CN103934006A - Method for preparing nanometer indium cadmium sulfide-indium hydroxide composite photocatalyst - Google Patents
Method for preparing nanometer indium cadmium sulfide-indium hydroxide composite photocatalyst Download PDFInfo
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Abstract
The invention relates to a method for preparing a nanometer indium cadmium sulfide-indium hydroxide composite photocatalyst. The chemical formula of the composite photocatalyst is CdIn2S4-In(OH)3. The catalyst is prepared from indium chloride, cadmium chloride, thiourea and deionized water by a hydrothermal method. According to the XRD (X-Ray Diffraction) spectrogram of the catalyst, along with the prolonging of hydrothermal time, the diffraction peak of In(OH)3 of a sample is gradually weakened and the diffraction peak of CdIn2S4 is gradually enhanced to form the CdIn2S4-In(OH)3 composite photocatalyst; no other impurity peak is found in the spectrogram. The method disclosed by the invention has the advantages that the method is simple in process and simple and convenient in operation; the obtained composite photocatalyst has very high photocatalytic activity and is used for performing catalytic reduction on CO2 to obtain methyl formate under the irradiation of ultraviolet light by taking methanol as a solvent, CO2 can be effectively reduced into organic ester and the green conversion is realized.
Description
Technical field
The present invention relates to the technology of preparing of composite photo-catalyst, particularly a kind of preparation method of nanometer indium sulfide cadmium-indium hydroxide composite catalyst.
Background technology
Photo catalytic reduction CO
2be photochemical catalyst under the irradiation of light, utilizing photoelectric effect is electric energy light energy conversion, it has more advantage compared with additive method.This reaction not only just can be carried out at normal temperatures and pressures, and utilizes clean energy resource sunshine can not produce unnecessary CO in the process of reaction
2.By easy hydro-thermal method and solvent method, prepare the sulfide semiconductor nano material of different performance, and set it as photochemical catalyst, the reduction CO taking methyl alcohol as solvent
2, convert it into the organic products with high added value as HCOOH, HCHO, CH
3oH, CH
4deng material, so both eliminated CO
2on the impact of environment, convert it into again industrial chemicals simultaneously, be both conducive to human environment protection, alleviate again energy crisis.So the photochemical catalyst of finding high catalytic activity and high selectivity becomes people in the last few years and endeavours the problem solving.
The catalytic efficiency of the various photochemical catalysts of development is lower at present, the problems such as semi-conductive light absorption wavelength narrow range (mainly at ultraviolet region) and balance low conversion rate and two or more catalyst cupport rate causing due to pattern problem are low, in addition, single semiconductor is difficult to meet the needed band gap width of catalytic reaction simultaneously, the inhibitory action of the position of valence band and conduction band and electronics and hole-recombination, so, the novel nano catalysis material that development of new has high activity and wide spectral response (comprising ultraviolet and visible ray) is main research direction.
The present invention is with CdIn
2s
4and In (OH)
3as base catalyst, develop one-step method and make the nanometer CdIn with coupling light catalytic activity
2s
4-In (OH)
3, improve photocatalytic activity, obtain higher methyl formate yield.
Summary of the invention
The object of the invention is for above-mentioned existing problem, a kind of preparation method of nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst is provided, this preparation method is simple, easy and simple to handle, prepared composite photo-catalyst has very high photocatalytic activity, for taking methyl alcohol as solvent under UV-irradiation catalytic reduction CO
2for methyl formate, can be effectively by CO
2reduction.
Technical scheme of the present invention:
A preparation method for nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst, adopts hydro-thermal method preparation, and step is as follows:
1) inidum chloride, caddy and thiocarbamide are added in deionized water and strong agitation 15 minutes, obtain mixed solution;
2) above-mentioned mixed solution is moved in water heating kettle, then water heating kettle is placed in to baking oven thermostatic crystallization at 140 DEG C, the time of thermostatic crystallization is 16h, 32h, 48h respectively;
3) after isothermal reaction finishes, take out water heating kettle, after room temperature, discard supernatant being cooled to;
4) collect the sediment in still, use respectively absolute ethyl alcohol and deionized water centrifuge washing 2-3 time, to remove the impurity in sediment;
5) by the constant temperature drying 6 hours at 80 DEG C of the sediment after washing;
6) sediment of oven dry is ground to form to powdery thing, can make nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst.
The amount ratio of described inidum chloride, caddy, thiocarbamide and deionized water is 0.35g:0.14g:0.35g:55mL.
An application for prepared nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst, for taking methyl alcohol as solvent under UV-irradiation catalytic reduction CO
2for methyl formate, method is as follows:
Utilize quartz reactor as photo catalytic reduction CO
2reactor, there is passage reactor both sides, are convenient to pass into reaction gas CO
2, reactor body is the steel flange that accompanies quartz plate, and quartz plate makes not lose ultraviolet ray intensity in During Illumination, and steel flange makes light-catalyzed reaction in enclosed environment; Reactor top high-pressure sodium lamp is as light source, and the dominant wavelength of light source is 365nm, and intensity of illumination is 5100 μ W/cm
2; First get a certain amount of composite photo-catalyst and chromatogram methyl alcohol in reactor, use magnetic stirrer suspension simultaneously; Then pass into CO
2, closed vent mouth, opens ultraviolet light and reacts; Product is used gas chromatograph-mass spectrometer GC-MS(Agilent 5975C after centrifugation) qualitative analysis, with gas chromatograph GC(Agilent 7890) hydrogen flame detector quantitative analysis, after calculating, draw product formic acid methyl esters productive rate.
Analysis on Mechanism of the present invention:
The chemical formulation of described indium sulfide cadmium-indium hydroxide composite photo-catalyst is CdIn
2s
4-In (OH)
3it is made by inidum chloride, caddy and sulphur source reagent and deionized water, different solvents is because the character such as boiling point, polarity, dielectric constant, dissolubility and viscosity have a lot of differences, so by hydro-thermal method and solvent-thermal method, can prepare the sulfide semiconductor nano material of many different performances.Adopt hydro-thermal method preparation can obtain the CdIn of pattern rule
2s
4-In (OH)
3microballoon, and the performance such as its specific area, light absorpting ability, photocatalytic activity all improves to some extent.Experimental result shows that the best hydro-thermal time is 32h.Under best hydrothermal condition, no matter this composite catalyst is to have extremely strong light absorpting ability in ultraviolet light region or in visible region.
Advantage of the present invention is: this preparation method's technique is simple, easy and simple to handle, and prepared composite photo-catalyst has very high photocatalytic activity, for taking methyl alcohol as solvent under UV-irradiation catalytic reduction CO
2for methyl formate, can be effectively by CO
2be reduced to organic ester, realize green conversion.
Brief description of the drawings
Fig. 1 is the SEM figure of nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst, and wherein: (a) the hydro-thermal time is 16h, (b) the hydro-thermal time is 32h, and (c) the hydro-thermal time is 48h.
Fig. 2 is the XRD figure of nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst.
Fig. 3 is the ultraviolet-visible absorption spectroscopy figure of indium sulfide cadmium and nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst, wherein: (a) being indium sulfide cadmium photochemical catalyst, is (b) nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst.
Fig. 4 is the photocatalytic activity comparison diagram of nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst.
Detailed description of the invention
Embodiment:
A preparation method for nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst, adopts hydro-thermal method preparation, and step is as follows:
1) 0.35g inidum chloride, 0.14g caddy and 0.35g thiocarbamide are added in 55mL deionized water and strong agitation 15 minutes, obtain mixed solution;
2) above-mentioned mixed solution is moved in water heating kettle, then water heating kettle is placed in to baking oven thermostatic crystallization at 140 DEG C, the time of thermostatic crystallization is 16h, 32h, 48h respectively;
3) after isothermal reaction finishes, take out water heating kettle, after room temperature, discard supernatant being cooled to;
4) collect the sediment in still, use respectively absolute ethyl alcohol and deionized water centrifuge washing 3 times, to remove the impurity in sediment;
5) by the constant temperature drying 6 hours at 80 DEG C of the sediment after washing;
6) sediment of oven dry is ground to form to powdery thing, can make nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst.
Fig. 1 is the SEM figure of nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst, and wherein: (a) the hydro-thermal time is 16h, (b) the hydro-thermal time is 32h, and (c) the hydro-thermal time is 48h.As can be seen from the figure: what the sample topography major part in the time that the hydro-thermal time is 16h was little cubic crystal and minority is irregular spherical; After the hydro-thermal time is increased to 32h, little cubic crystal polymerization has formed spherically, can observe not polymerization " semi-finished product " completely in the SEM figure of 32 hours; After the hydro-thermal time exceedes 32h, its appearance structure does not almost change, and is all particle diameter at 4 μ m left and right microballoons, can find cubic crystal polymerization vestige clearly from the surface of microballoon.
Fig. 2 is the XRD figure of nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst, shows: the hydro-thermal time is the spectrogram of 16h hour prepared sample Emission in Cubic In (OH) in figure
3diffraction maximum very strong, and CdIn
2s
4diffraction maximum a little less than; Along with the prolongation of hydro-thermal time, the In of sample (OH)
3diffraction maximum weakens gradually, and CdIn
2s
4diffraction maximum strengthen gradually, formed CdIn
2s
4-In (OH)
3composite photo-catalyst is not found other impurity peaks in spectrogram.
Fig. 3 is the ultraviolet-visible absorption spectroscopy figure of indium sulfide cadmium and nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst, wherein: (a) being indium sulfide cadmium photochemical catalyst, is (b) nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst.In figure, show: taking L-cysteine, thioacetamide, thiocarbamide as the corresponding optical absorption edge of indium sulfide cadmium photochemical catalyst of sulphur source synthesized is respectively 737nm, 592nm and 605nm, calculate their corresponding band gap magnitude of acquisition and be respectively 1.68eV, 2.09eV and 2.05eV; No matter and nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst is for visible ray or ultraviolet light has extremely strong absorbability, its optical absorption edge is 760nm, CdIn is compared on the band gap limit of compound
2s
4this composite obviously there is Red Shift Phenomena, so can be used as a kind of visible light catalyst of new molded breadth spectral response.
By prepared nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst for taking methyl alcohol as solvent under UV-irradiation catalytic reduction CO
2for methyl formate.The activity of closing photochemical catalyst detects as follows:
The activity of closing photochemical catalyst by photocatalysis under UV-irradiation by CO
2the reaction rate that is reduced to methyl formate is evaluated.Utilize quartz reactor as photo catalytic reduction CO
2reactor, there is passage reactor both sides, are convenient to pass into reaction gas CO
2, reactor body is the steel flange that accompanies quartz plate, and quartz plate makes not lose ultraviolet ray intensity in During Illumination, and steel flange makes light-catalyzed reaction in enclosed environment.Reactor top high-pressure sodium lamp is as light source, and the dominant wavelength of light source is 365nm, and intensity of illumination is 5100 μ W/cm
2.In evaluation response process, first get a certain amount of composite photo-catalyst and chromatogram methyl alcohol in reactor, use magnetic stirrer suspension simultaneously.Then pass into CO
2after, closed vent mouth.Open ultraviolet light, react.Product is used gas chromatograph-mass spectrometer GC-MS(Agilent 5975C after centrifugation) qualitative analysis, with gas chromatograph GC(Agilent 7890) hydrogen flame detector quantitative analysis, after calculating, draw product formic acid methyl esters productive rate.
Fig. 4 is the photocatalytic activity comparison diagram of nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst, in figure, show: in four groups of light-catalyzed reactions, MF productive rate is all higher, catalytic activity first increased afterwards and reduces with the hydro-thermal time, and the sample after compound shows higher than the photo catalytic reduction CO of sample separately
2activity, prepared material catalytic activity maximum in the time that the hydro-thermal time is 32h, up to 12278mmol/h/gcat.ABSORPTION EDGE is than simple sample red shift, and red-shift of absorption edge makes photochemical catalyst absorb wave-length coverage widely, and absorption peak strength strengthens makes photochemical catalyst more effectively utilize luminous energy, and this has just promoted photocatalytic activity.
Claims (3)
1. a preparation method for nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst, is characterized in that: adopt hydro-thermal method preparation, step is as follows:
1) inidum chloride, caddy and thiocarbamide are added in deionized water and strong agitation 15 minutes, obtain mixed solution;
2) above-mentioned mixed solution is moved in water heating kettle, then water heating kettle is placed in to baking oven thermostatic crystallization at 140 DEG C, the time of thermostatic crystallization is 16h, 32h, 48h respectively;
3) after isothermal reaction finishes, take out water heating kettle, after room temperature, discard supernatant being cooled to;
4) collect the sediment in still, use respectively absolute ethyl alcohol and deionized water centrifuge washing 2-3 time, to remove the impurity in sediment;
5) by the constant temperature drying 6 hours at 80 DEG C of the sediment after washing;
6) sediment of oven dry is ground to form to powdery thing, can make nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst.
2. the preparation method of nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst according to claim 1, the amount ratio that it is characterized in that described inidum chloride, caddy, thiocarbamide and deionized water is 0.35g:0.14g:0.35g:55mL.
3. an application for nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst as prepared in claim 1, is characterized in that: for taking methyl alcohol as solvent under UV-irradiation catalytic reduction CO
2for methyl formate, method is as follows: utilize quartz reactor as photo catalytic reduction CO
2reactor, there is passage reactor both sides, are convenient to pass into reaction gas CO
2, reactor body is the steel flange that accompanies quartz plate, and quartz plate makes not lose ultraviolet ray intensity in During Illumination, and steel flange makes light-catalyzed reaction in enclosed environment; Reactor top high-pressure sodium lamp is as light source, and the dominant wavelength of light source is 365nm, and intensity of illumination is 5100 μ W/cm
2; First get a certain amount of composite photo-catalyst and chromatogram methyl alcohol in reactor, use magnetic stirrer suspension simultaneously; Then pass into CO
2, closed vent mouth, opens ultraviolet light and reacts; Product is used gas chromatograph-mass spectrometer GC-MS(Agilent 5975C after centrifugation) qualitative analysis, with gas chromatograph GC(Agilent 7890) hydrogen flame detector quantitative analysis, after calculating, draw product formic acid methyl esters productive rate.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694864A (en) * | 2016-04-01 | 2016-06-22 | 苏州大学 | Manganese-doped metal sulfide red fluorescent powder and preparation method thereof |
| CN105983420A (en) * | 2015-02-16 | 2016-10-05 | 中国科学院理化技术研究所 | Method for reducing carbon dioxide through inorganic semiconductor photocatalysis system |
| CN107744814A (en) * | 2017-10-20 | 2018-03-02 | 福州大学 | A kind of preparation method and application of composite photo-catalyst |
| CN111871376A (en) * | 2020-06-15 | 2020-11-03 | 南昌大学 | Preparation and application of covalent organic framework porous nano composite material |
| CN115318308A (en) * | 2022-09-01 | 2022-11-11 | 闽南师范大学 | Simple and convenient solvent thermal method for preparing In (OH) 3 /CdIn 2 S 4 Composite catalyst |
| CN115400771A (en) * | 2022-09-01 | 2022-11-29 | 闽南师范大学 | Ni prepared by one-step solvothermal method 12 P 5 /In(OH) 3 /CdIn 2 S 4 Ternary composite catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927173A (en) * | 2010-02-01 | 2010-12-29 | 黑龙江省科学院石油化学研究院 | Photocatalyst for preparing hydrogen and sulphur by decomposing hydrogen sulfide and preparation method thereof |
| CN102101055A (en) * | 2011-01-31 | 2011-06-22 | 黑龙江省科学院石油化学研究院 | Method for preparing transition metal ion-doped porous CdIn2S4 photocatalyst |
| JP2013211498A (en) * | 2012-03-30 | 2013-10-10 | Honda Motor Co Ltd | Chalcopyrite solar cell and manufacturing method of the same |
-
2014
- 2014-05-07 CN CN201410189625.7A patent/CN103934006B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927173A (en) * | 2010-02-01 | 2010-12-29 | 黑龙江省科学院石油化学研究院 | Photocatalyst for preparing hydrogen and sulphur by decomposing hydrogen sulfide and preparation method thereof |
| CN102101055A (en) * | 2011-01-31 | 2011-06-22 | 黑龙江省科学院石油化学研究院 | Method for preparing transition metal ion-doped porous CdIn2S4 photocatalyst |
| JP2013211498A (en) * | 2012-03-30 | 2013-10-10 | Honda Motor Co Ltd | Chalcopyrite solar cell and manufacturing method of the same |
Non-Patent Citations (1)
| Title |
|---|
| WANLIN JIANG ET AL: ""Preparation of CdIn2S4 microspheres and application for photocatalytic reduction of carbon dioxide"", 《APPLIED SURFACE SCIENCE》, vol. 288, 9 October 2013 (2013-10-09) * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105983420A (en) * | 2015-02-16 | 2016-10-05 | 中国科学院理化技术研究所 | Method for reducing carbon dioxide through inorganic semiconductor photocatalysis system |
| CN105694864A (en) * | 2016-04-01 | 2016-06-22 | 苏州大学 | Manganese-doped metal sulfide red fluorescent powder and preparation method thereof |
| CN107744814A (en) * | 2017-10-20 | 2018-03-02 | 福州大学 | A kind of preparation method and application of composite photo-catalyst |
| CN111871376A (en) * | 2020-06-15 | 2020-11-03 | 南昌大学 | Preparation and application of covalent organic framework porous nano composite material |
| CN115318308A (en) * | 2022-09-01 | 2022-11-11 | 闽南师范大学 | Simple and convenient solvent thermal method for preparing In (OH) 3 /CdIn 2 S 4 Composite catalyst |
| CN115400771A (en) * | 2022-09-01 | 2022-11-29 | 闽南师范大学 | Ni prepared by one-step solvothermal method 12 P 5 /In(OH) 3 /CdIn 2 S 4 Ternary composite catalyst |
| CN115400771B (en) * | 2022-09-01 | 2023-11-17 | 闽南师范大学 | Ni prepared by one-step solvothermal method 12 P 5 /In(OH) 3 /CdIn 2 S 4 Ternary composite catalyst |
| CN115318308B (en) * | 2022-09-01 | 2023-11-24 | 闽南师范大学 | Simple solvothermal method for preparing In (OH) 3 /CdIn 2 S 4 Composite catalyst |
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