn
1-x-yThe agent of S novel photocatalysis has very high visible light catalysis activity under immunization with gD DNA vaccine, it produces the hydrogen performance far above independent doping or solid solution catalyst, as cuprum doped with sulfureous zinc, and sulphur zinc cadmium photochemical catalyst.The highest hydrogen-producing speed has reached 84 μ mol/h on this breadboard micro-reaction equipment, and the quantum efficiency at the 420nm place reaches 9.6%.This illustrates Cd
xCu
yZn
1-x-yThe agent of S novel photocatalysis has high activity, need not characteristics such as load.
Description of drawings
Fig. 1. change the vulcanized sodium addition to Cd
0.1Cu
0.01Zn
0.89The S catalyst produces the figure that influences of hydrogen activity;
Fig. 2 is mixing time is produced hydrogen activity to catalyst the figure that influences;
Fig. 3 is the vulcanized sodium rate of addition produces hydrogen activity to catalyst the figure that influences;
Fig. 4 is visible light product hydrogen figure and the quantum efficiency figure of different chemical metering than catalyst;
Fig. 5 is Cd
xCu
yZn
1-x-yThe transmission electron microscope picture of S;
Fig. 6 .Cd
xCu
yZn
1-x-yThe X-ray diffraction spectrogram of S; Wherein, (a) be Cd
0.1Cu
0.01Zn
0.89S (b) is Cd
0.1Zn
0.9S (c) is Cu
0.01Zn
0.99S;
Fig. 7 .Cd
xCu
yZn
1-x-yThe diffuse reflection spectrum of S; Wherein, (a) be Cd
0.1Cu
0.01Zn
0.89S (b) is Cd
0.1Zn
0.9S (c) is Cu
0.01Zn
0.99S;
Fig. 8 is a visible light photocatalysis decomposition water experimental system schematic diagram;
Fig. 9 is the product hydrogen figure by the synthetic catalyst of optimal processing parameter.
The present invention is described in further detail below in conjunction with embodiment that accompanying drawing and inventor provide.
The specific embodiment
Task of the present invention is sought a kind of simple, high-efficiency method exactly zinc sulphide is carried out modification, prepares to have the photochemical catalyst that high visible produces hydrogen activity and need not carried noble metal, in the hope of improving photocatalysis hydrogen production efficient greatly.
The present invention mixes by utilization simultaneously and two kinds of methods of synthetic solid solution have been carried out modification to ZnS, has obtained the novel photocatalysis agent Cd that produces the hydrogen height, need not load
xCu
yZn
1-x-yS.Below be the embodiment that the inventor provides, need to prove that these embodiment are some more excellent examples, the invention is not restricted to these embodiment.
Embodiment 1:
The preparation method of the cuprum doped with sulfureous, zincium cadmium photochemical catalyst of the non precious metal load that present embodiment provides, concrete processing step is as follows:
1) with cadmium nitrate, copper nitrate and zinc nitrate by stoichiometric proportion Cd: Cu: Zn=0.1: be dissolved in deionized water at 0.01: 0.89, the preparation salting liquid, the salting liquid total concentration is respectively 0.05mol/L, 0.1mol/L, 0.2mol/L;
2) vulcanized sodium is dissolved in deionized water, the preparation sodium sulfide solution, sodium sulfide solution concentration is respectively 0.25mol/L, 0.5mol/L, 1mol/L.
3) sodium sulfide solution of above-mentioned variable concentrations is slowly splashed into respectively in the salting liquid of variable concentrations of stirring by 5 multiple doses under the room temperature, the preparation mixed solution, the sodium sulfide solution rate of addition is 4ml/min; Drip follow-up continuous agitating solution 12h fully.
4) mixed solution that obtains is filtered, washing, place 60 ℃ in baking oven dry 6h down, after grinding, obtain final products.
Table 1 has provided the influence of reactant concentration variation to catalyst activity.
Embodiment 2:
The preparation method of the cuprum doped with sulfureous, zincium cadmium photochemical catalyst of the non precious metal load that present embodiment provides, concrete processing step is as follows:
1) with cadmium nitrate, copper nitrate and zinc nitrate by stoichiometric proportion Cd: Cu: Zn=0.1: be dissolved in deionized water at 0.01: 0.89, the preparation salting liquid, the salting liquid total concentration is 0.1mol/L;
2) vulcanized sodium is dissolved in deionized water, the preparation sodium sulfide solution, the concentration of sodium sulfide solution is 0.5mol/L.
3) respectively sodium sulfide solution is slowly splashed in the salting liquid of stirring by 1,3,5,7 multiple doses respectively under the room temperature, rate of addition is 4ml/min; The preparation mixed solution drips follow-up continuous agitating solution 12h fully.
4) mixed solution that obtains is filtered, washing, place 60 ℃ in baking oven dry 6h down, after grinding, obtain final products.
Fig. 1 has provided the variation along with the different catalysts hydrogen-producing speed of vulcanized sodium addition.
Table 1 solution concentration is to catalyst activity influence (unit: μ mol/h)
Embodiment 3:
The preparation method of the cuprum doped with sulfureous, zincium cadmium photochemical catalyst of the non precious metal load that present embodiment provides, concrete processing step is as follows:
1) with cadmium nitrate, copper nitrate and zinc nitrate by stoichiometric proportion Cd: Cu: Zn=0.1: be dissolved in deionized water at 0.01: 0.89, the preparation salting liquid, the salting liquid total concentration is 0.1mol/L;
2) vulcanized sodium is dissolved in deionized water, the preparation sodium sulfide solution, the concentration of sodium sulfide solution is 0.5mol/L.
3) sodium sulfide solution is slowly splashed in the salting liquid of stirring by 5 multiple doses under the room temperature, the preparation mixed solution, the rate of addition of sodium sulfide solution is respectively 2ml/min, 4ml/min, 8ml/min, 20ml/min; Drip follow-up continuous agitating solution 12h fully.
With the mixed solution that obtains filter, washing, place 60 ℃ in baking oven dry 6h down, after grinding, obtain final products.
Fig. 2 has provided the variation of producing hydrogen activity along with the different catalysts of vulcanized sodium rate of addition.
Embodiment 4:
The preparation method of the cuprum doped with sulfureous, zincium cadmium photochemical catalyst of the non precious metal load that present embodiment provides, concrete processing step is as follows:
1) with cadmium nitrate, copper nitrate and zinc nitrate by stoichiometric proportion Cd: Cu: Zn=0.1: be dissolved in deionized water at 0.01: 0.89, the preparation salting liquid, the salting liquid total concentration is 0.1mol/L;
2) vulcanized sodium is dissolved in the deionized water, the preparation sodium sulfide solution, the concentration of sodium sulfide solution is 0.5mol/L.
3) sodium sulfide solution is slowly splashed in the salting liquid of stirring by 5 multiple doses under the room temperature, the preparation mixed solution, the rate of addition of sodium sulfide solution is 4ml/min; Drip follow-up continuous agitating solution 1h, 6h, 12h and 24h fully.
4) mixed solution that obtains is filtered, washing, place 60 ℃ in baking oven dry 6h down, after grinding, obtain final products.
Fig. 3 has provided the influence of mixing time to catalyst activity.
Embodiment 5:
The preparation method of the cuprum doped with sulfureous, zincium cadmium photochemical catalyst of the non precious metal load that present embodiment provides, concrete processing step is as follows:
1) cadmium nitrate, copper nitrate and zinc nitrate are measured than being dissolved in the deionized water by different chemical, prepare salting liquid, the salting liquid total concentration is 0.1mol/L;
2) vulcanized sodium is dissolved in deionized water, the preparation sodium sulfide solution, the concentration of sodium sulfide solution is 0.5mol/L.
3) sodium sulfide solution is slowly splashed in the salting liquid of stirring by 5 multiple doses under the room temperature, the preparation mixed solution, the rate of addition of sodium sulfide solution is 4ml/min; Drip follow-up continuous agitating solution 1h, 6h, 12h and 24h fully.
4) mixed solution that obtains is filtered, washing, place 60 ℃ in baking oven dry 6h down, after grinding, obtain final products.
Fig. 4 is visible light product hydrogen and the quantum efficiency figure of different chemical metering than synthetic catalyst.
As long as all right exclusive list of above-mentioned EXPERIMENTAL EXAMPLE within the scope of the invention, all can obtain suitable cuprum doped with sulfureous, zincium cadmium photochemical catalyst, but in order further to simplify technology, the parameter of experimental selection embodiment 4 (mixing time is 12h) is optimal selection.
Fig. 5 is Cd
xCu
yZn
1-x-yThe transmission electron microscope photo figure of S.Can find that catalyst granules is to be reunited by the crystal grain about 4nm with forming.The nanometer grade diameter of catalyst granules has caused the generation of quantum effect, so the semiconductor catalyst energy gap broadens, corresponding conduction band position uprises, catalyst reduction ability grow.
Fig. 6 has provided Cd
xCu
yZn
1-x-yThe X-ray diffraction of S (XRD) figure, abscissa is represented scanning angle, ordinate is represented signal strength signal intensity.Can find that from figure catalyst is a zincblende lattce structure.Along with Cd
2+Adding, the diffraction maximum of catalyst moves to the low angle direction.This is because Cd
2+Radius is
Greater than Zn
2+Radius
This also illustrates Cd
2+Entered the lattice framework of ZnS.And Cu
2+Radius is
Near Zn
2+, and Cu
2+Doping less, so Cd
0.1Cu
0.01Zn
0.89S and Cd
0.1Zn
0.9There is not significant change between the diffraction peak of S.The tangible broadening of diffraction maximum causes owing to catalyst granules is that long-range is unordered, and this explanation catalyst granules is a nanoscale.Can estimate Cd by the Scherrer equation
0.1Cu
0.01Zn
0.89The particle of S the chances are 3.4nm, this result with transmission electron microscope is consistent.Thereby this has and is beneficial to carrier and moves to catalyst surface fast and restrain compound in catalyst inside of light induced electron and hole, and big specific area (150.88m
2/ g) can provide more product hydrogen activity site, thus the photo-catalysis capability of catalyst improved.
Fig. 7 has provided Cd
xCu
yZn
1-x-yThe ultraviolet-visible absorption spectroscopy of S.Cd
0.1Zn
0.9The ABSORPTION EDGE of S has reached 470nm, and precipitous ABSORPTION EDGE explanation has formed continuous conduction band, rather than doped energy-band.Because the conduction band of CdS and ZnS is made of the 5s5p track of Cd and the 4s4p track of Zn respectively, so can infer at Cd
0.1Zn
0.9The 4s4p rail interaction of the 5s5p track of Cd and Zn has constituted the conduction band of solid solution among the S.And Cu
0.01Zn
0.99The ABSORPTION EDGE of S has reached 500nm, and the absorption of catalyst in the visible region is because the electronic service guide band transition near the new impurity energy level that forms the valence band of Cu at ZnS causes.As can be seen from the figure contain the ABSORPTION EDGE maximum of the catalyst of Cd, two kinds of elements of Cu simultaneously, reached 560nm, and absorption coefficient is the highest.This has also illustrated the crystalline framework that Cd, Cu atom have all entered catalyst.Can estimate Cd from absorbing limit
0.1Cu
0.01Zn
0.89The energy gap of S is 2.23eV.
Cd of the present invention
xCu
yZn
1-x-yThe cuprum doped with sulfureous, zincium cadmium photochemical catalyst of the novel non precious metal load of S has good visible light absorption on the one hand, and ABSORPTION EDGE has reached 560nm, has guaranteed that catalyst can utilize the energy of visible light wave range fully; And owing to Zn in the catalyst accounts for main component, the conduction band position that has guaranteed catalyst is enough high, thereby make light induced electron have strong reducing power, so that catalyst need not still have very high product hydrogen activity under the situation of load, and this is the characteristics that most of at present catalyst of having reported do not possess.On the other hand,, make light induced electron and hole just can migrate to the catalyst surface active position in a short period of time, help restraining in the body of photo-generated carrier compound because the catalyst granules radius is very little; And Large ratio surface provides more reaction active site for catalytic reaction, when carrier mobility can be very fast during to catalyst surface with solution in oxidation, the reaction of reduction species, the surface recombination of having restrained carrier.Therefore, Cd
xCu
yZn
1-x-yThe agent of S novel photocatalysis has the performance that high visible produces hydrogen activity and need not the noble metal load.
It below is the concrete confirmatory experiment that the present invention provides.
(1). hydrogen performance evaluation is produced in photocatalysis
All visible light photocatalysis decomposition water experiments of the present invention are all finished in experimental system shown in Figure 8, mainly comprise following components: Pyrex glass reactor, magnetic stirring apparatus, 420nm optical filter and 300W xenon lamp device.300W xenon lamp device mainly comprises an xenon lamp control cabinet, a 300W xenon lamp, a reflective tile and a small electric fan.Because xenon lamp work the time can follow a large amount of heat to emit, to carry out air-cooledly so the rear portion has installed an electric fan additional, the temperature constant of practical measurement light-catalyzed reaction system is at 35 ± 5 ℃.
Experimental procedure:
1, in reactor, adds 0.3g catalyst, sacrifice agent employing 0.3mol/L Na
2SO
3, 0.2mol/LNa
2The S mixed liquor; The 200ml deionized water;
2, logical nitrogen purges 10min in the illumination forward reaction device, with the oxygen in the system of removing;
3, add optical filter, open the electric fan in the xenon lamp device, drive magnetic stirring apparatus;
4, open xenon lamp power supply;
5, behind the reaction certain hour, in reactor, get 100 μ L gases and be expelled to and carry out gas composition and constituent analysis (the SP-2100 type gas chromatograph that the BeiFen Instrument Techogy Co., Ltd., BeiJing City produces, TCD detector, 5A molecular sieve column) in the gas chromatograph.
Contrast by each catalyst in the example is found: the solution concentration overrich, and sodium sulfide amount is less, and rate of addition is very fast, and mixing time shortens, and all can reduce the product hydrogen activity of catalyst.Otherwise then catalyst product hydrogen activity uprises, but after arriving to a certain degree, these factors diminish gradually to the influence of catalyst.Its reason may be ZnS, CdS, the different solubility of CuS, when solution overrich or rate of addition too fast, ZnS, CdS, CuS not exclusively precipitate with the solid solution form, but have the separation phase individualism of partly precipitated with three kinds of materials, thereby have reduced the reactivity of catalyst.The vulcanized sodium addition is too little, and catalyst production is lower on the one hand, and reaction not exclusively; On the other hand, can form the sulphur room in the catalyst.Equally, mixing time is too short also can bring similar influence.The sulphur room can form the complex centre in light induced electron and hole, thereby can reduce the catalyst reaction activity.
From the contrast experiment, can find metal salt solution (0.1mol/l), Na
2S (0.5mol/l) presses with the volume hybrid reaction, rate of addition 4ml/min, and stirring 12 hours is best preparation scheme.
Table 2 has provided Cd
xCu
yZn
1-x-yThe product hydrogen contrast of S photochemical catalyst.From table, can find Cd
0.1Cu
0.01Zn
0.89The hydrogen-producing speed of S is far above Cd
0.1Zn
0.9S and Cu
0.01Zn
0.99The S catalyst has reached 84 μ mol/h.This result with uv-vis spectra is consistent.This illustrates that the method by doping and synthetic solid solution can effectively change the band structure of catalyst, has significantly improved the product hydrogen performance of catalyst.The main cause that significantly improves of the hydrogen-producing speed of novel photocatalysis agent of the present invention is exactly that bandwidth narrows down, and can effectively absorb more photon and generate photo-generated carrier.Fig. 9 has provided the long-time product hydrogen figure of catalyst, can find that from figure catalyst activity behind reaction 10h does not have significant change, illustrates that photochemical catalyst of the present invention has stable product hydrogen activity.
Table 2.Cd
xCu
yZn
1-x-yPhotocatalysis is produced hydrogen relatively under the S visible light
| Catalyst | Energy gap (eV) | Hydrogen-producing speed (μ mol/h) |
| Cd 0.1Cu 0.01Zn 0.89S | 2.23 | 84 |
| Cd 0.1Zn 0.9S | 2.66 | 23 |
| Cu 0.01Zn 0.99S | 2.5 | 3 |
(2) catalyst efficiency evaluation
Catalyst quantum efficient and light energy use efficiency computing formula are as follows:
The product hydrogen meter of light-catalyzed reaction is seen quantum efficiency and is calculated by following formula:
The quantum efficiency of the photocatalysis hydrogen production of catalyst adopts single line light method to measure.The 300W xenon source installs the single line light that dominant wavelength is the logical type optical filter acquisition of band 420 ± 5nm of 420nm additional.(photoelectric instrument factory of Beijing Normal University produces, and model is: (λ: 400-1000nm) probe records add 300W xenon lamp behind the optical filter average to see through unit light intensity is W=1.1mW/cm the UV-B type) subsidiary FZ-A type to adopt the light intensity irradiatometer
2. because of effective irradiated area of reactor is A=π R
2=π * 20
2=12.56cm
2Can be regarded as on average by Q=WA is Q=13.816mW through light intensity.With the photon of light intensity conversion for the 420nm place, this wavelength place, the energy of each photon is 4.73*10
-19J.Calculating in the 420nm place sub-efficient of hydrogen output by formula (1) is 9.6%.
Claims (2)
1. the preparation method of the cuprum doped with sulfureous, zincium cadmium photochemical catalyst of a non precious metal load is characterized in that, carries out according to the following steps:
Step 1 is dissolved in cadmium nitrate, copper nitrate and zinc nitrate in the deionized water by stoichiometric proportion, obtains salting liquid, and the salting liquid total concentration is 0.05mol/L-0.2mol/L;
Step 2 is dissolved in deionized water with vulcanized sodium, obtains sodium sulfide solution, and the concentration of sodium sulfide solution is 0.25mol/L-1mol/L;
Step 3 is a benchmark with precipitation metal required chemical dose vulcanized sodium under the room temperature, and 1-7 vulcanized sodium is doubly slowly splashed into the solution form in the salting liquid of stirring, and rate of addition is 2ml/min-20ml/min; Drip follow-up continuous stirring fully 1 hour-24 hours, obtain mixed solution;
Step 4 is filtered mixed solution, wash, and places 60 ℃ of following dry 6h of baking oven, promptly obtains cuprum doped with sulfureous, zincium cadmium photochemical catalyst after grinding,
The chemical expression that makes this cuprum doped with sulfureous, zincium cadmium photochemical catalyst is Cd
0.1Cu
0.01Zn
0.89S;
Cadmium nitrate, copper nitrate and zinc nitrate are pressed stoichiometric proportion Cd: Cu: Zn=0.1 in the described step 1: 0.01: 0.89.
2. the cuprum doped with sulfureous, zincium cadmium photochemical catalyst of preparation method's preparation of the cuprum doped with sulfureous, zincium cadmium photochemical catalyst of a kind of non precious metal load according to claim 1, it is characterized in that: described cuprum doped with sulfureous, zincium cadmium photochemical catalyst is Cd
0.1Cu
0.01Zn
0.89S, described Cd
0.1Cu
0.01Zn
0.89The hydrogen-producing speed of S has reached 84 μ mol/h.
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| CN110055557B (en) * | 2019-04-11 | 2020-03-03 | 中国科学院化学研究所 | Three-dimensional nickel-doped iron-based oxygen evolution catalyst and preparation method and application thereof |
| CN112604697B (en) * | 2020-12-20 | 2022-06-17 | 桂林理工大学 | Copper ion doped zinc oxide/cadmium sulfide high-performance water decomposition hydrogen production photocatalyst and preparation method thereof |
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