CN104338529A - Preparation method of MnOx-CeO2 composite semiconductor catalyst - Google Patents

Preparation method of MnOx-CeO2 composite semiconductor catalyst Download PDF

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CN104338529A
CN104338529A CN201410556944.7A CN201410556944A CN104338529A CN 104338529 A CN104338529 A CN 104338529A CN 201410556944 A CN201410556944 A CN 201410556944A CN 104338529 A CN104338529 A CN 104338529A
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ceo
mno
catalyst
formaldehyde
preparation
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王文中
蒋东
郑雅丽
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to a preparation method of a MnOx-CeO2 composite semiconductor catalyst which has the function of low-temperature photo-thermal concerted catalytic purification of VOCs and the light-assisted self repairing function. The chemical formula of the MnOx-CeO2 composite semiconductor catalyst is Ce<1-a>MnaO<2-Delta>, wherein a is larger than 0 and smaller than 0.7; the method comprises the following steps: (1) weighing Ce salt and KMnO4, and dissolving in an alkaline solution to obtain a mixed suspension solution; (2) sealing the mixed suspension solution to have a hydrothermal reaction to obtain a precipitate; (3) separating the prepared precipitate, washing, drying and then grinding to obtain the MnOx-CeO2 composite semiconductor catalyst.

Description

A kind of MnO x-CeO 2the preparation method of composite semiconductor catalyst
Technical field
The present invention relates to a kind of MnO x-CeO 2the preparation method of composite semiconductor catalyst, belongs to low temperature photo-thermal concerted catalysis degraded VOCs and light assists selfreparing field.
Background technology
Along with the progress of society and urbanization, the going deep into of process of industrialization, volatile organic contaminant (VOCs) as: formaldehyde, benzene, toluene, acetone etc., not only have great harm to health, and will cause serious environmental pollution.Particularly formaldehyde etc. are extensively present in people and live central noxious pollutant, and the moment threatens the health and environment of people.
Current research comparatively widely VOCs Treatment process comprises absorption, bio-absorbable, catalytic oxidation and photocatalytic degradation etc., wherein with the adsorption technology that is adsorbent such as active carbon, with the research report of the noble-metal-supported semiconductor catalytic oxidation technologies that is catalyst at most, it seems at present also the most effectively, application be also extensive.But be subject to the restriction of adsorption capacity, adsorption technology needs market to carry out regeneration process to adsorbent, and is limited to absorption and the restriction of non-degradable, and its secondary pollution phenomenon can not be avoided.Although noble metal carrier catalyst activity is higher and there is not secondary pollution problems, but undeniable is due to noble metal fancy price, it is caused to be in a disadvantageous position in Cost Competition, greatly limit its daily use, and if not carried noble metal greatly will promote its operative temperature and be unfavorable for that it is applied.In addition, TiO is the most widely studied at present in photocatalysis technology 2although type catalyst green is clean, cost is lower, because its semi-conducting material spectral response is narrower, catalytic degradation VOCs limited efficiency, be faced with a lot of restriction and problem equally.Therefore, from present case, threaten day by day serious severe situation to tackle VOCs, be badly in need of research and development low cost, green thoroughly, the new catalysis material of efficient degradation purifying VOCs and technology.
CeO 2, MnO 2oxide gets more and more people's extensive concerning because possessing good catalytic oxidation performance.US Patent No. 6458741 adopts dipping decomposition method, precipitation sedimentation and coprecipitation to prepare cerium base binary or multicomponent composite oxide, and precious metals pt, Pd are carried on these composite oxides, the composite oxide catalysts of gained has good low-temperature catalytic oxidation VOCs ability.The people such as the Nobuhito Imanaka of Japan prepare the CeO of different component proportioning by coprecipitation, mechanical milling method etc. 2-Bi 2o 3-ZrO 2composite catalyst, and by itself and precious metals pt, Pd etc. and Al 2o 3carry out compound, the composite catalyst obtained has good low-temperature catalytic oxidation ability (N.Imanaka to toluene, ethene, acetaldehyde etc., T.Masui.Chemical Record 2009,9,40.N.Imanaka, T.Masui, K.Koyabu, et al.Advanced Materials 2007,19,1608.N.Imanaka, T.Masui, K.Minami, et al.Chemistry of Materials 2005,17,6511.N.Imanaka, T.Masui, K.Yasuda.Chemistry Letters 2011,40,780.).Chinese patent CN200510093318.2 adopts infusion process to prepare support type Mn-Ce composite oxide catalysts, and this catalyst has good catalytic oxidation activity to VOCs.The people such as Tang are with (NH 4) 2ce (NO 3) 6, Mn (NO 3) 26H 2o and citric acid are raw material, adopt coprecipitation to prepare MnO x-CeO 2composite oxide catalysts, this catalyst is at 100 DEG C, and the degraded of PARA FORMALDEHYDE PRILLS(91,95) reaches 100%, and has good stability (F.Tang, Y.G.Li, M.Huang, et al.Applied Catalysis B 2006,62,265).The people such as Delimars are with Ce (NO 3) 36H 2o, Mn (NO 3) 2be raw material with urea, the MnO that adopted urea-nitrate combustion legal system standby x-CeO 2composite oxide catalysts, this catalyst has good catalytic oxidation activity (D.Delimaris, T.Ioannides.Applied Catalysis B 2008,84,303) to VOCs.Chinese patent CN102553575 adopts hydro-thermal method to prepare CeO 2-MnO 2composite oxide catalysts, this catalyst has good catalytic oxidation activity to volatile organic matter benzene, and shows photo-thermal synergisticing performance at certain temperature (200 DEG C).
CeO 2oxide not only has good catalytic oxidation ability, also possesses certain photocatalysis performance as a kind of broad-band gap n-type semiconductor.The people such as nearest Li have found mesoporous nano CeO 2there is good oxygen ion conduction coupling photo-thermal concerted catalysis performance, under the acting in conjunction of 240 DEG C and UV-irradiation, efficient catalytic oxidation activity and stability (Y.Z.Li are shown for volatile organic contaminants such as benzene, cyclohexane, acetone, Q.Sun, M.Kong, et al.Journal of Physical Chemistry C, 2011,115,14050).The people such as Jiang are with Ce (NO 3) 36H 2o, Bi (NO 3) 35H 2o and NaOH is raw material, adopts CeO prepared by hydrothermal method 2-Bi 2o 3composite oxide catalysts, this catalyst has ion, the electronic conductance of coupling, under the acting in conjunction of 30 DEG C-80 DEG C and simulated solar light source Xe light irradiation, PARA FORMALDEHYDE PRILLS(91,95) shows efficient low temperature light, hot concerted catalysis oxidation activity and good stability (D.Jiang, W.Wang, E.Gao, et al.Journal of Physical Chemistry C, 2013,117,24242).
Therefore, how MnO is prepared by easy mode x-CeO 2, remain one of this those skilled in the art's research direction.
Summary of the invention
The present invention is intended to expand MnO further x-CeO 2preparation method, the invention provides a kind of MnO x-CeO 2the preparation method of composite semiconductor catalyst.
The invention provides a kind of MnO x-CeO 2the preparation method of composite semiconductor catalyst, described MnO x-CeO 2the chemical formula of composite semiconductor catalyst is Ce 1-amn ao 2-δ, wherein 0<a<0.7; Described method comprises:
1) Ce salt and KMnO is taken 4, be dissolved in aqueous slkali, obtain mixing suspension, wherein, Ce salt and KMnO 4the ratio of mole and described MnO x-CeO 2in composite semiconductor catalyst, the proportionate relationship of Ce element, Mn element is consistent;
2) by step 1) the mix suspending liquid sealing prepared, carries out hydro-thermal reaction at 80-200 DEG C, is precipitated thing;
3) isolate step 2) sediment prepared, washing, dry after grinding namely obtain described MnO x-CeO 2composite semiconductor catalyst.
The present invention utilizes CeO 2good photo-thermal concerted catalysis oxidative function, MnO xgood low-temperature catalytic oxidation ability and MnO xto visible-near-infrared good absorbability, with Ce (III, IV) salt and high price Mn source KMnO 4for source metal, to adopt in strong alkali environment precipitated nanocrystals crystal seed, thermal and hydric environment redox, nano material grown and dry run the series of measures such as nano material crystal transfer, under simple gentle reaction environment, novelty devise MnO x-CeO 2semiconductors coupling method for preparing catalyst.
Preferably, in described Ce salt, the chemical valence of Ce is trivalent or tetravalence, and described Ce salt comprises cerous nitrate, cerous chlorate, cerous sulfate, cerous sulfate and/or ammonium ceric nitrate.
Preferably, the concentration of described aqueous slkali neutral and alkali material is 1-8mol/L, and described alkaline matter comprises NaOH, KOH, Na 2cO 3and/or K 2cO 3.
Preferably, Ce salt and KMnO 4mole sum and aqueous slkali volume between ratio be (1-6) mmol:40ml.
Preferably, the time of described hydro-thermal reaction is 8-72 hour.
Preferably, described sedimentary baking temperature is 60-120 DEG C.
Beneficial effect of the present invention:
1) MnO prepared by the present invention x-CeO 2composite catalyst, catalytic activity and the light simple and easy to operate with efficient cryogenic photo-thermal concerted catalysis oxidation VOCs assist self-repair function, its catalysed oxidn temperature lower (lower than 50 DEG C) is easy to realize, be conducive to the utilization to common light sources place heat energy in sunshine mid-infrared light energy and daily life, its light assists selfreparing can carry out under simulated solar light source, be conducive to the utilization to occurring in nature day alternates with night phenomenon, realize its in daily life practical;
2) MnO prepared by the present invention x-CeO 2composite catalyst, the addition of photo-thermal synergistic activity and both activities active far above the thermocatalytic at the photocatalytic activity under its room temperature, same temperature, far above simple CeO 2the photo-thermal synergistic activity of catalyst, improves catalytic purification efficiency;
3) MnO prepared by the present invention x-CeO 2composite catalyst, without the need to any noble-metal-supported, significantly reduces the cost of catalyst;
4) MnO that invents of this patent x-CeO 2method for preparing composite catalyst, raw material is cheap and easy to get, technique is simple, easy controlled operation, performance reproducibility good and be easy to technical scaleization produces.
Accompanying drawing explanation
Fig. 1 shows the MnO prepared in an embodiment of the invention x-CeO 2composite catalyst (Ce/Mn mol ratio 3:1) is at 50 DEG C, and photo-thermal concerted catalysis and thermocatalytic, photocatalytic degradation 250ppm formaldehyde generate CO 2change in concentration comparison diagram;
Fig. 2 shows the MnO prepared in an embodiment of the invention x-CeO 2composite catalyst (Ce/Mn mol ratio 3:1) is at 75 DEG C, and photo-thermal concerted catalysis and thermocatalytic, photocatalytic degradation 250ppm formaldehyde generate CO 2change in concentration comparison diagram;
Fig. 3 shows the MnO prepared in an embodiment of the invention x-CeO 2composite catalyst (Ce/Mn mol ratio 3:1) and CeO 2at 75 DEG C, photo-thermal concerted catalysis, thermocatalytic and photocatalytic degradation 250ppm formaldehyde generate CO 2change in concentration comparison diagram;
Fig. 4 shows the MnO prepared in an embodiment of the invention x-CeO 2composite catalyst (the Ce/Mn mol ratio 3:1) CO that thermocatalytic circulation degraded 250ppm formaldehyde produces under 60 DEG C of conditions 2change in concentration and time chart;
Fig. 5 shows the MnO prepared in an embodiment of the invention x-CeO 2composite catalyst (Ce/Mn mol ratio 3:1) after the circulation of 30 thermocatalytics, then after 3 hours Xe lamp original position irradiation, the CO that thermocatalytic degraded 250ppm formaldehyde produces under 60 DEG C of conditions 2change in concentration and time chart;
Fig. 6 shows the MnO prepared in an embodiment of the invention x-CeO 2composite catalyst (Ce/Mn mol ratio 3:1) after the circulation of 30 thermocatalytics, then after 6 hours Xe lamp original position irradiation, the CO that thermocatalytic degraded 250ppm formaldehyde produces under 60 DEG C of conditions 2change in concentration and time chart;
Fig. 7 shows the MnO prepared in an embodiment of the invention x-CeO 2composite catalyst (Ce/Mn mol ratio 3:1) experiences in the cyclic process that three thermocatalytics degraded 250ppm formaldehyde and 6 hours Xe lamp original position irradiation regenerate, and under 60 DEG C of conditions, thermocatalytic is degraded the CO of 250ppm formaldehyde generation 2change in concentration and time chart;
Fig. 8 shows the MnO prepared in a way of contrast of the present invention x-CeO 2composite catalyst (Ce/Mn mol ratio 3:1) is at 50 DEG C, and thermocatalytic degraded 250ppm formaldehyde generates CO 2change in concentration and time chart;
Wherein, curve A is photo-thermal concerted catalysis, and curve B is thermocatalytic, and curve C is photocatalysis.
Detailed description of the invention
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.
The present invention relates to a kind of MnO x-CeO 2the preparation method of composite semiconductor catalyst.This composite semiconductor catalyst, can the volatile organic contaminant (VOCs) such as efficient catalytic degradation of formaldehyde, benzene, acetone under the light, hot synergy condition of low temperature; Meanwhile, in-situ regeneration can be realized under the effect of light irradiation through the long-time catalyst continuing dark reaction inactivation.
The present invention relates to and a kind ofly there is low temperature photo-thermal concerted catalysis degraded VOCs and light assists the MnO of self-repair function x-CeO 2the preparation method of composite semiconductor catalyst, comprises the following steps:
1) Ce (III, IV) salt and KMnO is taken 4, be dissolved in deionized water, get a uniform mixture, the aqueous slkali prepared is added above-mentioned mixed solution, obtains unit for uniform suspension, namely according to CeO 2with MnO xthe amount proportioning of the different material of semiconductor is (100-30): (0-70) takes Ce (III, IV) salt and KMnO 4, be dissolved in certain density aqueous slkali, and choose for (1-6) mmol:40ml according to the proportioning of the total amount of substance of slaine and solvent.Slaine is joined in solvent, obtain mixing suspension;
2) suspension is transferred in reactor, after sealing, under certain temperature and pressure, carries out hydro-thermal reaction;
3) after having reacted, question response still is cooled to room temperature, takes out inner bag, by precipitate and separate wherein, washing, and grinding after drying at a certain temperature, obtains having the MnO that the concerted catalysis of efficient cryogenic photo-thermal and light help repair function x-CeO 2composite catalyst.
Described Ce (III) salt is cerous nitrate, cerous chlorate or cerous sulfate, and Ce (IV) salt is cerous sulfate, ammonium ceric nitrate.
Described certain density aqueous slkali is NaOH, KOH, Na of 1-8mol/L 2cO 3or K 2cO 3.
The reaction temperature of described hydro-thermal reaction is 80 DEG C-200 DEG C, and the reaction time is 8-72 hour, and after reaction, sample drying environment is 60 DEG C-120 DEG C.
The present invention utilizes CeO 2good photo-thermal concerted catalysis oxidative function, MnO xgood low-temperature catalytic oxidation ability and MnO xto visible-near-infrared good absorbability, with Ce (III, IV) salt and high price Mn source KMnO 4for source metal, to adopt in strong alkali environment precipitated nanocrystals crystal seed, thermal and hydric environment redox, nano material grown and dry run the series of measures such as nano material crystal transfer, under simple gentle reaction environment, novelty devise MnO x-CeO 2semiconductors coupling method for preparing catalyst.Wherein the use of water-heat process neutral and alkali environment will accelerate the generation of mixed oxide crystal seed greatly, contributes to prepared MnO simultaneously x-CeO 2composite catalyst possesses the defect and the surface hydroxyl isoreactivity site that are conducive to catalytic oxidation process more.Find and traditional heat catalytic oxidation process, Photocatalytic Oxidation and CeO 2photo-thermal concerted catalysis oxidizing process compare, under photo-thermal (lower than 50 DEG C) the acting in conjunction environment of gentleness, the MnO of gained x-CeO 2composite catalyst, shows the Low Temperature Thermal catalytic performance, the photocatalysis performance that significantly promote simultaneously, and the synergisticing performance of the two.Significant low temperature photo-thermal cooperative effect has its source in MnO x-CeO 2composite catalyst has electronics, the ionic conduction of coupling, and intercoupling between the two is conducive to promoting the synergy between light, thermocatalytic.In addition, MnO xsolid solution enter the low temperature oxygen release ability making composite catalyst, namely low-temperature catalytic oxidation ability promotes greatly; Largely expand the visible-near-infrared responding ability of composite catalyst simultaneously, and then promote its photocatalysis performance.The MnO of gained of the present invention x-CeO 2the photo-thermal concerted catalysis oxidation activity of composite catalyst is far above the CeO with photo-thermal cooperative ability reported before 2catalyst and CeO 2-Bi 2o 3performance under the similarity condition of composite catalyst, greatly reduces the effective serviceability temperature of catalyst, the MnO of gained x-CeO 2composite catalyst can under low temperature (lower than 50 DEG C) condition the gas phase volatile organic contaminant such as efficient catalytic degradation of formaldehyde, benzene, acetone.What is more important, the MnO of gained of the present invention x-CeO 2composite catalyst has simple and easy to do light and assists self-repair function, can realize in-situ regeneration through the long-time catalyst continuing dark reaction inactivation under the effect of simulated solar light source irradiation, and this inactivation-regeneration cycle process repeatability is good.
Beneficial effect of the present invention is also:
1) MnO prepared by the present invention x-CeO 2composite catalyst, catalytic activity and the light simple and easy to operate with efficient cryogenic photo-thermal concerted catalysis oxidation VOCs assist self-repair function, its catalysed oxidn temperature lower (lower than 50 DEG C) is easy to realize, be conducive to the utilization to common light sources place heat energy in sunshine mid-infrared light energy and daily life, its light assists selfreparing can carry out under simulated solar light source, be conducive to the utilization to occurring in nature day alternates with night phenomenon, realize its in daily life practical;
2) MnO prepared by the present invention x-CeO 2composite catalyst, the addition of photo-thermal synergistic activity and both activities active far above the thermocatalytic at the photocatalytic activity under its room temperature, same temperature, far above simple CeO 2the photo-thermal synergistic activity of catalyst, improves catalytic purification efficiency;
3) MnO prepared by the present invention x-CeO 2composite catalyst, without the need to any noble-metal-supported, significantly reduces the cost of catalyst;
4) MnO of the present invention x-CeO 2method for preparing composite catalyst, raw material is cheap and easy to get, technique is simple, easy controlled operation, performance reproducibility good and be easy to technical scaleization produces.
Below some exemplary embodiments are listed further better the present invention to be described.Should understand; the above-mentioned embodiment that the present invention describes in detail; and following examples are only not used in for illustration of the present invention and limit the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.In addition, concrete proportioning, time, temperature etc. in following technological parameter are also only exemplary, and those skilled in the art can select suitable value in the scope of above-mentioned restriction.
Embodiment 1
There is low temperature photo-thermal concerted catalysis degraded VOCs and light assists the MnO of self-repair function x-CeO 2the preparation method of composite semiconductor catalyst (Ce/Mn mol ratio 3:1) is as follows:
(1) 3mmolCe (NO is taken 3) 36H 2o and 1mmolKMnO 4, joining 40ml molar concentration is in the NaOH aqueous solution of 6M, and room temperature lower magnetic force stirs, and obtains the nanosized seeds suspension forming precipitation;
(2) mixed solution being moved to 50ml is with in the stainless steel cauldron of polytetrafluoroethylliner liner, through sealing, and hydro-thermal reaction 24 hours at 110 DEG C of temperature;
(3) after having reacted, question response still is cooled to room temperature, takes out polytetrafluoroethylliner liner, filter, washing, at 60 DEG C dry 12 hours, obtain MnO x-CeO 2composite catalyst (Ce/Mn mol ratio 3:1).
Embodiment 2
By the MnO that embodiment 1 obtains x-CeO 2composite catalyst is used for photo-thermal concerted catalysis degraded 250ppm formaldehyde, and catalytic reaction temperature is 50 DEG C, and concrete implementation step is as follows:
(1) MnO of embodiment 1 gained is taken x-CeO 2composite catalyst 0.1g grinding is positioned over bottom experimental reactor, evenly spreads out;
(2) specific experiment device is described as: experimental reactor is the 650ml cylindrical glass reactor with leading to recirculated water chuck, and top is high printing opacity quartz glass; Top is that 500W Xe lamp is as simulated solar light source at a distance of 10cm; Chuck is connected to constant temperature water bath groove, accurately can carry out the temperature of reactor bottom catalyst in process by Control release; Reactor is connected to 7,890 I type chromatography of gases, carries out sample analysis in predetermined time interval to the mist in reactor;
(3) by temperature regulating device, experimental reactor temperature is controlled at 50 DEG C, open Xe lamp source by Current adjustment to 20A, sealing cylinder shape glass reactor, the CO of mist in timing detection reaction device 2component ratio, until CO 2constant concentration is constant, reaches catalyst for CO 2adsorption-desorption balance;
(4) start the experiment of photo-thermal degradation of formaldehyde, extract in 250ppm formaldehyde injecting reactor with microsyringe, specific time interval extracts the component of mist in detection reaction device, records wherein CO 2the change in concentration of gas;
Embodiment 2 CO that photo-thermal concerted catalysis degraded 250ppm formaldehyde produces under 50 DEG C of conditions 2change in concentration and time relationship are shown in curve A in Fig. 1.At 50 DEG C, after photo-thermal concerted catalysis degradation of formaldehyde 3h, CO 2increment is 151.5ppm.
Embodiment 3
By the MnO that embodiment 1 obtains x-CeO 2composite catalyst thermocatalytic degraded 250ppm formaldehyde, specific experiment step is substantially the same manner as Example 2, and difference is, in catalytic reaction process, closes Xe lamp source;
The CO that in embodiment 3, at 50 DEG C, thermocatalytic degraded 250ppm formaldehyde produces 2the relation of concentration curve is shown in the curve B in Fig. 1, after thermocatalytic degraded 3h, and CO 2increment is 41ppm.
Embodiment 4
By the MnO that embodiment 1 obtains x-CeO 2composite catalyst photocatalytic degradation 250ppm formaldehyde, specific experiment step is substantially the same manner as Example 2, and difference is, in catalytic reaction process, reaction temperature is controlled at 25 DEG C;
The CO that in embodiment 4, at 25 DEG C, photocatalytic degradation 250ppm formaldehyde produces 2the relation of concentration curve is shown in the curve C in Fig. 1, after photocatalytic degradation 3h, and CO 2increment is 105.7ppm;
As shown in Figure 1, MnO at 50 DEG C x-CeO 2the CO of composite catalyst (Ce/Mn mol ratio 3:1) photo-thermal concerted catalysis degraded 250ppm formaldehyde 2generating rate is thermocatalytic 3.7 times, is light-catalysed 1.4 times.
Embodiment 5
By the MnO that embodiment 1 obtains x-CeO 2composite catalyst photo-thermal concerted catalysis degraded 250ppm formaldehyde, catalytic reaction temperature is 75 DEG C, and concrete implementation step is as follows:
(1) MnO of embodiment 1 gained is taken x-CeO 2composite catalyst 0.1g grinding is positioned over bottom experimental reactor, evenly spreads out;
(2) specific experiment device is described as: experimental reactor is the 650ml cylindrical glass reactor with leading to recirculated water chuck, and top is high printing opacity quartz glass; Top is that 500W Xe lamp is as simulated solar light source at a distance of 10cm; Chuck is connected to constant temperature water bath groove, accurately can carry out the temperature of reactor bottom catalyst in process by Control release; Reactor is connected to 7,890 I type chromatography of gases, carries out sample analysis in predetermined time interval to the mist in reactor;
(3) by temperature regulating device, experimental reactor temperature is controlled at 75 DEG C, open Xe lamp source by Current adjustment to 20A, sealing cylinder shape glass reactor, the CO of mist in timing detection reaction device 2component ratio, until CO 2constant concentration is constant, reaches catalyst for CO 2adsorption-desorption balance;
(4) start the experiment of photo-thermal degradation of formaldehyde, extract in 250ppm formaldehyde injecting reactor with microsyringe, specific time interval extracts the component of mist in detection reaction device, records wherein CO 2the change in concentration of gas;
Embodiment 5 CO that photo-thermal concerted catalysis degraded 250ppm formaldehyde produces under 75 DEG C of conditions 2change in concentration and time relationship are shown in curve A in Fig. 2.At 75 DEG C, after photo-thermal concerted catalysis degraded 3h, CO 2increment is 226ppm.
Embodiment 6
By the MnO that embodiment 1 obtains x-CeO 2composite catalyst thermocatalytic degraded 250ppm formaldehyde, specific experiment step is substantially the same manner as Example 5, and difference is, in catalytic reaction process, closes Xe lamp source;
The CO that in embodiment 6, at 75 DEG C, thermocatalytic degraded 250ppm formaldehyde produces 2the relation of concentration curve is shown in the curve B in Fig. 2, after thermocatalytic degraded 3h, and CO 2increment is 67.7ppm.
Embodiment 7
By the MnO that embodiment 1 obtains x-CeO 2composite catalyst photocatalytic degradation 250ppm formaldehyde, specific experiment step is substantially the same manner as Example 5, and difference is, in catalytic reaction process, reaction temperature is controlled at 25 DEG C;
The CO that in embodiment 7, at 25 DEG C, photocatalytic degradation 250ppm formaldehyde produces 2the relation of concentration curve is shown in the curve C in Fig. 2, after photocatalytic degradation 3h, and CO 2increment is 105.7ppm;
As shown in Figure 2, MnO at 75 DEG C x-CeO 2the CO of composite catalyst (Ce/Mn mol ratio 3:1) photo-thermal concerted catalysis degraded 250ppm formaldehyde 2generating rate is thermocatalytic 3.3 times, is light-catalysed 2.1 times.
Embodiment 8
By the MnO that embodiment 1 obtains x-CeO 2composite catalyst, thermocatalytic circulation degraded 250ppm formaldehyde and light assist selfreparing, and heat catalysis temperature is 60 DEG C, and concrete implementation step is as follows:
(1) MnO of embodiment 1 gained is taken x-CeO 2composite catalyst 0.1g grinding is positioned over bottom experimental reactor, evenly spreads out;
(2) specific experiment device is described as: experimental reactor is the 650ml cylindrical glass reactor with leading to recirculated water chuck, and top is high printing opacity quartz glass; Top is that 500W Xe lamp is as simulated solar light source at a distance of 10cm; Chuck is connected to constant temperature water bath groove, accurately can carry out the temperature of reactor bottom catalyst in process by Control release; Reactor is connected to 7,890 I type chromatography of gases, carries out sample analysis in predetermined time interval to the mist in reactor;
(3) by temperature regulating device, experimental reactor temperature is controlled at 60 DEG C, sealing cylinder shape glass reactor, the CO of mist in timing detection reaction device 2component ratio, until CO 2constant concentration is constant, reaches catalyst for CO 2adsorption-desorption balance;
(4) start the experiment of thermocatalytic degradation of formaldehyde, extract in 250ppm formaldehyde injecting reactor with microsyringe, specific time interval extracts the component of mist in detection reaction device, records wherein CO 2the change in concentration of gas.Above-mentioned thermocatalytic degradation of formaldehyde process circulates 30 times;
(5) by the MnO of above-described embodiment 1 gained x-CeO 2composite catalyst 60 DEG C of thermocatalytics degraded 250ppm formaldehyde sample after 30 times that circulates carries out original position light irradiation, and open Xe lamp source by Current adjustment to 20A, control at 25 DEG C by temperature regulating device by experimental reactor temperature, exposure time continues 3 hours;
(6) by above-mentioned MnO after 3 hours Xe lamp irradiation x-CeO 2composite catalyst carries out original position light irradiation again, opens Xe lamp source by Current adjustment to 20A, controls at 25 DEG C by temperature regulating device by experimental reactor temperature, and exposure time continues 3 hours;
In embodiment 8, the CO that thermocatalytic degraded 250ppm formaldehyde produces under 60 DEG C of conditions 2change in concentration and time relationship are shown in Fig. 4.At 60 DEG C, after 30 circulations of thermocatalytic degraded experience, MnO x-CeO 2the formaldehyde percentage that composite catalyst (Ce/Mn mol ratio 3:1) was degraded in the first hour is about 10% of fresh sample initial performance;
In embodiment 8, after 30 60 DEG C of thermocatalytics circulation degraded 250ppm formaldehyde again after 3 hours original position Xe lamp irradiation, the CO that thermocatalytic degraded 250ppm formaldehyde produces under 60 DEG C of conditions 2change in concentration and time relationship are shown in Fig. 5.After experiencing 3 hours Xe lamp irradiation, MnO x-CeO 2the formaldehyde percentage that composite catalyst (Ce/Mn mol ratio 3:1) was degraded in the first hour is about 30% of fresh sample initial performance;
In embodiment 8, after 30 60 DEG C of thermocatalytics circulation degraded 250ppm formaldehyde again after 6 hours original position Xe lamp irradiation, the CO that thermocatalytic degraded 250ppm formaldehyde produces under 60 DEG C of conditions 2change in concentration and time relationship are shown in Fig. 6.After experiencing 6 hours Xe lamp irradiation, MnO x-CeO 2the formaldehyde percentage that composite catalyst (Ce/Mn mol ratio 3:1) was degraded in the first hour is about 50% of fresh sample initial performance.
Embodiment 9
By the MnO that embodiment 1 obtains x-CeO 2composite catalyst, carries out thermocatalytic degraded 250ppm formaldehyde and light assists selfreparing circulation experiment, and heat catalysis temperature is 60 DEG C, and concrete implementation step is as follows:
(1) by embodiment 8 after 6 hours Xe lamp irradiation gained MnO x-CeO 2composite catalyst is used for 60 DEG C of thermocatalytic degraded 250ppm formaldehyde, and thermocatalytic process carries out 10 circulations;
(2) the thermocatalytic degraded 250ppm formaldehyde sample after 10 times that circulates carries out original position light irradiation, and open Xe lamp source by Current adjustment to 20A, control at 25 DEG C by temperature regulating device by experimental reactor temperature, exposure time continues 6 hours;
(3) (1), (2) step of above-described embodiment 9 is repeated once;
In embodiment 9, in 2 thermocatalytic inactivations and original position light irradiation regeneration cycle process, the CO that thermocatalytic degraded 250ppm formaldehyde produces under 60 DEG C of conditions 2change in concentration and time relationship are shown in Fig. 7.MnO x-CeO 2the light of composite catalyst (Ce/Mn mol ratio 3:1) assists self-repair function repeatability good, not decay.
Comparative example 1
Take 4mmolCe (NO 3) 36H 2o, joining and 40ml molar concentration is housed is in the NaOH aqueous solution of 6M, and room temperature lower magnetic force stirs, and obtains the nanosized seeds suspension forming precipitation; Mixed solution being moved to 50ml is with in the stainless steel cauldron of polytetrafluoroethylliner liner, through sealing, and hydro-thermal reaction 24 hours at 110 DEG C of temperature; After having reacted, band reactor is cooled to room temperature, takes out polytetrafluoroethylliner liner, filter, washing, at 60 DEG C dry 12 hours, obtain nano Ce O 2powder; By obtained nano Ce O 2powder photo-thermal concerted catalysis degraded 250ppm formaldehyde, open Xe lamp source by Current adjustment to 20A, catalytic reaction temperature is 75 DEG C.CeO 2the CO that photo-thermal concerted catalysis degraded 250ppm formaldehyde produces under 75 DEG C of conditions 2change in concentration and time relationship are shown in shadow region A ' in Fig. 3, the MnO that comparative example 1 obtains x-CeO 2composite catalyst (in Fig. 3 shadow region A), reacts MnO after 3 hours x-CeO 2the CO of composite catalyst photo-thermal degradation of formaldehyde 2generating rate is CeO 23.8 times.
Comparative example 2
By comparative example 1 obtain nano Ce O 2powder thermocatalytic degraded 250ppm formaldehyde, close Xe lamp source, catalytic reaction temperature is 75 DEG C.CeO 2the CO that thermocatalytic degraded 250ppm formaldehyde produces under 75 DEG C of conditions 2change in concentration and time relationship are shown in shadow region B ' in Fig. 3, the MnO that comparative example 1 obtains x-CeO 2composite catalyst (in Fig. 3 shadow region B), reacts MnO after 3 hours x-CeO 2the CO of composite catalyst thermocatalytic degradation of formaldehyde 2generating rate is CeO 28.5 times.
Comparative example 3
By comparative example 1 obtain nano Ce O 2powder photocatalytic degraded 250ppm formaldehyde, open Xe lamp source by Current adjustment to 20A, catalytic reaction temperature is 25 DEG C.CeO 2the CO that photocatalytic degradation 250ppm formaldehyde produces under 25 DEG C of conditions 2change in concentration and time relationship are shown in shadow region C ' in Fig. 3, the MnO that comparative example 1 obtains x-CeO 2composite catalyst (in Fig. 3 shadow region C), reacts MnO after 3 hours x-CeO 2the CO of composite catalyst formaldehyde degradation by photocatalytic oxidation process 2generating rate is CeO 26.9 times.
Comparative example 4
Adopt method in embodiment 1, difference is only not add sodium hydroxide solution, preparation MnO x-CeO 2(Ce/Mn mol ratio 3:1) mixed oxide catalyst; By the MnO that comparative example 4 obtains x-CeO 2composite catalyst is used for thermocatalytic degraded 250ppm formaldehyde, and catalytic reaction temperature is 50 DEG C, and concrete implementation step is substantially the same manner as Example 2, and difference is the MnO using catalyst to obtain for comparative example 4 x-CeO 2composite catalyst, in addition, in catalytic reaction process, closes Xe lamp source;
Prepared MnO x-CeO 2with the MnO in embodiment 1 x-CeO 2difference is: the MnO that in embodiment 1, Hydrothermal Synthesis obtains in finite concentration alkali lye x-CeO 2(Ce/Mn mol ratio 3:1) composite oxide catalysts possesses larger specific area, less crystallite dimension, more abundant blemish and surface hydroxyl; Gained catalyst in embodiment 1 is made in the process of light, thermocatalytic degradation of formaldehyde, to have outstanding catalytic performance than the catalyst obtained in comparative example 4;
The MnO obtained in comparative example 4 x-CeO 2composite catalyst is used for CO in 50 DEG C of thermocatalytic degraded 250ppm formaldehyde processes 2change in concentration and time relationship as Fig. 8.As shown in Figure 8, the MnO synthesized by alkali liquor hydrothermal in embodiment 1 x-CeO 2(Ce/Mn mol ratio 3:1) composite catalyst is in the thermocatalytic degradation process of 3 hours, and degrade 250ppm formaldehyde CO 2generating rate is without MnO prepared by Hydrothermal Synthesis under alkaline environment in comparative example 4 x-CeO 23.1 times of (Ce/Mn mol ratio 3:1) composite catalyst.

Claims (6)

1. one kind has the MnO that low temperature photo-thermal concerted catalysis purifying VOCs and light assist self-repair function x-CeO 2the preparation method of composite semiconductor catalyst, is characterized in that, described MnO x-CeO 2the chemical formula of composite semiconductor catalyst is Ce 1-amn ao 2-δ, wherein 0<a<0.7; Described method comprises:
1) Ce salt and KMnO is taken 4, be dissolved in aqueous slkali, obtain mixing suspension, wherein, Ce salt and KMnO 4the ratio of mole and described MnO x-CeO 2in composite semiconductor catalyst, the proportionate relationship of Ce element, Mn element is consistent;
2) mix suspending liquid sealing step 1) prepared, carries out hydro-thermal reaction at 80-200 DEG C, is precipitated thing;
3) isolate step 2) sediment prepared, washing, dry after grinding namely obtain described MnO x-CeO 2composite semiconductor catalyst.
2. preparation method according to claim 1, is characterized in that, in described Ce salt, the chemical valence of Ce is trivalent or tetravalence, and described Ce salt comprises cerous nitrate, cerous chlorate, cerous sulfate, cerous sulfate and/or ammonium ceric nitrate.
3. preparation method according to claim 1 and 2, is characterized in that, the concentration of described aqueous slkali neutral and alkali material is 1-8mol/L, and described alkaline matter comprises NaOH, KOH, Na 2cO 3and/or K 2cO 3.
4., according to described preparation method arbitrary in claim 1-3, it is characterized in that, Ce salt and KMnO 4mole sum and aqueous slkali volume between ratio be (1-6) mmol:40ml.
5., according to described preparation method arbitrary in claim 1-4, it is characterized in that, the time of described hydro-thermal reaction is 8-72 hour.
6., according to described preparation method arbitrary in claim 1-5, it is characterized in that, described sedimentary baking temperature is 60-120 DEG C.
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CN106975479A (en) * 2017-04-18 2017-07-25 南京工业大学 Sea urchin-shaped CeO2‑MnO2Process for producing composite oxide catalyst
CN106975479B (en) * 2017-04-18 2019-06-04 南京工业大学 Sea urchin-shaped CeO2-MnO2Process for producing composite oxide catalyst
CN108452795A (en) * 2018-01-31 2018-08-28 太原理工大学 Load the fiber and the preparation method and application thereof of manganese dioxide-ceria bimetallic oxide
CN110314680A (en) * 2018-03-30 2019-10-11 香港理工大学深圳研究院 The catalyst and its preparation method and application of constant temperature catalyzing degradation of formaldehyde
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CN113262801A (en) * 2021-05-31 2021-08-17 中国科学院兰州化学物理研究所 Ce-Mn-based solid solution catalyst and preparation method and application thereof
CN114558566A (en) * 2022-03-12 2022-05-31 福州大学 Hydrogen sulfide selective oxidation catalyst and preparation method and application thereof
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