CN103934006B - A kind of preparation method of nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst - Google Patents
A kind of preparation method of nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst Download PDFInfo
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Abstract
A preparation method for nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst, described composite photo-catalyst chemical formulation is CdIn
2s
4-In (OH)
3, utilize inidum chloride, caddy and thiocarbamide and deionization to adopt hydro-thermal method preparation, the XRD diffraction maximum of this catalyst along with the prolongation of hydro-thermal time, the In (OH) of sample
3diffraction maximum weakens gradually, and CdIn
2s
4diffraction maximum strengthen gradually, define CdIn
2s
4-In (OH)
3composite photo-catalyst, other impurity peaks are not found in spectrogram, advantage of the present invention is: this preparation method's technique is simple, easy and simple to handle, and obtained composite photo-catalyst has very high photocatalytic activity, for taking methyl alcohol as solvent catalytic reduction CO under UV-irradiation
2for methyl formate, can effectively by CO
2be reduced to organic ester, realize green conversion.
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, utilize photoelectric effect to be 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, preparing the sulfide semiconductor nano material of different performance, and it can be used as photochemical catalyst, take methyl alcohol as solvent reduction CO
2, convert it into there is high added value organic products as HCOOH, HCHO, CH
3oH, CH
4deng material, both eliminate CO like this
2on the impact of environment, convert it into industrial chemicals again simultaneously, be both conducive to human environment protection, and alleviated energy crisis again.So the photochemical catalyst finding high catalytic activity and high selectivity becomes the problem that people in the last few years endeavour solution.
The catalytic efficiency of the various photochemical catalysts of current development is lower, the light absorption wavelength narrow range (mainly at ultraviolet region) of semiconductor and balance low conversion rate and the problem such as two or more catalyst cupport rate caused due to topography issues is low, in addition, single semiconductor is difficult to the band gap width simultaneously met required for catalytic reaction, 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
4with In (OH)
3based on 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, obtained composite photo-catalyst has very high photocatalytic activity, for taking methyl alcohol as solvent catalytic reduction CO under UV-irradiation
2for methyl formate, can effectively by CO
2reduction.
Technical scheme of the present invention:
A preparation method for nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst, adopt hydro-thermal method preparation, step is as follows:
1) inidum chloride, caddy and thiocarbamide to be 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 baking oven thermostatic crystallization at 140 DEG C, time 16h, 32h, 48h respectively of thermostatic crystallization;
3) after isothermal reaction terminates, take out water heating kettle, discard supernatant after cooling to room temperature;
4) collect the sediment in still, use absolute ethyl alcohol and deionized water centrifuge washing 2-3 time respectively, 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 powder, nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst can be obtained.
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 catalytic reduction CO under UV-irradiation
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 accompanying quartz plate, and quartz plate makes not lose ultraviolet ray intensity in During Illumination, and steel flange makes light-catalyzed reaction be in enclosed environment; Above reactor, 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 CO is passed into
2, closed vent mouth, opens ultraviolet light and reacts; Product uses gas chromatograph-mass spectrometer GC-MS(Agilent 5975C after centrifugation) qualitative analysis, with gas chromatograph GC(Agilent 7890) hydrogen flame detector quantitative analysis, draw product formic acid methyl esters productive rate after calculating.
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 obtained by inidum chloride, caddy and sulphur source reagent and deionized water, different solvents has a lot of difference due to character such as boiling point, polarity, dielectric constant, dissolubility and viscosity, so by hydro-thermal method and solvent-thermal method, the sulfide semiconductor nano material of many different performances can be prepared.Adopt hydro-thermal method preparation can obtain the CdIn of pattern rule
2s
4-In (OH)
3microballoon, and the performances such as its specific area, light absorpting ability, photocatalytic activity all improve to some extent.Experimental result shows that the best hydro-thermal time is 32h.Under best hydrothermal condition, no matter this composite catalyst is have extremely strong light absorpting ability in UV 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 obtained composite photo-catalyst has very high photocatalytic activity, for taking methyl alcohol as solvent catalytic reduction CO under UV-irradiation
2for methyl formate, can effectively by CO
2be reduced to organic ester, realize green conversion.
Accompanying drawing explanation
Fig. 1 is the SEM figure of nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst, and wherein: (a) hydro-thermal time is 16h, (b) hydro-thermal time is 32h, and (c) 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, and wherein: (a) is indium sulfide cadmium photochemical catalyst, (b) is 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, adopt hydro-thermal method preparation, step is as follows:
1) 0.35g inidum chloride, 0.14g caddy and 0.35g thiocarbamide to be 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 baking oven thermostatic crystallization at 140 DEG C, time 16h, 32h, 48h respectively of thermostatic crystallization;
3) after isothermal reaction terminates, take out water heating kettle, discard supernatant after cooling to room temperature;
4) collect the sediment in still, use absolute ethyl alcohol and deionized water centrifuge washing 3 times respectively, 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 powder, nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst can be obtained.
Fig. 1 is the SEM figure of nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst, and wherein: (a) hydro-thermal time is 16h, (b) hydro-thermal time is 32h, and (c) hydro-thermal time is 48h.As can be seen from the figure: what sample topography when the hydro-thermal time is 16h major part was little cubic crystal and minority is irregular spherical; Cubic crystal polymerization little after the hydro-thermal time is increased to 32h defines spherical, can observe and not be polymerized completely " semi-finished product " in the SEM figure of 32 hours; The hydro-thermal time, its appearance structure had almost no change more than after 32h, was all particle diameter at about 4 μm 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 spectrogram of the sample of hydro-thermal time prepared by 16h hour, Emission in Cubic In (OH) in figure
3diffraction maximum very strong, and CdIn
2s
4diffraction maximum more weak; Along with the prolongation of hydro-thermal time, the In (OH) of sample
3diffraction maximum weakens gradually, and CdIn
2s
4diffraction maximum strengthen gradually, define CdIn
2s
4-In (OH)
3composite photo-catalyst, does not find 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, and wherein: (a) is indium sulfide cadmium photochemical catalyst, (b) is nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst.Show in figure: be respectively 737nm, 592nm and 605nm with the optical absorption edge corresponding to indium sulfide cadmium photochemical catalyst synthesized by sulphur source of L-cysteine, thioacetamide, thiocarbamide, calculate and obtain their corresponding band gap magnitude and be respectively 1.68eV, 2.09eV and 2.05eV; No matter and nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst has extremely strong absorbability for visible ray or ultraviolet light, its optical absorption edge is 760nm, and CdIn is compared on the band gap limit of compound
2s
4obviously there is Red Shift Phenomena, so this composite can as a kind of visible light catalyst of novel wide spectral response.
Being used for by prepared nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst take methyl alcohol as solvent catalytic reduction CO under UV-irradiation
2for methyl formate.The Activity determination closing photochemical catalyst is as follows:
Close the activity of photochemical catalyst by photocatalysis under UV-irradiation by CO
2the reaction rate being 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 accompanying quartz plate, and quartz plate makes not lose ultraviolet ray intensity in During Illumination, and steel flange makes light-catalyzed reaction be in enclosed environment.Above reactor, 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.For 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 CO is passed into
2after, closed vent mouth.Open ultraviolet light, react.Product uses gas chromatograph-mass spectrometer GC-MS(Agilent 5975C after centrifugation) qualitative analysis, with gas chromatograph GC(Agilent 7890) hydrogen flame detector quantitative analysis, draw product formic acid methyl esters productive rate after calculating.
Fig. 4 is the photocatalytic activity comparison diagram of nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst, show in figure: in four groups of light-catalyzed reactions, MF productive rate is all higher, catalytic activity first increases rear reduction with the hydro-thermal time, and the sample after compound shows the photo catalytic reduction CO higher than independent sample
2activity, when the hydro-thermal time is 32h, prepared material catalyzes activity is maximum, 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, this promotes photocatalytic activity.
Claims (2)
1. a preparation method for nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst, adopt hydro-thermal method preparation, step is as follows:
1) inidum chloride, caddy and thiocarbamide to be 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 baking oven thermostatic crystallization at 140 DEG C, time 16h, 32h, 48h respectively of thermostatic crystallization;
3) after isothermal reaction terminates, take out water heating kettle, discard supernatant after cooling to room temperature;
4) collect the sediment in still, use absolute ethyl alcohol and deionized water centrifuge washing 2-3 time respectively, 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 powder, nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst can be obtained;
It is characterized in that: the amount ratio of described inidum chloride, caddy, thiocarbamide and deionized water is 0.35g:0.14g:0.35g:55mL.
2. an application for the nanometer indium sulfide cadmium-indium hydroxide composite photo-catalyst prepared by claim 1, is characterized in that: for taking methyl alcohol as solvent catalytic reduction CO under UV-irradiation
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 accompanying quartz plate, and quartz plate makes not lose ultraviolet ray intensity in During Illumination, and steel flange makes light-catalyzed reaction be in enclosed environment; Above reactor, 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 CO is passed into
2, closed vent mouth, opens ultraviolet light and reacts; Product with gas chromatograph-mass spectrometer GC-MS qualitative analysis, with the quantitative analysis of gas chromatograph GC hydrogen flame detector, draws product formic acid methyl esters productive rate after centrifugation after calculating.
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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 by inorganic semiconductor photocatalytic 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 |
| CN111871376B (en) * | 2020-06-15 | 2022-09-13 | 南昌大学 | Preparation and application of covalent organic framework porous nano composite material |
| 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 |
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 |
-
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| 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 |
|---|
| "Preparation of CdIn2S4 microspheres and application for photocatalytic reduction of carbon dioxide";Wanlin Jiang et al;《Applied Surface Science》;20131009;第288卷;第2.1节、2.3节 * |
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