CN105293492A - Method for thermally reducing CO2 to synthesize CO through graphene-based catalyst - Google Patents
Method for thermally reducing CO2 to synthesize CO through graphene-based catalyst Download PDFInfo
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- CN105293492A CN105293492A CN201510664371.4A CN201510664371A CN105293492A CN 105293492 A CN105293492 A CN 105293492A CN 201510664371 A CN201510664371 A CN 201510664371A CN 105293492 A CN105293492 A CN 105293492A
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Abstract
The invention discloses a method for thermally reducing CO2 to synthesize CO through a graphene-based catalyst. The method includes the steps that the graphene-based catalyst is prepared, and a CO2-thermal-reducing CO-synthesizing experimental method and a thermal catalytic efficiency evaluating method are set. The method is characterized in that firstly, according to the catalyst, flaky graphite serves as a precursor, and graphene oxide is prepared according to a Hummers method; secondly, various kinds of oxide are prepared; finally, an oxide composite graphene catalyst is prepared with a chemistry stripping method. The catalyst is good in stability and high in dispersity, and the CO2-thermal-reducing CO-synthesizing catalytic efficiency of the catalyst is much higher than that of pure oxide and graphene. The method is carried out in a closed glass reactor under the low-temperature condition (without illumination), and has the advantages of being low in device requirement, easy to operate, free of illumination, easy to apply and the like. By means of the method, the new direction is developed for preparing of a novel efficient thermal catalyst and an application to the environment governance field and the new energy field.
Description
[technical field]
The invention discloses one and utilize graphene-based catalyzer thermal reduction CO
2the method of synthesis CO, the thermocatalysis reduction CO of this catalyzer
2the efficiency of synthesis CO is far above pure-oxide and Graphene.The invention belongs to thermocatalysis technical field, prepare carbon monoxide for utilizing catalysis technique reducing carbon dioxide and water and provide a kind of novel and easy method.
[background technology]
Environmental pollution and energy shortage have become the main crisis that the world today faces, and people constantly probe into the novel method of Environment control and exploitation renewable energy source.In 1972, Fujishima and Honda report adopted TiO
2optoelectronic pole and platinum electrode composition photoelectrochemistry system break water into hydrogen and oxygen, thus open this new research field of semi-conductor catalysis.In recent years, by CO
2be reduced into the study hotspot that hydrocarbon fuel has become energy environment scientific domain.This research is for exploitation renewable energy source and remove CO in air
2gas, reduces Greenhouse effect and has important scientific meaning.
The open one of the present invention utilizes graphene-based catalyzer thermal reduction CO
2the method of synthesis CO.The method is the graphene-based catalyzer thermal reduction CO under cryogenic utilizing development
2synthesis CO, and the method conditional request is simple, without the need to illumination and applicability is strong; Utilize this catalyst thermo-catalytic reducing carbon dioxide and water to generate carbon monoxide, its thermocatalysis efficiency is far above pure-oxide and Graphene.At present, the research work that under low temperature, thermocatalysis reducing carbon dioxide and water prepare carbon monoxide has no report, and this achievement in research is by for opening up new direction in Environment control and the field such as to tap a new source of energy.
[summary of the invention]
The present invention discloses one and utilizes graphene-based catalyzer thermal reduction CO
2the method of synthesis CO, its summary of the invention comprises following aspect: 1. first is presoma with flaky graphite, method with reference to Hummers prepares graphene oxide, then prepares various oxide compound, obtains oxide compound composite graphite alkene catalyzer finally by Chemical peeling legal system.2. establish and utilize this catalyzer (25 ~ 90 DEG C) thermal reduction CO effectively under cryogenic
2the experimental technique of synthesis CO and the evaluation method of generation CO efficiency.3. utilize graphene-based catalyzer to carry out thermal reduction CO
2the experiment of synthesis CO.Result shows: graphene-based catalyzer has very high thermocatalysis efficiency under cryogenic, and its thermocatalysis efficiency is far above pure-oxide and Graphene; Simple and the implementation condition of the method technique requires low, and by force, the evaluation method of thermocatalysis activity is accurately feasible for easy to operate and applicability.
Concrete grammar of the present invention is as follows:
1. the preparation of graphite alkenyl nanometer materials
First is presoma with flaky graphite, and the method with reference to Hummers prepares graphene oxide, then prepares various oxide compound, obtains oxide compound composite graphite alkene catalyzer finally by Chemical peeling legal system.
2. thermocatalysis reduction CO
2the experimental technique of synthesis CO and the evaluation method of generation CO efficiency
Thermocatalysis reduction CO
2and H
2the experiment of O carries out in 280ml cylinder shape glass reactor under cryogenic.First take 100mg catalyzer, be laid on the slide glass of 2.5 × 7.5cm.Again slide glass is placed in reactor center.Then in reactor, CO is passed into
2gas, gas purity is 99.999%, and flow is 0.2Lmin
-1, the time is 35min, makes CO in order to the air got rid of in reactor
2gas reaches capacity.Inflation terminates rear injection 1.5ml deionized water in reactor and seals.Recently whole reaction system is fixed in thermostatic drying chamber under cryogenic.The gas of the 0.4ml in 4h abstraction reaction device, adopts the concentration of gas chromatograph for determination product C O, and carries out the thermal synthesis contrast experiment of catalyst-free under the same conditions.
Further technical scheme is, described cold condition is 25 ~ 90 DEG C.
Further technical scheme is, described oxide compound can be WO
3, ZnO, ZrO
2, CeO
2, MnO
2or TiO
2in any one.
For a better understanding of the present invention, below in conjunction with embodiment, the present invention is described in further detail, but the scope of protection of present invention is not limited to the scope represented by embodiment.
[accompanying drawing explanation]
The XRD figure spectrum of sample in Fig. 1 embodiment 1;
The thermocatalysis reduction CO of sample in Fig. 2 embodiment 1
2the activity figure of synthesis CO;
20%WO under differing temps in Fig. 3 embodiment 1
3the thermocatalysis activity figure of/graphene sample;
The thermocatalysis reduction CO of sample in Fig. 4 embodiment 2
2the activity figure of synthesis CO;
Below in conjunction with specific embodiments and the drawings, the present invention is described further, and illustrates thermocatalysis effect of the present invention.
[embodiment]
Embodiment 1
WO
3preparation: claim 3g sodium wolframate and 0.01g cetyl trimethylammonium bromide (CTAB), be dissolved in 10mL deionized water.After stirring 0.5h, with 3mol/LHCl regulator solution PH=0.3.Continue to stir 1h, be transferred in reactor and fill 80%, place 24h in 120 DEG C, thermostatic drying chamber case.Centrifugal settling, gained precipitation distilled water, acetone repetitive scrubbing, in 60 DEG C of dry 10h.Finally 300 DEG C of calcination 3h in retort furnace, obtained WO
3powder.
Hummers legal system is as follows for the technical process that graphite oxide is concrete: preparation method is as follows for Graphene composite titanium dioxide based nano-material: the beaker assembling 1L in ice-water bath, adds the vitriol oil of 115mL.Add the solid mixture of 5g crystalline flake graphite and 2.5g SODIUMNITRATE under continuous stirring, then gradation adds 15g potassium permanganate, control temperature of reaction and be no more than 20 DEG C.Then liquid is warmed up to 35 DEG C, continues to stir 60min.Slowly add the deionized water of 230mL again, liquid acutely seethes with excitement and maintains the temperature at about 98 DEG C 15min.And add 0.7L distilled water and 12.5mL hydrogen peroxide, finally with 1L5%HCl solution and deionized water wash until in filtrate sulfate radical-free be detected.Last fully dry in the vacuum drying oven of 60 DEG C, obtain graphene oxide.
WO
3/ graphene method for preparing catalyst is as follows: 1: 9 ~ 1: 1 WO3 and graphene oxide are placed in 500ml beaker in mass ratio, add 280ml dehydrated alcohol, the ultrasonic 1h of normal temperature.Then add 2mlNaOH solution (8mol/L), continue ultrasonic 5h, temperature remains 75 DEG C.Ultrasonic end leaves standstill 24h afterwards, is outwelled by supernatant liquid, finally uses ethanol purge 5 times, dry at 50 DEG C, i.e. obtained WO
3/ graphene catalyzer.
Embodiment 2
The preparation of ZnO: claim in 3.67g zinc nitrate and 0.1g hexadecyl ammonium bromide solution 50ml deionized water, then add 50ml sodium carbonate solution (0.25mol/L).Keep agitation 2h, makes two kinds of solution fully react.Centrifugal, washing, in 60 DEG C of dryings, obtains zinc subcarbonate.Finally in the retort furnace of 600 DEG C, calcine 2.5h, obtained ZnO sample.
All the other experiment conditions, step are with embodiment 1.
Below brief description is done to accompanying drawing:
Fig. 1 shows successfully to prepare WO
3, graphene and WO
3/ graphene catalyzer.
Fig. 2 shows pure WO
3thermocatalysis reduction CO
2the activity of synthesis CO is very low, only has 0.155 μm of olCO to generate.When reaction is after 32 hours, it is 1.03 μm of ol that pure graphene generates CO amount.For the sample of compound, 20%WO
3it is active that/graphene shows the highest thermocatalysis, and have the CO of 4.53 μm of ol to generate, its thermocatalysis activity is pure WO respectively
3with 29 times and 4.5 times of graphene.
Fig. 3 shows along with temperature raises, 20%WO
3the also corresponding raising of/graphene sample thermocatalysis activity.
Fig. 4 is the thermocatalysis activity figure of ZnO/graphene series of samples.After result shows compound, 15%ZnO/graphene sample thermocatalysis activity is the highest, and reacting after 10 hours and have the CO of 2.38 μm of ol to generate, is 65.5 times and 4.1 times of pure ZnO and graphene respectively.
As can be seen from above example, oxide compound composite graphite alkene sample is compared with Graphene with pure-oxide, and the catalytic activity that its thermal reduction CO2 synthesizes CO is greatly improved.
Claims (3)
1. one kind utilizes graphene-based catalyzer thermal reduction CO
2the method of synthesis CO, it comprises: prepare graphene-based catalyzer, sets up thermocatalysis reduction CO
2the synthesis experimental technique of CO and the evaluation method of thermocatalysis efficiency; The feature of described graphene-based catalyzer is that first is presoma with flaky graphite, and the method with reference to Hummers prepares graphene oxide, then prepares various oxide compound, prepares oxide compound composite graphite alkene catalyzer finally by Chemical peeling method; This catalyst stability is good, dispersed strong and its thermal reduction CO
2the catalytic efficiency of synthesis CO is far above pure-oxide and Graphene; Thermocatalysis reduction CO
2the feature of the synthesis experimental technique of CO and the evaluation method of thermocatalysis efficiency is thermal reduction CO
2and H
2the experiment of O carries out in 280ml cylinder shape glass reactor under cryogenic; First take a certain amount of catalyzer, be laid on the slide glass of 2.5 × 7.5cm; Again slide glass is placed in reactor center; Then in reactor, CO is passed into
2gas, gas purity is 99.999%, and flow is 0.2Lmin
-1, the time is 35min, makes CO in order to the air got rid of in reactor
2gas reaches capacity, and inflation terminates inject 1.5ml deionized water in backward reactor and seal; Recently whole reaction system is fixed in thermostatic drying chamber under cryogenic, the gas of the 0.4ml in 4h abstraction reaction device, adopt the concentration of gas chromatograph for determination product C O, and carry out the thermal synthesis contrast experiment of catalyst-free under the same conditions.
2. according to claim 1ly utilize graphene-based catalyzer thermal reduction CO
2the method of synthesis CO, it is characterized in that, described cold condition is 25 ~ 90 DEG C.
3. according to claim 1 and 2ly utilize graphene-based catalyzer thermal reduction CO
2the method of synthesis CO, it is characterized in that, described oxide compound can be WO
3, ZnO, ZrO
2, C
eo
2, MnO
2or TiO
2in any one.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622235A (en) * | 2016-12-05 | 2017-05-10 | 中国科学院上海硅酸盐研究所 | Graphene coated alloy nano catalyst for converting carbon dioxide into carbon monoxide and preparation method thereof |
| CN110252372A (en) * | 2019-05-31 | 2019-09-20 | 江苏大学 | A kind of two dimension rGO/R-CeO2The preparation method of/CNNS hierarchical structure composite photo-catalyst |
| CN112889774A (en) * | 2021-01-21 | 2021-06-04 | 庄玉林 | LED display screen of protection against insects destruction |
| CN115487850A (en) * | 2022-10-28 | 2022-12-20 | 南京工程学院 | Photo-thermal catalytic composite material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103097289A (en) * | 2010-10-26 | 2013-05-08 | 三井金属矿业株式会社 | Method for producing carbon monoxide and production apparatus |
| CN104302575A (en) * | 2012-04-16 | 2015-01-21 | 赛尔斯通股份有限公司 | Method for producing solid carbon by reducing carbon dioxide |
-
2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103097289A (en) * | 2010-10-26 | 2013-05-08 | 三井金属矿业株式会社 | Method for producing carbon monoxide and production apparatus |
| CN104302575A (en) * | 2012-04-16 | 2015-01-21 | 赛尔斯通股份有限公司 | Method for producing solid carbon by reducing carbon dioxide |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622235A (en) * | 2016-12-05 | 2017-05-10 | 中国科学院上海硅酸盐研究所 | Graphene coated alloy nano catalyst for converting carbon dioxide into carbon monoxide and preparation method thereof |
| CN106622235B (en) * | 2016-12-05 | 2019-08-16 | 中国科学院上海硅酸盐研究所 | For being the graphene coated alloy nano catalyst and preparation method thereof of carbon monoxide by carbon dioxide conversion |
| CN110252372A (en) * | 2019-05-31 | 2019-09-20 | 江苏大学 | A kind of two dimension rGO/R-CeO2The preparation method of/CNNS hierarchical structure composite photo-catalyst |
| CN112889774A (en) * | 2021-01-21 | 2021-06-04 | 庄玉林 | LED display screen of protection against insects destruction |
| CN115487850A (en) * | 2022-10-28 | 2022-12-20 | 南京工程学院 | Photo-thermal catalytic composite material and preparation method and application thereof |
| CN115487850B (en) * | 2022-10-28 | 2023-10-24 | 南京工程学院 | Photo-thermal catalytic composite material and preparation method and application thereof |
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