CN103464172A - Compound photocatalyst for reducing carbon dioxide into organic ester and preparation method of compound photocatalyst - Google Patents

Compound photocatalyst for reducing carbon dioxide into organic ester and preparation method of compound photocatalyst Download PDF

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CN103464172A
CN103464172A CN2013104207321A CN201310420732A CN103464172A CN 103464172 A CN103464172 A CN 103464172A CN 2013104207321 A CN2013104207321 A CN 2013104207321A CN 201310420732 A CN201310420732 A CN 201310420732A CN 103464172 A CN103464172 A CN 103464172A
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CN103464172B (en
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尹晓红
蒋万林
王斌
马帅华
毕亚东
刘勇
李霞
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Tianjin University of Technology
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Abstract

The invention provides a compound photocatalyst for reducing carbon dioxide into an organic ester. A chemical formula of the compound photocatalyst is expressed as NaNbO3-Zn0.42Cd0.58S. The compound photocatalyst is composed of prismatic crystals NaNbO3 and particles Zn0.42Cd0.58S attached on the surfaces of the prismatic crystals; the XRD (X Ray Diffracmeter) diffraction peak of the catalyst is basically identical with the diffraction peaks of NaNbO3, ZnS and CdS, and no other impurity peak is formed. The compound photocatalyst is prepared through adopting the steps: 1) preparing a NaNbO3 photocatalyst through a hydrothermal process; and 2) preparing the NaNbO3-Zn0.42Cd0.58S compound photocatalyst through a hydrothermal process. The compound photocatalyst and the preparation method thereof provided by the invention have the advantages that the preparation method is simple and easy to operate, the obtained compound photocatalyst is capable of reducing CO2 into methyl formate through photocatalysis under ultraviolet irradiation with methanol as a solvent, and has extremely high photocatalytic activity and thus is capable of effectively reducing the CO2, and with the methanol as the solvent, the catalytic efficiency is capable of reaching 6204 micro-mol/h/g.cat.

Description

Composite photo-catalyst that a kind of reducing carbon dioxide is organic ester and preparation method thereof
Technical field
The present invention relates to the technology of preparing of composite photo-catalyst, composite photo-catalyst and technology of preparing thereof that especially a kind of reducing carbon dioxide is organic ester.
Background technology
Photo catalytic reduction CO 2, utilizing clean, eternal, priceless solar energy, the easy easy control of its course of reaction, therefore become the important directions that people endeavour research.Photo catalytic reduction CO 2be photochemical catalyst under the irradiation of light, utilizing photoelectric effect is light energy conversion electric energy, by CO 2be converted into HCOOH, HCHO, CH 3oH, CH 4deng material, can eliminate CO 2on the impact of environment, simultaneously by CO 2convert industrial chemicals to, so not only be conducive to human environment protection but also alleviated energy crisis.Simultaneously, the photochemical catalyst of finding high catalytic activity and high selectivity has become people in recent years and has endeavoured the problem solved.
The problem also existed in research at present is that the catalytic efficiency of various photochemical catalysts is lower, and distance is promoted practical application and also had some gaps; Secondly traditional catalysis material can only the long ultraviolet light of radiothermy, and sunshine utilization rate and quantum efficiency are low.Fan Jun etc., referring to: petrochemical industry. 2009; 38 (7): 789-794, studied Fe 3+dopen Nano TiO 2catalyst photo catalytic reduction CO 2/ H 2o system methanol, Na 2sO 3as hole trapping agents, NaOH is as reaction environment, and methanol yield reaches 308.76 μ mol/h/gcat, and its catalytic activity is still lower.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 NaNbO 3with sulfide solid solution Zn 0.42cd 0.58s, as photochemical catalyst, develops the heterojunction type photocatalytic agent NaNbO with coupling light catalytic activity 3-Zn 0.42cd 0.58s, improved photocatalytic activity, obtained high methyl formate yield.
Summary of the invention
The objective of the invention is for above-mentioned existing problems, composite photo-catalyst that a kind of reducing carbon dioxide is organic ester and preparation method thereof is provided, the preparation method is simple, easy and simple to handle, prepared composite photo-catalyst take methyl alcohol as solvent under UV-irradiation photocatalysis by CO 2be reduced to methyl formate, there is very high photocatalytic activity, can be effectively by CO 2reduction.
Technical scheme of the present invention:
The composite photo-catalyst that a kind of reducing carbon dioxide is organic ester, chemical formulation is NaNbO 3-Zn 0.42cd 0.58s, it is by iris NaNbO 3and be attached to surperficial Zn 0.42cd 0.58the S particle forms, XRD diffraction maximum and the NaNbO of this catalyst 3, ZnS and CdS diffraction maximum substantially identical, without other impurity peaks, produce.
The preparation method of the composite photo-catalyst that a kind of described reducing carbon dioxide is organic ester, with NaNbO 3with sulfide solid solution Zn 0.42cd 0.58s, as photochemical catalyst, adopts hydro-thermal method to prepare NaNbO 3-Zn 0.42cd 0.58the S composite photocatalyst, step is as follows:
1) adopt hydro-thermal method to prepare NaNbO 3photochemical catalyst
NaOH is dissolved in to deionized water for stirring 0.5 hour, obtain sodium hydroxide solution, niobium pentaoxide is added in above-mentioned sodium hydroxide solution, magnetic agitation obtains solution a after it being mixed in 2 hours; Above-mentioned solution a is moved in water heating kettle, then be placed in thermostatic drying chamber, 180 othermostatic crystallization 24h under C, obtain solution b; Treat that the water heating kettle temperature is down to room temperature, the supernatant of solution b is poured in waste liquid bottle, the suspension of bottom is poured in centrifuge tube, with deionized water centrifuge washing 6-7 time repeatedly, obtain NaNbO 3the photochemical catalyst crude product; By above-mentioned NaNbO 3the photochemical catalyst crude product is placed in thermostatic drying chamber, 80 ofreeze-day with constant temperature 6h under C, then, by gained solid abrasive powdered, can make NaNbO 3photochemical catalyst;
2) adopt hydro-thermal method to prepare NaNbO 3-Zn 0.42cd 0.58the S composite photocatalyst
NaNbO by above-mentioned preparation 3dissolve in deionized water for stirring 0.5 hour, obtain NaNbO 3solution; 0.34g cadmium acetate, 0.38g zinc nitrate and 0.58g thiocarbamide are added to above-mentioned NaNbO 3after in solution, magnetic agitation mixes it in 2 hours, obtain solution c; Above-mentioned solution c is moved in water heating kettle, then be placed in thermostatic drying chamber, 140 othermostatic crystallization 12h under C, obtain solution d; Treat that the water heating kettle temperature is down to room temperature, the supernatant of solution d is poured in waste liquid bottle, the bottom suspension is poured in centrifuge tube, with absolute ethyl alcohol and deionized water centrifuge washing 6-7 time repeatedly, obtain NaNbO 3-Zn 0.42cd 0.58the S crude product; By above-mentioned NaNbO 3-Zn 0.42cd 0.58the S crude product is placed in thermostatic drying chamber, 80 oc freeze-day with constant temperature 6h, then, by gained solid abrasive powdered, can make NaNbO 3-Zn 0.42cd 0.58the S composite photo-catalyst.
The amount ratio of described NaOH and deionized water is 1.88g:60ml; The mass ratio of niobium pentaoxide and NaOH is 0.4:1.88.
Described NaNbO 3with the amount ratio of deionized water be 0.41g:50ml; NaNbO 3, cadmium acetate, zinc nitrate and thiocarbamide mass ratio be 0.41:0.34:0.38:0.58.
Advantage of the present invention is: the preparation method is simple, easy and simple to handle, prepared composite photo-catalyst take methyl alcohol as solvent under UV-irradiation photocatalysis by CO 2be reduced to methyl formate, there is very high photocatalytic activity, can be effectively by CO 2reduction, the methyl alcohol of take can reach 6204 μ mol/h/gcat as solvent catalysis efficiency.
The accompanying drawing explanation
Fig. 1 (a) is (b) NaNbO 3-Zn 0.42cd 0.58the SEM figure of S.
Fig. 2 is NaNbO 3-Zn 0.42cd 0.58the XRD figure of S.
Fig. 3 is NaNbO 3-Zn 0.42cd 0.58s, NaNbO 3and Zn 0.42cd 0.58the UV-vis DRS spectrogram of S.
Fig. 4 is NaNbO 3-Zn 0.42cd 0.58the photocatalytic activity of S relatively.
The specific embodiment
Embodiment:
The preparation method of the composite photo-catalyst that a kind of reducing carbon dioxide is organic ester, step is as follows
1) adopt hydro-thermal method to prepare NaNbO 3photochemical catalyst
1.88g NaOH is dissolved in to the 60ml deionized water for stirring 0.5 hour, obtain sodium hydroxide solution, the 0.4g niobium pentaoxide is added in above-mentioned sodium hydroxide solution, magnetic agitation obtains solution a after it being mixed in 2 hours; Above-mentioned solution a is moved in the water heating kettle of 75ml, then be placed in thermostatic drying chamber, 180 othermostatic crystallization 24h under C, obtain solution b; Treat that the water heating kettle temperature is down to room temperature, the supernatant of solution b is poured in waste liquid bottle, the bottom suspension is poured in the 4ml centrifuge tube, with deionized water centrifuge washing 6-7 time repeatedly, obtain NaNbO 3the photochemical catalyst crude product; By above-mentioned NaNbO 3the photochemical catalyst crude product is placed in thermostatic drying chamber, 80 ofreeze-day with constant temperature 6h under C, then, by gained solid abrasive powdered grain, can make NaNbO 3photochemical catalyst;
2) adopt hydro-thermal method to prepare NaNbO 3-Zn 0.42cd 0.58the S composite photocatalyst
NaNbO by the above-mentioned preparation of 0.41g 3dissolve in after the 50ml deionized water for stirring mixes it in 0.5 hour, obtain NaNbO 3solution; 0.34g cadmium acetate, 0.38g zinc nitrate and 0.58g thiocarbamide are added to above-mentioned NaNbO 3in solution, magnetic agitation is 2 hours, obtains solution c; Above-mentioned solution c is moved in the water heating kettle of 75ml, then be placed in thermostatic drying chamber, 140 othermostatic crystallization 12h under C, obtain solution d; Treat that the water heating kettle temperature is down to room temperature, the supernatant of solution d is poured in waste liquid bottle, the bottom suspension is poured in the 4ml centrifuge tube, with absolute ethyl alcohol and deionized water centrifuge washing 6-7 time repeatedly, obtain NaNbO 3-Zn 0.42cd 0.58the S crude product; By above-mentioned NaNbO 3-Zn 0.42cd 0.58the S crude product is placed in thermostatic drying chamber, 80 oc freeze-day with constant temperature 6h, then, by gained solid abrasive powdered, can make NaNbO 3-Zn 0.42cd 0.58the S composite photo-catalyst.
Fig. 1 (a) is (b) NaNbO 3-Zn 0.42cd 0.58the SEM figure of S, show in figure: in compound, can see orthorhombic NaNbO 3, size is 2 μ m, and orthorhombic eight edges and corners and six faces attached Zn that expires the 200nm size all 0.42cd 0.58the S granule, and two kinds of crystal grain closely combine.
Fig. 2 is NaNbO 3-Zn 0.42cd 0.58the XRD of S figure, in figure, show: sample has strong diffraction maximum, in 2 θ=22.7 °, 32.5 °, 46.8 °, 52.3 °, 58.0 °, 68.0 °, 72.9 ° and the 77.7 ° corresponding NaNbO of the diffraction maximum of locating 3(101) of JCPDS-33-1270, (141), (080), (311), (143), (371), (044) and (1121) crystal face, and match with most of peak of ZnS JCPDS-05-0566 and CdS JCPDS-25-0863, because the generation of solid solution effect makes (100) and (101) crystal face of CdS, the low-angle skew occurs.
Fig. 3 is NaNbO 3-Zn 0.42cd 0.58s, NaNbO 3and Zn 0.42cd 0.58the UV-vis DRS spectrogram of S, show in figure: NaNbO 3-Zn 0.42cd 0.58naNbO is compared on the band gap limit of S compound 3and Zn 0.42cd 0.58red Shift Phenomena obviously appears in S, and in the absorption peak strength at ultraviolet wavelength 350nm and infrared wavelength 500nm place also than NaNbO 3and Zn 0.42cd 0.58s strengthens.
The NaNbO made 3-Zn 0.42cd 0.58the activity of S composite photo-catalyst detects:
The activity of composite photo-catalyst by photocatalysis under UV-irradiation by CO 2the reaction rate that is reduced to methyl formate is estimated.Utilize quartz reactor as photo catalytic reduction CO 2reactor, there is passage the reactor both sides, are convenient to pass into reaction gas CO 2, the reactor body is the steel flange that accompanies quartz plate, and quartz plate makes in During Illumination not lose ultraviolet ray intensity, 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 the evaluation response process, at 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, the closed vent mouth.Open ultraviolet light, reacted.Product is used gas chromatograph-mass spectrometer GC-MS(Agilent 5975C after centrifugation) qualitative analysis, with gas chromatograph GC(Agilent 7890) the hydrogen flame detector quantitative analysis, show after calculating that product formic acid methyl esters productive rate reaches 6204 μ mol/h/gcat.
Fig. 4 is NaNbO 3-Zn 0.42cd 0.58the photocatalytic activity of S relatively, shows in figure: the sample after compound shows the photo catalytic reduction CO higher than independent sample 2activity.Also can find out that by Fig. 3 the sample that compound photochemical catalyst optical absorption peak strength ratio is simple is strong, and ABSORPTION EDGE is than simple sample red shift.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 (4)

1. the composite photo-catalyst that reducing carbon dioxide is organic ester, it is characterized in that: chemical formulation is NaNbO 3-Zn 0.42cd 0.58s, it is by iris NaNbO 3and be attached to surperficial Zn 0.42cd 0.58the S particle forms, XRD diffraction maximum and the NaNbO of this catalyst 3, ZnS and CdS diffraction maximum substantially identical, without other impurity peaks, produce.
2. the preparation method of the composite photo-catalyst that reducing carbon dioxide is organic ester as claimed in claim 1, is characterized in that: with NaNbO 3with sulfide solid solution Zn 0.42cd 0.58s, as photochemical catalyst, adopts hydro-thermal method to prepare NaNbO 3-Zn 0.42cd 0.58the S composite photocatalyst, step is as follows:
1) adopt hydro-thermal method to prepare NaNbO 3photochemical catalyst
NaOH is dissolved in to deionized water for stirring 0.5 hour, obtain sodium hydroxide solution, niobium pentaoxide is added in above-mentioned sodium hydroxide solution, magnetic agitation obtains solution a after it being mixed in 2 hours; Above-mentioned solution a is moved in water heating kettle, then be placed in thermostatic drying chamber, 180 othermostatic crystallization 24h under C, obtain solution b; Treat that the water heating kettle temperature is down to room temperature, the supernatant of solution b is poured in waste liquid bottle, the suspension of bottom is poured in centrifuge tube, with deionized water centrifuge washing 6-7 time repeatedly, obtain NaNbO 3the photochemical catalyst crude product; By above-mentioned NaNbO 3the photochemical catalyst crude product is placed in thermostatic drying chamber, 80 ofreeze-day with constant temperature 6h under C, then, by gained solid abrasive powdered, can make NaNbO 3photochemical catalyst;
2) adopt hydro-thermal method to prepare NaNbO 3-Zn 0.42cd 0.58the S composite photocatalyst
NaNbO by above-mentioned preparation 3dissolve in deionized water for stirring 0.5 hour, obtain NaNbO 3solution; 0.34g cadmium acetate, 0.38g zinc nitrate and 0.58g thiocarbamide are added to above-mentioned NaNbO 3after in solution, magnetic agitation mixes it in 2 hours, obtain solution c; Above-mentioned solution c is moved in water heating kettle, then be placed in thermostatic drying chamber, 140 othermostatic crystallization 12h under C, obtain solution d; Treat that the water heating kettle temperature is down to room temperature, the supernatant of solution d is poured in waste liquid bottle, the bottom suspension is poured in centrifuge tube, with absolute ethyl alcohol and deionized water centrifuge washing 6-7 time repeatedly, obtain NaNbO 3-Zn 0.42cd 0.58the S crude product; By above-mentioned NaNbO 3-Zn 0.42cd 0.58the S crude product is placed in thermostatic drying chamber, 80 oc freeze-day with constant temperature 6h, then, by gained solid abrasive powdered, can make NaNbO 3-Zn 0.42cd 0.58the S composite photo-catalyst.
3. the preparation method of the composite photo-catalyst that reducing carbon dioxide is organic ester according to claim 2 is characterized in that: the amount ratio of described NaOH and deionized water is 1.88g:60ml; The mass ratio of niobium pentaoxide and NaOH is 0.4:1.88.
4. the preparation method of the composite photo-catalyst that reducing carbon dioxide is organic ester according to claim 2, is characterized in that: described NaNbO 3with the amount ratio of deionized water be 0.41g:50ml; NaNbO 3, cadmium acetate, zinc nitrate and thiocarbamide mass ratio be 0.41:0.34:0.38:0.58.
CN201310420732.1A 2013-09-16 2013-09-16 Compound photocatalyst for reducing carbon dioxide into organic ester and preparation method of compound photocatalyst Expired - Fee Related CN103464172B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105174948A (en) * 2014-06-04 2015-12-23 江南大学 Preparation method of niobate solid solution material
CN111111695A (en) * 2019-12-12 2020-05-08 电子科技大学 Three-dimensional flower-shaped zinc-sulfur-cadmium photocatalytic material and preparation method and application thereof

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CN101254467A (en) * 2008-04-11 2008-09-03 浙江大学 Precipitating-hydrothermal preparation with high visible light catalytic activity nano CdxZn1-xS photocatalyst

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Publication number Priority date Publication date Assignee Title
CN101254467A (en) * 2008-04-11 2008-09-03 浙江大学 Precipitating-hydrothermal preparation with high visible light catalytic activity nano CdxZn1-xS photocatalyst

Non-Patent Citations (2)

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Title
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105174948A (en) * 2014-06-04 2015-12-23 江南大学 Preparation method of niobate solid solution material
CN111111695A (en) * 2019-12-12 2020-05-08 电子科技大学 Three-dimensional flower-shaped zinc-sulfur-cadmium photocatalytic material and preparation method and application thereof
CN111111695B (en) * 2019-12-12 2021-12-03 电子科技大学 Three-dimensional flower-shaped zinc-sulfur-cadmium photocatalytic material and preparation method and application thereof

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