CN102861597A - Catalyst capable of responding to visible light and being used for producing hydrogen by photocatalytic water splitting and preparation method of catalyst - Google Patents
Catalyst capable of responding to visible light and being used for producing hydrogen by photocatalytic water splitting and preparation method of catalyst Download PDFInfo
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- CN102861597A CN102861597A CN2012103703705A CN201210370370A CN102861597A CN 102861597 A CN102861597 A CN 102861597A CN 2012103703705 A CN2012103703705 A CN 2012103703705A CN 201210370370 A CN201210370370 A CN 201210370370A CN 102861597 A CN102861597 A CN 102861597A
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Abstract
The invention discloses a catalyst capable of responding to visible light and being used for producing hydrogen by photocatalytic water splitting and a preparation method of the catalyst. The catalyst comprises CdS and an auxiliary loaded on the CdS, and the auxiliary is a mixture of NiS and an optional one of PdS, Ru2S3, Rh2S3 and Ag2S. The CdS is added into aqueous solution containing an S compound, and a Ni compound and a compound containing an optional one of Pd, Ru, Rh and Ag are added into the aqueous solution under the condition of stirring to obtain the catalyst capable of producing the hydrogen by photocatalytic water splitting via stirring. The auxiliary of the photochemical catalyst capable of absorbing the visible light is added with Ni metal, load of auxiliaries which are precious metals is obviously reduced, and the cost for preparing the catalyst can be lowered.
Description
Technical field
The present invention relates to a kind of photolysis water hydrogen Catalysts and its preparation method of responding to visible light, belong to the photocatalyst technology field.
Background technology
Photocatalysis is a kind of emerging depollution of environment and energy conversion technology.Aspect the depollution of environment, photochemical catalyst can effectively be degraded and is adsorbed on its lip-deep pernicious gas molecule, kill bacteria, inhibition virus, harmful organic substance, bacterium etc. is converted into the innocuous substances such as water and carbon dioxide, and without any secondary pollution.Aspect energy conversion, utilize photocatalysis technology light energy conversion can be chemical energy, more commonly the photolysis water hydrogen technology directly is converted to Hydrogen Energy with solar energy.Along with the development of photocatalysis technology, be expected to utilize sunshine, directly from various water bodys, obtain the most energy-Hydrogen Energy of cleaning, solve from now on global energy and environmental problem.Extensively and effectively utilizing of photocatalysis technology depended on the efficient of light-catalyzed reaction.The photodissociation water catalyst of early stage research and development all is that ultraviolet light is partly had preferably response, and the cadmium sulfide of research and development is that catalysis material is the Typical Representative catalyst system and catalyzing that visible light is had response in the recent period.Cadmium sulfide energy strong absorption visible light, formation has free electron and the electron hole of extremely strong reduction and oxidability, when the surface of the free electron that produces and hole migration arrival particle, hydrate produces the various free radicals such as OH, and water directly resolves into hydrogen and oxygen the most at last.Therefore, improving properties of catalyst is the key that improves photocatalysis efficiency.Can improve by following approach the activity of photochemical catalyst: (1) catalysis material nanometer and increasing specific surface area; (2) improve degree of crystallinity, reduce lattice defect; (3) modulation forbidden band structure improves visible Optical Absorption and utilization; (4) utilize the load auxiliary agent to promote electronics to shift and provide Adsorption and formation hetero-junctions.In above method, approach (3) and (4) technology space maximum and application prospect are the most extensive, and technology is relatively simply raised the efficiency obviously in (4) simultaneously, again to a certain extent improving stability, therefore in recent years extremely people's attention and research.
The TiO such as Japanese scientist Fujishima in 1972 and Honda
2Single Crystalline Electrodes has been realized photocatalytic hydrogen production by water decomposition, thereby solar energy is converted into Hydrogen Energy, realizes the artificial photosynthesis, for the energy problem that solves the whole world provides fabulous technological approaches.In recent decades, around how to prepare cheapness, highly active catalysis material various countries scientific worker has done large quantity research, with TiO
2With CdS be that a large amount of highly active photochemical catalyst of representative is in the news.For the CdS catalyst system and catalyzing of responding to visible light, domestic existing patented technology is open.The preparation method that the patent CN1803278 of Xi'an Communications University has invented a kind of tantalum titanate cadmium sulphide platinum-carried laminated composite catalyst; the highest hydrogen-producing speed 144umol/h; quantum efficiency at the 420nm place is 6.3%, is 1.67% to the light energy use efficiency in visible light all band zone, and the gained catalyst stability is better; but complex steps on this method for preparing catalyst; raw material is complicated, and manufacturing cycle is longer, and the catalyst light energy conversion efficiency is lower; the possibility of therefore, accomplishing scale production is limited.The patent CN102266787A of Physical Chemistry Technology Inst., Chinese Academy of Sciences discloses a kind of novel preparation method who does not contain noble metal photolysis water hydrogen catalyst, and this technology is to utilize Graphene as co-catalyst, preparation CdS-graphene composite material.Grapheme material has good electronics to be assembled and transfer function, has promoted the effective separation of electron hole, has reduced the compound probability of proton, has increased photocatalysis efficiency and the light hydrogen production by water decomposition efficient of photochemical catalyst.And the grapheme material preparation method is simple, and is more with low cost and environment do not polluted than noble metal, is beneficial to extensive preparation production.But its weak point is that Graphene itself still is difficult to produce on a large scale, and price is high, and quality is difficult to guarantee that simultaneously, its visible light catalytic efficient and light hydrogen production by water decomposition efficient remain further to be studied to improve.
Summary of the invention
The photolysis water hydrogen Catalysts and its preparation method that the purpose of this invention is to provide a kind of responding to visible light, catalyst provided by the invention has stronger visible absorption ability, can effectively absorb up to the visible light about 540nm, it is active to show efficient photolysis water hydrogen under visible light.
The photolysis water hydrogen catalyst of a kind of responding to visible light provided by the present invention is comprised of with the auxiliary agent that loads on the CdS CdS;
Described auxiliary agent is NiS and PdS, Ru
2S
3, Rh
2S
3And Ag
2Any mixture among the S.
In the above-mentioned photolysis water hydrogen catalyst, the quality percentage composition of described NiS (being load capacity) can be 0.22 ~ 5.5%, such as 1% ~ 3.5%, 1%, 1.5% or 3.5%; Described PdS, Ru
2S
3, Rh
2S
3And Ag
2Any quality percentage composition (being load capacity) can be 0.1 ~ 3.0% among the S, as the content of PdS can be 0.4%, Ru
2S
3Content can be 0.38%, Rh
2S
3Content can be 0.31% and Ag
2The content of S can be 0.16%.
The preparation method of above-mentioned photolysis water hydrogen catalyst provided by the present invention, comprise the steps: described CdS is added in the aqueous solution that contains the S compound, under the condition that stirs, continue to add again the compound that contains the Ni compound and contain among Pd, Ru, Rh and the Ag any, namely get described photolysis water hydrogen catalyst through stirring, the method is sedimentation.
Among the above-mentioned preparation method, after adding the described Ni of containing compound and containing among Pd, Ru, Rh and the Ag any compound, namely got described catalyst in 1 ~ 2 hour through stirring.
This law also provides the preparation method of another kind of above-mentioned photolysis water hydrogen catalyst, comprise the steps: described CdS, contain the S compound, contain the Ni compound, contain Pd, any compound and water are added in the autoclave among Ru, Rh and the Ag, then namely get described photolysis water hydrogen catalyst through hydro-thermal reaction, the method is hydro-thermal method.
Among the above-mentioned preparation method, the temperature of described hydro-thermal reaction can be 105 ~ 240 ℃, and the time can be 2 ~ 8 hours; As reacting 8h under 105 ℃ the condition, under the condition of reaction 6h or 240 ℃ under 140 ℃ the condition, reacting 2h.
Among the above-mentioned preparation method, described method also can comprise the steps that described photolysis water hydrogen catalyst placed 80 ~ 95 ℃ of lower dryings.
Among the above-mentioned preparation method, the described S of containing compound can be in vulcanized sodium and the thiocarbamide any; The described Ni of containing compound can be in nickel nitrate, nickel acetate, nickel chloride and the nickelous sulfate any; The described Pd of containing compound can be palladium bichloride, and the described Ru of containing compound can be ruthenic chloride, and the described Rh of containing compound can be radium chloride, and the described Ag of containing compound can be silver nitrate.
Among the above-mentioned preparation method, described CdS is according to the preparation of the method that comprises the steps: will contain and carry out hydro-thermal reaction after Cd compound and the described S of the containing compound and namely get described CdS; The described Cd of containing compound can be in cadmium nitrate, cadmium acetate, caddy and the cadmium sulfate any; The temperature of described hydro-thermal reaction can be 140 ~ 210 ℃, as reacting 48h under 140 ℃ the condition, reacting 36h under 200 ℃ the condition or react 24h under 210 ℃ condition.
The present invention has following beneficial effect: the energy that the sun discharges reaches earth surface in 1 year total amount is 5.5X1026J, by the present whole mankind 1 year 10,000 times of consumption energy summation.The low-density of solar energy and unstability thereof have limited its application, particularly are converted into the direct utilization of electric energy.Water and sunlight can claim it is inexhaustible material.The hydrogen that obtains from water as the form of having got back to again water after the energy use, is a kind of completely sustainable exploitation and use.Utilize photocatalysis technology solar energy directly can be converted to chemical energy---Hydrogen Energy.Can photodissociation water practically depend on energy conversion efficiency the most at last.The photochemical catalyst great majority that can be used for photodissociation water that people found and developed up to now only can absorb its wavelength less than the ultraviolet ray of 400nm.And ultraviolet ray only accounts for about 3% in sunshine.So photochemical catalyst provided by the present invention can absorb visible light, can greatly utilize sunshine, realize efficient photolysis water hydrogen, have positive meaning to solving the following energy and environmental problem.In addition, introduce the Ni metal in the auxiliary agent of the photochemical catalyst that can absorb visible light provided by the present invention, significantly reduced the load capacity of precious metal additive, can reduce the preparation cost of catalyst.
The specific embodiment
Employed experimental technique is conventional method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
Among the following embodiment, the testing conditions of gas-chromatography on-line quantitative analysis is: the Ar carrier gas; 5A molecular sieve chromatography post; 40 ℃ of column temperatures; The thermal conductance temperature 60 C; Bridge stream 80mA.
Embodiment 1, (1wt%) NiS-(0.4wt%) sedimentation preparation and the catalysis thereof of PdS/CdS produces the hydrogen effect
1) 200ml 0.2M sodium sulfide solution is slowly added in the 250ml 0.2M cadmium acetate aqueous solution, stir and left standstill 24 hours after 24 hours, change sediment over to the high pressure water heating kettle and carry out hydro-thermal; Hydrothermal temperature is 210 ℃, hydro-thermal 24 hours; Suction filtration then, 80 ℃ of dryings can get CdS.
2) with 0.15g(0.001mol) CdS that makes puts into 50ml sodium sulfide solution (5M), constantly stirs, and slowly adds 0.8ml nickel sulfate solution (0.02M) and 0.2ml palladium chloride aqueous solution (Pd:0.00236g/ml).Stirred 1 hour, and then filtered, can get NiS-PdS/CdS in 8 hours in 80 ℃ of lower dryings again.
Getting the NiS-PdS/CdS that makes is scattered in the 80mL30vol% lactic acid, place photo catalysis reactor, with 300W xenon lamp radiation of visible light (utilizing the following light of sodium nitrite solution elimination 420nm), the gas-chromatography on-line quantitative analysis of the hydrogen that reaction generates with conductance cell, the hydrogen-producing speed of 0.15g NiS-PdS/CdS is 4650 μ molh
-1
Embodiment 2, (1wt%) NiS-(0.4wt%) sedimentation preparation and the catalysis thereof of PdS/CdS produces the hydrogen effect
1) 200ml 0.2M sodium sulfide solution is slowly added in the 250ml 0.2M cadmium acetate aqueous solution, stir and left standstill 24 hours after 24 hours, change sediment over to the high pressure water heating kettle and carry out hydro-thermal.Hydrothermal temperature is 140 ℃, hydro-thermal 48 hours.Suction filtration then, 80 ℃ of dryings can get CdS.
2) with 0.15g(0.001mol) CdS that makes puts into 50ml sodium sulfide solution (5M), constantly stirs, and slowly adds 0.8ml nickel nitrate aqueous solution (0.02M) and 0.2ml palladium chloride aqueous solution (Pd:0.00236g/ml).Stirred 1 hour, then filtration, 80 ℃ of dryings can get NiS-PdS/CdS in 8 hours.
Getting the NiS-PdS/CdS that makes is scattered in the 80mL30vol% lactic acid, place photo catalysis reactor, with 300W xenon lamp radiation of visible light (utilizing the following light of sodium nitrite solution elimination 420nm), the gas-chromatography on-line quantitative analysis of the hydrogen that reaction generates with conductance cell, the hydrogen-producing speed of 0.15g NiS-PdS/CdS is 4210 μ molh
-1
Embodiment 3, (1wt%) NiS-(0.4wt%) sedimentation preparation and the catalysis thereof of PdS/CdS produces the hydrogen effect
1) 200ml 0.2M sodium sulfide solution is slowly added in the 250ml 0.2M cadmium acetate aqueous solution, stir and left standstill 24 hours after 24 hours, change sediment over to the high pressure water heating kettle and carry out hydro-thermal.Hydrothermal temperature is 200 ℃, hydro-thermal 36 hours.Suction filtration then, 80 ℃ of dryings can get CdS.
2) with 0.15g(0.001mol) CdS that makes puts into 50ml sodium sulfide solution (5M), constantly stirs, and slowly adds 0.8ml nickel chloride aqueous solution (0.02M) and 0.2ml palladium chloride aqueous solution (Pd:0.00236g/ml).Stirred 1 hour, then filtration, 80 ℃ of dryings can get NiS-PdS/CdS in 8 hours.
Getting the NiS-PdS/CdS that makes is scattered in the 80mL30vol% lactic acid, place photo catalysis reactor, with 300W xenon lamp radiation of visible light (utilizing the following light of sodium nitrite solution elimination 420nm), the gas-chromatography on-line quantitative analysis of the hydrogen that reaction generates with conductance cell, the hydrogen-producing speed of 0.15g NiS-PdS/CdS is 4350 μ molh
-1
Embodiment 4, (1.5wt%) NiS-(0.4wt%) hydro-thermal preparation and the catalysis thereof of PdS/CdS produces the hydrogen effect
1) 200ml 0.2M sodium sulfide solution is slowly added in the 250ml 0.2M cadmium acetate aqueous solution, stir and left standstill 24 hours after 24 hours, change sediment over to the high pressure water heating kettle and carry out hydro-thermal.Hydrothermal temperature is 200 ℃, hydro-thermal 24 hours.Suction filtration then, 80 ℃ of dryings can get CdS.
2) with 0.15g(0.001mol) CdS joins in the 80ml high pressure water heating kettle, get successively again 5ml nickel acetate aqueous solution (5mmol/l), 0.2ml palladium chloride aqueous solution (Pd:0.00236g/ml), 1g thiocarbamide adding high pressure water heating kettle, then stirred 1 hour, ultrasonic 1 hour, then hydro-thermal is 2 hours, and hydrothermal temperature is 240 ℃.Suction filtration then, 80 ℃ of dry NiS-PdS/CdS.
Getting the NiS-PdS/CdS that makes is scattered in the 80mL 30vol% lactic acid, place photo catalysis reactor, with 300W xenon lamp radiation of visible light (utilizing the following light of sodium nitrite solution elimination 420nm), the gas-chromatography on-line quantitative analysis of the hydrogen that reaction generates with conductance cell, the hydrogen-producing speed of 0.15g NiS-PdS/CdS is 6240 μ molh
-1
Embodiment 5, (3.5wt%) NiS-(0.4wt%) hydro-thermal preparation and the catalysis thereof of PdS/CdS produces the hydrogen effect
1) 200ml 0.2M sodium sulfide solution is slowly added in the 250ml 0.2M cadmium acetate aqueous solution, stir and left standstill 24 hours after 24 hours, change sediment over to the high pressure water heating kettle and carry out hydro-thermal.Hydrothermal temperature is 200 ℃, hydro-thermal 24 hours.Suction filtration then, 80 ℃ of dryings can get CdS.
2) with 0.15g(0.001mol) CdS joins in the 80ml high pressure water heating kettle, get successively again 11.5ml nickel acetate aqueous solution (5mmol/l), 0.2ml palladium chloride aqueous solution (Pd:0.00236g/ml), 1g thiocarbamide adding water heating kettle, then stirred 1 hour, ultrasonic 1 hour, then hydro-thermal is 6 hours, and hydrothermal temperature is 140 ℃.Suction filtration then, 80 ℃ of dry NiS-PdS/CdS.
Getting the NiS-PdS/CdS that makes is scattered in the 80mL30vol% lactic acid, place photo catalysis reactor, with 300W xenon lamp radiation of visible light (utilizing the following light of sodium nitrite solution elimination 420nm), the gas-chromatography on-line quantitative analysis of the hydrogen that reaction generates with conductance cell, the hydrogen-producing speed of 0.15g NiS-PdS/CdS is 7510 μ molh
-1
Embodiment 6, (1wt%) NiS-(0.38wt%) Ru
2S
3The hydrogen effect is produced in sedimentation preparation and the catalysis thereof of/CdS
1) 200ml 0.2M sodium sulfide solution is slowly added in the 250ml 0.2M cadmium acetate aqueous solution, stir and left standstill 24 hours after 24 hours, change sediment over to the high pressure water heating kettle and carry out hydro-thermal.Hydrothermal temperature is 200 ℃, hydro-thermal 24 hours.Suction filtration then, 80 ℃ of dryings can get CdS.
2) with 0.15g(0.001mol) CdS that makes is put into 50ml sodium sulfide solution (5M), constantly stir, slowly add 0.8ml nickel sulfate solution (0.02M) and 0.2ml ruthenium chloride aqueous solution (Ru:1.9489mg/ml).Stirred 1 hour, then filtration, 80 ℃ of dryings can get NiS-Ru in 8 hours
2S
3/ CdS.
Get the NiS-Ru that makes
2S
3/ CdS is scattered in the 80mL30vol% lactic acid, place photo catalysis reactor, with 300W xenon lamp radiation of visible light (utilizing the following light of sodium nitrite solution elimination 420nm), the gas-chromatography on-line quantitative analysis of the hydrogen that reaction generates with conductance cell, 0.15g NiS-Ru
2S
3The hydrogen-producing speed of/CdS is 3850 μ molh
-1
Embodiment 7, (1.5wt%) NiS-(0.38wt%) Ru
2S
3The hydrogen effect is produced in hydro-thermal preparation and the catalysis thereof of/CdS
1) 200ml 0.2M sodium sulfide solution is slowly added in the 250ml 0.2M cadmium acetate aqueous solution, stir and left standstill 24 hours after 24 hours, change sediment over to the high pressure water heating kettle and carry out hydro-thermal.Hydrothermal temperature is 200 ℃, hydro-thermal 24 hours.Suction filtration then, 80 ℃ of dryings can get CdS.
2) with 0.15g(0.001mol) CdS joins in the 80ml high pressure water heating kettle, get successively again 5ml nickel acetate aqueous solution (5mmol/l), 0.2ml ruthenium chloride aqueous solution (Ru:1.9489mg/ml), 1g thiocarbamide adding water heating kettle, then stirred 1 hour, ultrasonic 1 hour, then hydro-thermal is 8 hours, and hydrothermal temperature is 105 ℃.Suction filtration then, 80 ℃ of dry NiS-Ru
2S
3/ CdS.
Get the NiS-Ru that makes
2S
3/ CdS is scattered in the 80mL 30vol% lactic acid, place photo catalysis reactor, with 300W xenon lamp radiation of visible light (utilizing the following light of sodium nitrite solution elimination 420nm), the gas-chromatography on-line quantitative analysis of the hydrogen that reaction generates with conductance cell, 0.15g NiS-Ru
2S
3The hydrogen-producing speed of/CdS is 4230 μ molh
-1
Embodiment 8, (3.5wt%) NiS-(0.38wt%) Ru
2S
3The hydrogen effect is produced in hydro-thermal preparation and the catalysis thereof of/CdS
1) 200ml 0.2M sodium sulfide solution is slowly added in the 250ml 0.2M cadmium acetate aqueous solution, stir and left standstill 24 hours after 24 hours, change sediment over to the high pressure water heating kettle and carry out hydro-thermal.Hydrothermal temperature is 200 ℃, hydro-thermal 24 hours.Suction filtration then, 80 ℃ of dryings can get CdS.
2) with 0.15g(0.001mol) CdS joins in the 80ml high pressure water heating kettle, get successively again 11.5ml nickel acetate aqueous solution (5mmol/l), 0.2ml ruthenium chloride aqueous solution (Ru:1.9489mg/ml), 1g thiocarbamide adding water heating kettle, then stirred 1 hour, ultrasonic 1 hour, then hydro-thermal is 4 hours, and hydrothermal temperature is 140 ℃.Suction filtration then, 80 ℃ of dry NiS-Ru
2S
3/ CdS.
Get the NiS-Ru that makes
2S
3/ CdS is scattered in the 80mL 30vol% lactic acid, place photo catalysis reactor, with 300W xenon lamp radiation of visible light (utilizing the following light of sodium nitrite solution elimination 420nm), the gas-chromatography on-line quantitative analysis of the hydrogen that reaction generates with conductance cell, 0.15g NiS-Ru
2S
3The hydrogen-producing speed of/CdS is 5130 μ molh
-1
Embodiment 9, (1wt%) NiS-(0.31wt%) Rh
2S
3The hydrogen effect is produced in sedimentation preparation and the catalysis thereof of/CdS
1) 200ml 0.2M sodium sulfide solution is slowly added in the 250ml 0.2M cadmium acetate aqueous solution, stir and left standstill 24 hours after 24 hours, change sediment over to the high pressure water heating kettle and carry out hydro-thermal.Hydrothermal temperature is 200 ℃, hydro-thermal 24 hours.Suction filtration then, 80 ℃ of dryings can get CdS.
2) with 0.15g(0.001mol) CdS that makes is put into 50ml sodium sulfide solution (5M), constantly stir, slowly add 0.8ml nickel sulfate solution (0.02M) and the 0.2ml radium chloride aqueous solution (Rh:0.0016g/ml).Stirred suction filtration then, 80 ℃ of dry NiS-Rh 1 hour
2S
3/ CdS.
Get the NiS-Rh that makes
2S
3/ CdS is scattered in the 80mL 30vol% lactic acid, place photo catalysis reactor, with 300W xenon lamp radiation of visible light (utilizing the following light of sodium nitrite solution elimination 420nm), the gas-chromatography on-line quantitative analysis of the hydrogen that reaction generates with conductance cell, 0.15g NiS-Rh
2S
3The hydrogen-producing speed of/CdS is 3280 μ molh
-1
Embodiment 10, (1.5wt%) NiS-(0.31wt%) Rh
2S
3The hydrogen effect is produced in hydro-thermal preparation and the catalysis thereof of/CdS
1) 200ml 0.2M sodium sulfide solution is slowly added in the 250ml 0.2M cadmium acetate aqueous solution, stir and left standstill 24 hours after 24 hours, change sediment over to the high pressure water heating kettle and carry out hydro-thermal.Hydrothermal temperature is 200 ℃, hydro-thermal 24 hours.Suction filtration then, 80 ℃ of dryings can get CdS.
2) with 0.15g(0.001mol) CdS joins in the 80ml high pressure water heating kettle, get successively again 5ml nickel acetate aqueous solution (5mmol/l), the 0.2ml radium chloride aqueous solution (Rh:0.0016g/ml), 1g thiocarbamide adding water heating kettle, then stirred 1 hour, ultrasonic 1 hour, then hydro-thermal is 4 hours, and hydrothermal temperature is 140 ℃.Suction filtration then, 80 ℃ of dry NiS-Rh
2S
3/ CdS.
Get the NiS-Rh that makes
2S
3/ CdS is scattered in the 80mL30vol% lactic acid, place photo catalysis reactor, with 300W xenon lamp radiation of visible light (utilizing the following light of sodium nitrite solution elimination 420nm), the gas-chromatography on-line quantitative analysis of the hydrogen that reaction generates with conductance cell, 0.15g NiS-Rh
2S
3The hydrogen-producing speed of/CdS is 4480 μ molh
-1
Embodiment 11, (3.5wt%) NiS-(0.31wt%) Rh
2S
3The hydrogen effect is produced in hydro-thermal preparation and the catalysis thereof of/CdS
1) 200ml 0.2M sodium sulfide solution is slowly added in the 250ml 0.2M cadmium acetate aqueous solution, stir and left standstill 24 hours after 24 hours, change sediment over to the high pressure water heating kettle and carry out hydro-thermal.Hydrothermal temperature is 200 ℃, hydro-thermal 24 hours.Suction filtration then, 80 ℃ of dryings can get CdS.
2) with 0.15g(0.001mol) CdS joins in the 80ml high pressure water heating kettle, get successively again 11.5ml nickel acetate aqueous solution (5mmol/l), the 0.2ml radium chloride aqueous solution (Rh:0.0016g/ml), 1g thiocarbamide adding water heating kettle, then stirred 1 hour, ultrasonic 1 hour, then hydro-thermal is 4 hours, and hydrothermal temperature is 140 ℃.Suction filtration then, 80 ℃ of dry NiS-Rh
2S
3/ CdS.
Get the NiS-Rh that makes
2S
3/ CdS is scattered in the 80mL 30vol% lactic acid, place photo catalysis reactor, with 300W xenon lamp radiation of visible light (utilizing the following light of sodium nitrite solution elimination 420nm), the gas-chromatography on-line quantitative analysis of the hydrogen that reaction generates with conductance cell, 0.15g NiS-Rh
2S
3The hydrogen-producing speed of/CdS is 5620 μ molh
-1
Embodiment 12, (1wt%) NiS-(0.16wt%) Ag
2The hydrogen effect is produced in sedimentation preparation and the catalysis thereof of S/CdS
1) 200ml 0.2M sodium sulfide solution is slowly added in the 250ml 0.2M cadmium acetate aqueous solution, stir and left standstill 24 hours after 24 hours, change sediment over to the high pressure water heating kettle and carry out hydro-thermal.Hydrothermal temperature is 200 ℃, hydro-thermal 24 hours.Suction filtration then, 80 ℃ of dryings can get CdS.
2) with 0.15g(0.001mol) CdS that makes is put into 50ml sodium sulfide solution (5M), constantly stir, slowly add 0.8ml nickel sulfate solution (0.02M) and 5ml silver nitrate aqueous solution (2mmol/l).Stirred suction filtration then, 80 ℃ of dry NiS-Ag 1 hour
2S/CdS.
Get the NiS-Ag that makes
2S/CdS is scattered in the 80mL30vol% lactic acid, place photo catalysis reactor, with 300W xenon lamp radiation of visible light (utilizing the following light of sodium nitrite solution elimination 420nm), the gas-chromatography on-line quantitative analysis of the hydrogen that reaction generates with conductance cell, the hydrogen-producing speed of 0.15g NiS-AgS/CdS is 2060 μ molh
-1
Embodiment 13, (1.5wt%) NiS-(0.16wt%) Ag
2The hydrogen effect is produced in hydro-thermal preparation and the catalysis thereof of S/CdS
1) 200ml 0.2M sodium sulfide solution is slowly added in the 250ml 0.2M cadmium acetate aqueous solution, stir and left standstill 24 hours after 24 hours, change sediment over to the high pressure water heating kettle and carry out hydro-thermal.Hydrothermal temperature is 200 ℃, hydro-thermal 24 hours.Suction filtration then, 80 ℃ of dryings can get CdS.
2) with 0.15g(0.001mol) CdS joins in the 80ml high pressure water heating kettle, get successively again 5ml nickel acetate aqueous solution (5mmol/l), 5ml silver nitrate aqueous solution (2mmol/l), 1g thiocarbamide adding water heating kettle, then stirred 1 hour, ultrasonic 1 hour, then hydro-thermal is 4 hours, and hydrothermal temperature is 140 ℃.Suction filtration then, 80 ℃ of dry NiS-Ag
2S/CdS.
Get the NiS-Ag that makes
2S/CdS is scattered in the 80mL 30vol% lactic acid, place photo catalysis reactor, with 300W xenon lamp radiation of visible light (utilizing the following light of sodium nitrite solution elimination 420nm), the gas-chromatography on-line quantitative analysis of the hydrogen that reaction generates with conductance cell, the hydrogen-producing speed of 0.15g NiS-AgS/CdS is 3560 μ molh
-1
Embodiment 14, (3.5wt%) NiS-(0.16wt%) Ag
2The hydrogen effect is produced in hydro-thermal preparation and the catalysis thereof of S/CdS
1) 200ml 0.2M sodium sulfide solution is slowly added in the 250ml 0.2M cadmium acetate aqueous solution, stir and left standstill 24 hours after 24 hours, change sediment over to the high pressure water heating kettle and carry out hydro-thermal.Hydrothermal temperature is 200 ℃, hydro-thermal 24 hours.Suction filtration then, 80 ℃ of dryings can get CdS.
2) with 0.15g(0.001mol) CdS joins in the 80ml high pressure water heating kettle, get successively again 11.5ml nickel acetate aqueous solution (5mmol/l), 5ml silver nitrate aqueous solution (2mmol/l), 1g thiocarbamide adding water heating kettle, then stirred 1 hour, ultrasonic 1 hour, then hydro-thermal is 4 hours, and hydrothermal temperature is 140 ℃.Suction filtration then, 80 ℃ of dry NiS-AgS/CdS.
3) getting the NiS-AgS/CdS that makes is scattered in the 80mL 30vol% lactic acid, place photo catalysis reactor, with 300W xenon lamp radiation of visible light (utilizing the following light of sodium nitrite solution elimination 420nm), the gas-chromatography on-line quantitative analysis of the hydrogen that reaction generates with conductance cell, the hydrogen-producing speed of 0.15g NiS-AgS/CdS is 4100 μ molh
-1
Embodiment 15, (1.5wt%) NiS-(0.4wt%) hydro-thermal preparation and the catalysis thereof of PdS/CdS produces the hydrogen effect
1) 200ml 0.2M sodium sulfide solution is slowly added in the 250ml 0.2M cadmium sulfate aqueous solution, stir and left standstill 24 hours after 24 hours, change sediment over to the high pressure water heating kettle and carry out hydro-thermal.Hydrothermal temperature is 200 ℃, hydro-thermal 24 hours.Suction filtration then, 80 ℃ of dryings can get CdS.
2) with 0.15g(0.001mol) CdS joins in the 80ml high pressure water heating kettle, get successively again 5ml nickel acetate aqueous solution (5mmol/l), 0.2ml palladium chloride aqueous solution (Pd:0.00236g/ml), 1g thiocarbamide adding water heating kettle, then stirred 1 hour, ultrasonic 1 hour, then hydro-thermal is 4 hours, and hydrothermal temperature is 140 ℃.Suction filtration then, 80 ℃ of dry NiS-PdS/CdS.
Getting the NiS-PdS/CdS that makes is scattered in the 80mL 30vol% lactic acid, place photo catalysis reactor, with 300W xenon lamp radiation of visible light (utilizing the following light of sodium nitrite solution elimination 420nm), the gas-chromatography on-line quantitative analysis of the hydrogen that reaction generates with conductance cell, the hydrogen-producing speed of 0.15g NiS-PdS/CdS is 5040 μ molh
-1
Embodiment 16, (1.5wt%) NiS-(0.4wt%) hydro-thermal preparation and the catalysis thereof of PdS/CdS produces the hydrogen effect
1) 200ml 0.2M sodium sulfide solution is slowly added in the 250ml 0.2M caddy aqueous solution, stir and left standstill 24 hours after 24 hours, change sediment over to the high pressure water heating kettle and carry out hydro-thermal.Hydrothermal temperature is 200 ℃, hydro-thermal 24 hours.Suction filtration then, 80 ℃ of dryings can get CdS.
2) with 0.15g(0.001mol) CdS joins in the 80ml high pressure water heating kettle, get successively again 5ml nickel acetate aqueous solution (5mmol/l), 0.2ml palladium chloride aqueous solution (Pd:0.00236g/ml), 1g thiocarbamide adding water heating kettle, then stirred 1 hour, ultrasonic 1 hour, then hydro-thermal is 4 hours, and hydrothermal temperature is 140 ℃.Suction filtration then, 80 ℃ of dry NiS-PdS/CdS.
Getting the NiS-PdS/CdS that makes is scattered in the 80mL 30vol% lactic acid, place photo catalysis reactor, with 300W xenon lamp radiation of visible light (utilizing the following light of sodium nitrite solution elimination 420nm), the gas-chromatography on-line quantitative analysis of the hydrogen that reaction generates with conductance cell, the hydrogen-producing speed of 0.15g NiS-PdS/CdS is 4500 μ molh
-1
Embodiment 17, (1.5wt%) NiS-(0.4wt%) hydro-thermal preparation and the catalysis thereof of PdS/CdS produces the hydrogen effect
1) 200ml 0.2M sodium sulfide solution is slowly added in the 250ml 0.2M cadmium nitrate aqueous solution, stir and left standstill 24 hours after 24 hours, change sediment over to the high pressure water heating kettle and carry out hydro-thermal.Hydrothermal temperature is 200 ℃, hydro-thermal 24 hours.Suction filtration then, 80 ℃ of dryings can get CdS.
2) with 0.15g(0.001mol) CdS joins in the 80ml high pressure water heating kettle, get successively again 5ml nickel acetate aqueous solution (5mmol/l), 0.2ml palladium chloride aqueous solution (Pd:0.00236g/ml), 1g thiocarbamide adding water heating kettle, then stirred 1 hour, ultrasonic 1 hour, then hydro-thermal is 4 hours, and hydrothermal temperature is 140 ℃.Suction filtration then, 80 ℃ of dry NiS-PdS/CdS.
Getting the NiS-PdS/CdS that makes is scattered in the 80mL 30vol% lactic acid, place photo catalysis reactor, with 300W xenon lamp radiation of visible light (utilizing the following light of sodium nitrite solution elimination 420nm), the gas-chromatography on-line quantitative analysis of the hydrogen that reaction generates with conductance cell, the hydrogen-producing speed of 0.15g NiS-PdS/CdS is 4080 μ molh
-1
Claims (10)
1. the photolysis water hydrogen catalyst of a responding to visible light is characterized in that: described catalyst is comprised of CdS and the auxiliary agent that loads on the CdS;
Described auxiliary agent is NiS and PdS, Ru
2S
3, Rh
2S
3And Ag
2Any mixture among the S.
2. photolysis water hydrogen catalyst according to claim 1, it is characterized in that: in the described catalyst, the quality percentage composition of described NiS is 0.22 ~ 5.5%, described PdS, Ru
2S
3, Rh
2S
3And Ag
2Any quality percentage composition is 0.1 ~ 3.0% among the S.
3. the preparation method of claim 1 or 2 described photolysis water hydrogen catalyst, comprise the steps: described CdS is added in the aqueous solution that contains the S compound, under the condition that stirs, continue to add again the compound that contains the Ni compound and contain among Pd, Ru, Rh and the Ag any, namely get described photolysis water hydrogen catalyst through stirring.
4. preparation method according to claim 3 is characterized in that: after adding the described Ni of containing compound and containing among Pd, Ru, Rh and the Ag any compound, namely got described catalyst in 1 ~ 2 hour through stirring.
5. the preparation method of claim 1 or 2 described photolysis water hydrogen catalyst, comprise the steps: described CdS, contain the S compound, contain the Ni compound, contain Pd, any compound and water are added in the autoclave among Ru, Rh and the Ag, then namely get described photolysis water hydrogen catalyst through hydro-thermal reaction.
6. preparation method according to claim 5, it is characterized in that: the temperature of described hydro-thermal reaction is 105 ~ 240 ℃, the time is 2 ~ 8 hours.
7. each described preparation method according to claim 3-6 is characterized in that: described method also comprises the steps that described photolysis water hydrogen catalyst placed 80 ~ 95 ℃ of lower dryings.
8. each described preparation method according to claim 3-7 is characterized in that: the described S of containing compound be in vulcanized sodium and the thiocarbamide any; The described Ni of containing compound be in nickel nitrate, nickel acetate, nickel chloride and the nickelous sulfate any; The described Pd of containing compound is palladium bichloride, and the described Ru of containing compound is ruthenic chloride, and the described Rh of containing compound is radium chloride, and the described Ag of containing compound is silver nitrate.
9. each described preparation method according to claim 3-8 is characterized in that: described CdS is according to the preparation of the method that comprises the steps: will contain and carry out hydro-thermal reaction after Cd compound and the described S of the containing compound and namely get described CdS.
10. preparation method according to claim 9 is characterized in that: the described Cd of containing compound be in cadmium nitrate, cadmium acetate, caddy and the cadmium sulfate any;
The temperature of described hydro-thermal reaction is 140 ~ 210 ℃, and the time is 24 ~ 48 hours.
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