CN108707925B - A kind of preparation method for the RGO/Mn/TNTs optoelectronic pole improving photogenerated charge separation and carbon dioxide reduction performance - Google Patents

A kind of preparation method for the RGO/Mn/TNTs optoelectronic pole improving photogenerated charge separation and carbon dioxide reduction performance Download PDF

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CN108707925B
CN108707925B CN201810582659.0A CN201810582659A CN108707925B CN 108707925 B CN108707925 B CN 108707925B CN 201810582659 A CN201810582659 A CN 201810582659A CN 108707925 B CN108707925 B CN 108707925B
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CN108707925A (en
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冯玉杰
吴晶
刘佳
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Harbin Institute of Technology
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    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes

Abstract

A kind of preparation method for the RGO/Mn/TNTs optoelectronic pole improving photogenerated charge separation and carbon dioxide reduction performance, the present invention relates to what photogenerated charge separation improved to be used to restore CO2Optoelectronic pole preparation method field.The invention solves existing TiO2Nanotube array photoelectrode is in photo catalytic reduction CO2The technical problem that existing visible light utilization efficiency is low in the process and photogenerated charge separation is poor.Method: the one, TiO of MnOx modification2The preparation of nanotube array photoelectrode；Two, RGO and MnOx co-modified TiO2The preparation of nanotube array photoelectrode.The present invention realizes the co-modified TiO of RGO and MnOx2Nanotube array photoelectrode is applied to photo catalytic reduction CO2Process, the optoelectronic pole of the preparation is placed in the KHCO containing 0.05M~5M3Electrolyte solution, long 4cm, wide 3cm, side are that a certain amount of liquid assay reduzate therein is extracted after illumination 1h in the organic glass reactor of quartz glass.The present invention is used to prepare the co-modified reduction CO of RGO and MnOx2TiO2Nanotube array photoelectrode.

Description

A kind of RGO/Mn/TNTs improving photogenerated charge separation and carbon dioxide reduction performance The preparation method of optoelectronic pole
Technical field
The present invention relates to what photogenerated charge separation improved to be used to restore CO2Optoelectronic pole preparation method field.
Background technique
The fast development of modern society brings serious environmental pollution and energy problem.The burning of a large amount of fossil fuels makes Obtain the CO in air2Content rapidly increases, and causes serious destruction to nature original carbon cycle balance, results in serious Greenhouse effects.How in air CO is reduced2Concentration, effectively utilize CO2, built environment is friendly, energy conservation low-carbon warp Ji has become the hot spot studied extensively both at home and abroad.At the same time, CO2As a kind of resource, examined from angle economical and environmentally friendly Consider, if organic matter can be converted it into and be used, so that it may reduce CO2Concentration, while solving environmental problem, A kind of recycling resource is obtained, so that shortage of resources problem is also well solved.
The catalyzed conversion that carbon dioxide is carried out using conductor photocatalysis, by CO2It is converted into liquid fuel, is that solution is above-mentioned The desirable route of problem.Since the transform mode carries out at room temperature, and the H in reaction+It is more environmentally friendly from water, by The concern of many researchers.Photocatalysis CO2Reduction refers to that Nano semiconductor catalyst is excited in the case where illumination, photoproduction Electronics is excited to conduction band by valence band.It is conducted since light induced electron has very strong reducing power, after being excited molten to electrolyte Reduction CO is used in liquid2。
In in the past few decades, researcher always strives to find a kind of efficient, cheap and stable semiconductor light and urges Agent is used for photo catalytic reduction CO2, in numerous photochemical catalysts, TiO2Stablized with its chemical property, it is nontoxic, it is without secondary pollution The advantages that, it gets the favour of people.With the TiO of pure powdered form2It compares, using metal Ti substrate as the source Ti, using anodic oxidation Method, the one-dimensional TiO with hollow structure directly grown on Ti substrate surface2Nano-tube array has large specific surface area, inhales Attached ability is strong, and more smoothly carrier transport performance.But TiO2There is also defects for itself: (1) wider band gap makes It can only absorb the ultraviolet light that 2~4% are only accounted in solar spectrum, it is seen that light utilization efficiency is low.(2) the compound probability of photogenerated charge is high, Quantum yield is lower, typically exhibits the photo catalytic reduction CO of difference2Activity.To solve the above-mentioned problems, currently used method There is dye sensitization, dye sensitization, which refers to, modifies the photosensitizer substance with visible light absorption in semiconductor surface, with this Expand its visible absorption range, to improve its visible light catalysis activity, common functional dye mainly has chlorophyllin, glimmering Light element derivative and thionine etc..But exists under many functional dye illumination and easily decompose, cause the drawbacks of secondary pollution.
In addition, constructing hetero-junctions compound system is also the effective ways for improving its photogenerated charge separative efficiency.Such as WO3/ TiO2、CdS/TiO2、Fe2O3/TiO2Equal hetero-junctions system is constructed.Light induced electron can be flowed to from the higher side of fermi level to A lower side thus forms Schottky barrier in interface junction, to increase the photoproduction electricity of compound system Its visible light absorption capacity and catalytic activity are improved in son-hole to separating effect.But semiconductors coupling also has potential disadvantage End, this is mainly due to the holes being retained in valence band, and " photetching " phenomenon may be generated with semiconductor, causes secondary pollution.
Summary of the invention
The invention solves existing TiO2Nanotube array photoelectrode is in photo catalytic reduction CO2Existing visible light in the process Utilization rate is low and the technical problem of photogenerated charge separation difference, and provides a kind of raisings photogenerated charge and separate and carbon dioxide reduction The preparation method of the RGO/Mn/TNTs optoelectronic pole of performance.
A kind of preparation method for the RGO/Mn/TNTs optoelectronic pole improving photogenerated charge separation and carbon dioxide reduction performance, Specifically sequentially include the following steps:
One, using pretreated metal Ti foil as anode, Pt piece is as cathode, and the glycerin solution of ammonium fluoride is as electricity Electrolyte solution is handled metal Ti foil using anodizing, and control anodic oxidation voltage is 5~20V, and oxidization time is 1~5h is taken out metal Ti foil, is cleaned using deionized water, dry, is placed into Muffle furnace, controlled at 100~800 DEG C, 2~10h is calcined, TiO is obtained2Nano-tube array；
Two, acetic acid is added to KMnO4In solution, 5~100min of magnetic agitation adds the TiO that step 1 obtains2It receives Then mitron array impregnates 1~10h in a vacuum drying oven, take out, place into vacuum oven, controlled at 10~ 100 DEG C, dry 1h~10h, in N2In atmosphere, under the conditions of temperature is 10~600 DEG C, 1h~10h is calcined, MnO is obtainedxModification TiO2Nanotube array photoelectrode, i.e. Mn/TNTs optoelectronic pole；Wherein x is the atomicity of O；
Three, using the Mn/TNTs optoelectronic pole of step 2 preparation as working electrode, Pt piece is used as to electrode, is saturated calomel electricity Pole is as reference electrode, the Na of graphene oxide2SO4For solution as electrolyte, control constant potential is -0.1V~-2V, reaction 1min~50min is obtained the Mn/TNTs optoelectronic pole of RGO deposition, is rinsed using deionized water, then controlled at 10~200 DEG C, it is dried in vacuo 1h~20h, the RGO/Mn/TNTs optoelectronic pole is made.
This method uses simple infusion process, utilizes metal oxide MnOxTo prepared TiO2Nano-tube array photoelectricity Pole is surface modified, and passes through MnOxPhotohole is regulated and controled to the capture effect of photohole；Modifying metal oxide MnOxTiO2Nanotube array photoelectrode surface uses electrodeposition process, and TiO is arrived in redox graphene (RGO) modification2Nanometer Pipe array photoelectric pole surface realizes MnOxIt is co-modified with RGO, light induced electron is transmitted and shifted using RGO, is realized to photoproduction The double regulation control of electrons and holes.With only modify MnOxOr the one direction of RGO regulates and controls photohole or light induced electron TiO2Nanotube array photoelectrode is compared, the optoelectronic pole light induced electron of this double regulation control and hole it is isolated further It improves, photo catalytic reduction CO2Performance also gets a promotion.
The beneficial effects of the present invention are:
1, the present invention is by utilizing RGO and MnOxTo TiO2Nanotube array photoelectrode progress is co-modified, successfully realizes To the double regulation control of light induced electron and hole, TiO is improved2The photogenerated charge of nanotube array photoelectrode separates and to visible light Absorption.
2, the present invention utilizes the co-modified optoelectronic pole, compared to merely with RGO or MnOxTo TiO2Nanotube array photoelectrode For the optoelectronic pole individually modified, CO2Reducing property is significantly improved, and photoelectric properties have also obtained greatly mentioning It is high.
3, RGO/Mn/TNTs optoelectronic pole prepared by the present invention has good stability.
The present invention realizes RGO and MnOxCo-modified TiO2Nanotube array photoelectrode is applied to photo catalytic reduction CO2's The optoelectronic pole of the preparation is placed in the KHCO containing 0.05M~5M by process3Electrolyte solution, long 4cm, wide 3cm, side are stone In the organic glass reactor of English glass, a certain amount of liquid assay reduzate therein is extracted after illumination 1h.
The present invention is used to prepare the co-modified reduction CO of RGO and MnOx of the reduction carbon dioxide of photogenerated charge separation2's TiO2Nanotube array photoelectrode.
Detailed description of the invention
Fig. 1 is that embodiment one prepares RGO/Mn/TNTs optoelectronic pole in catalysis reduction CO2Light induced electron and hole pass in the process It passs and transfer process figure；
Fig. 2 is the scanning electron microscope diagram of RGO/Mn/TNTs optoelectronic pole prepared by embodiment one；
Fig. 3 is the Mn/TNTs photoelectricity of the TNTs optoelectronic pole of one step 1 of embodiment preparation, the preparation of one step 2 of embodiment The RGO/Mn/TNTs optoelectronic pole of RGO/TNTs optoelectronic pole, the preparation of embodiment one prepared by pole, embodiment two carries out photo catalytic reduction CO2Test data, wherein a represents acetic acid, and b represents formic acid, and c represents methanol.
Specific embodiment
Technical solution of the present invention is not limited to the specific embodiment of act set forth below, further include each specific embodiment it Between any combination.
Specific embodiment 1: a kind of RGO/ for improving photogenerated charge separation and carbon dioxide reduction performance of present embodiment The preparation method of Mn/TNTs optoelectronic pole, specifically sequentially includes the following steps:
One, using pretreated metal Ti foil as anode, Pt piece is as cathode, and the glycerin solution of ammonium fluoride is as electricity Electrolyte solution is handled metal Ti foil using anodizing, and control anodic oxidation voltage is 5~20V, and oxidization time is 1~5h is taken out metal Ti foil, is cleaned using deionized water, dry, is placed into Muffle furnace, controlled at 100~800 DEG C, 2~10h is calcined, TiO is obtained2Nano-tube array；
Two, acetic acid is added to KMnO4In solution, 5~100min of magnetic agitation adds the TiO that step 1 obtains2It receives Then mitron array impregnates 1~10h in a vacuum drying oven, take out, place into vacuum oven, controlled at 10~ 100 DEG C, dry 1h~10h, in N2In atmosphere, under the conditions of temperature is 10~600 DEG C, 1h~10h is calcined, MnO is obtainedxModification TiO2Nanotube array photoelectrode, i.e. Mn/TNTs optoelectronic pole；
Three, using the Mn/TNTs optoelectronic pole of step 2 preparation as working electrode, Pt piece is used as to electrode, is saturated calomel electricity Pole is as reference electrode, the Na of graphene oxide2SO4For solution as electrolyte, control constant potential is -0.1V~-2V, reaction 1min~50min is obtained the Mn/TNTs optoelectronic pole of RGO deposition, is rinsed using deionized water, then controlled at 10~200 DEG C, it is dried in vacuo 1h~20h, the RGO/Mn/TNTs optoelectronic pole is made.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: oxalic acid pair is used in step 1 Metal Ti foil is pre-processed.It is other same as the specific embodiment one.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that: ammonium fluoride in step 1 Glycerin solution in ammonium fluoride mass concentration be 0.5%.It is other the same as one or two specific embodiments.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three: being done in step 1 Dry temperature is 50~100 DEG C, and drying time is 1~10h.It is other identical as one of specific embodiment one to three.
Specific embodiment 5: unlike one of present embodiment and specific embodiment one to four: horse in step 1 Not the heating rate of furnace is 1~10 DEG C of min-1.It is other identical as one of specific embodiment one to four.
Specific embodiment 6: unlike one of present embodiment and specific embodiment one to five: in step 2 KMnO4The concentration of solution is 0.01g/mL.It is other identical as one of specific embodiment one to five.
Specific embodiment 7: unlike one of present embodiment and specific embodiment one to six: second in step 2 The additional amount of acid is 5~100mL.It is other identical as one of specific embodiment one to six.
Specific embodiment 8: unlike one of present embodiment and specific embodiment one to seven: being soaked in step 2 Stain temperature is 20 DEG C.It is other identical as one of specific embodiment one to seven.
Specific embodiment 9: unlike one of present embodiment and specific embodiment one to eight: being forged in step 2 Heating rate when burning is 1~10 DEG C of min-1.It is other identical as one of specific embodiment one to eight.
Specific embodiment 10: unlike one of present embodiment and specific embodiment one to nine: oxygen in step 3 The Na of graphite alkene2SO4The concentration of graphene oxide is 0.5mol/L in solution.One of other and specific embodiment one to nine It is identical.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one:
A kind of system for the RGO/Mn/TNTs optoelectronic pole for improving photogenerated charge separation and carbon dioxide reduction performance of the present embodiment Preparation Method specifically sequentially includes the following steps:
One, using pretreated metal Ti foil as anode, Pt piece is as cathode, and the glycerin solution of ammonium fluoride is as electricity Electrolyte solution is handled metal Ti foil using anodizing, control anodic oxidation voltage be 15V, oxidization time 2h, Metal Ti foil is taken out, is cleaned using deionized water, it is dry, it places into Muffle furnace, controlled at 500 DEG C, calcines 3h, obtain TiO2Nano-tube array, i.e. TNTs optoelectronic pole；
Two, acetic acid is added to KMnO4In solution, magnetic agitation 30min adds the TiO that step 1 obtains2Nanotube Then array impregnates 2h in a vacuum drying oven, take out, place into vacuum oven, controlled at 70 DEG C, dry 4h, In N2In atmosphere, under the conditions of temperature is 550 DEG C, 2h is calcined, MnO is obtainedxThe TiO of modification2Nanotube array photoelectrode, i.e. Mn/ TNTs optoelectronic pole；Wherein MnOxFor MnO and Mn2O3；
Three, using the Mn/TNTs optoelectronic pole of step 2 preparation as working electrode, Pt piece is used as to electrode, is saturated calomel electricity Pole is as reference electrode, the Na of graphene oxide2SO4For solution as electrolyte, control constant potential is -0.8V, reacts 15min, obtains The Mn/TNTs optoelectronic pole deposited to RGO, is rinsed using deionized water, then controlled at 70 DEG C, is dried in vacuo 4h, is made The RGO/Mn/TNTs optoelectronic pole.
The Mn/TNTs photoelectricity extremely 0.8Mn/TNTs of the present embodiment step 2 preparation；The RGO/Mn/TNTs of step 3 preparation Photoelectricity extremely 6RGO/0.8Mn/TNTs.
Metal Ti foil is pre-processed using oxalic acid in step 1；The concentration of the glycerin solution of ammonium fluoride in step 1 Mass concentration for middle ammonium fluoride is 0.5%；Drying temperature is 70 DEG C in step 1, drying time 2h；Muffle in step 1 The heating rate of furnace is 5 DEG C of min-1；
KMnO in step 24The concentration of solution is 0.01g/mL；The additional amount of acetic acid is 20mL in step 2；In step 2 Dipping temperature is 20 DEG C；Heating rate when calcining in step 2 is 5 DEG C of min-1；
The Na of graphene oxide in step 32SO4The concentration of graphene oxide is 0.5mol/L in solution.
A kind of embodiment two: TiO of RGO modification of present embodiment2The preparation method of nanotube array photoelectrode is as follows:
One, using pretreated metal Ti foil as anode, Pt piece is as cathode, and the glycerin solution of ammonium fluoride is as electricity Electrolyte solution is handled metal Ti foil using anodizing, control anodic oxidation voltage be 15V, oxidization time 2h, Metal Ti foil is taken out, is cleaned using deionized water, it is dry, it places into Muffle furnace, controlled at 500 DEG C, calcines 3h, obtain TiO2Nano-tube array；
Two, the TiO for preparing step 12As working electrode, Pt piece is used as to electrode nano-tube array, is saturated calomel electricity Pole is as reference electrode, the Na of graphene oxide2SO4For solution as electrolyte, control constant potential is -0.8V, reacts 15min, obtains The TiO deposited to RGO2Nano-tube array is rinsed using deionized water, then controlled at 70 DEG C, is dried in vacuo 4h, is made The TiO of RGO modification2Nanotube array photoelectrode, i.e. RGO/TNTs optoelectronic pole.
RGO/TNTs photoelectricity extremely 6RGO/TNTs manufactured in the present embodiment.
Embodiment one prepares RGO/Mn/TNTs optoelectronic pole light induced electron and hole-transfer and transfer process in catalytic process Figure, as shown in Figure 1；
The scanning electron microscope diagram of RGO/Mn/TNTs optoelectronic pole prepared by embodiment one, as shown in Fig. 2, can from figure To find out, MnOxThe surface of TNTs optoelectronic pole has been successfully introduced with RGO.
The TNTs optoelectronic pole of one step 1 of embodiment preparation, the Mn/TNTs optoelectronic pole of one step 2 of embodiment preparation, implementation The RGO/Mn/TNTs optoelectronic pole of RGO/TNTs optoelectronic pole, the preparation of embodiment one prepared by example two carries out photo catalytic reduction CO2Survey Data are tried, as shown in figure 3, wherein a represents acetic acid, b represents formic acid, and c represents methanol, as can be seen that TNTs light is urged from data Change reduction CO2Primary product be formic acid, acetic acid and methanol, modify MnOxWith the primary product after RGO be formic acid and acetic acid, and Individually modification MnOxOr the yield of formic acid and acetic acid is improved after RGO.And compared with pure TNTs optoelectronic pole, MnOxIt is total with RGO The formic acid and yield of acetic acid of the TNTs optoelectronic pole of modification greatly improve.Illustrate in RGO/Mn/TNTs optoelectronic pole prepared by the present invention MnOxThe double regulation control function to photohole and electronics is played with RGO.

Claims (9)

1. a kind of preparation method for the RGO/Mn/TNTs optoelectronic pole for improving photogenerated charge separation and carbon dioxide reduction performance, It is characterized in that this method specifically sequentially includes the following steps:
One, using pretreated metal Ti foil as anode, Pt piece is as cathode, and the glycerin solution of ammonium fluoride is as electrolyte Solution is handled metal Ti foil using anodizing, control anodic oxidation voltage be 5~20V, oxidization time be 1~ 5h is taken out metal Ti foil, is cleaned using deionized water, dry, is placed into Muffle furnace, controlled at 100~800 DEG C, is forged 2~10h is burnt, TiO is obtained2Nano-tube array；
Two, acetic acid is added to KMnO4In solution, 5~100min of magnetic agitation adds the TiO that step 1 obtains2Nanotube Then array impregnates 1~10h in a vacuum drying oven, take out, place into vacuum oven, controlled at 10~100 DEG C, dry 1h~10h, in N2In atmosphere, under the conditions of temperature is 10~600 DEG C, 1h~10h is calcined, MnO is obtainedxThe TiO of modification2 Nanotube array photoelectrode, i.e. Mn/TNTs optoelectronic pole；Wherein x is the atomicity of O；
Three, using the Mn/TNTs optoelectronic pole of step 2 preparation as working electrode, Pt piece is used as to electrode, and saturated calomel electrode is made For reference electrode, the Na of graphene oxide2SO4For solution as electrolyte, control constant potential is -0.1V~-2V, reaction 1min~ 50min is obtained the Mn/TNTs optoelectronic pole of RGO deposition, is rinsed using deionized water, then controlled at 10~200 DEG C, very Dry 1h~the 20h of sky, is made the RGO/Mn/TNTs optoelectronic pole；
Metal Ti foil is pre-processed using oxalic acid in step 1.
2. a kind of RGO/Mn/TNTs for improving photogenerated charge separation and carbon dioxide reduction performance according to claim 1 The preparation method of optoelectronic pole, it is characterised in that the mass concentration of ammonium fluoride is in the glycerin solution of ammonium fluoride in step 1 0.5%.
3. a kind of RGO/Mn/TNTs for improving photogenerated charge separation and carbon dioxide reduction performance according to claim 1 The preparation method of optoelectronic pole, it is characterised in that drying temperature is 50~100 DEG C in step 1, and drying time is 1~10h.
4. a kind of RGO/Mn/TNTs for improving photogenerated charge separation and carbon dioxide reduction performance according to claim 1 The preparation method of optoelectronic pole, it is characterised in that the heating rate of Muffle furnace is 1~10 DEG C of min in step 1-1。
5. a kind of RGO/Mn/TNTs for improving photogenerated charge separation and carbon dioxide reduction performance according to claim 1 The preparation method of optoelectronic pole, it is characterised in that KMnO in step 24The concentration of solution is 0.01g/mL.
6. a kind of RGO/Mn/TNTs for improving photogenerated charge separation and carbon dioxide reduction performance according to claim 1 The preparation method of optoelectronic pole, it is characterised in that the additional amount of acetic acid is 5~100mL in step 2.
7. a kind of RGO/Mn/TNTs for improving photogenerated charge separation and carbon dioxide reduction performance according to claim 1 The preparation method of optoelectronic pole, it is characterised in that dipping temperature is 20 DEG C in step 2.
8. a kind of RGO/Mn/TNTs for improving photogenerated charge separation and carbon dioxide reduction performance according to claim 1 The preparation method of optoelectronic pole, it is characterised in that heating rate when calcining in step 2 is 1~10 DEG C of min-1。
9. a kind of RGO/Mn/TNTs for improving photogenerated charge separation and carbon dioxide reduction performance according to claim 1 The preparation method of optoelectronic pole, it is characterised in that the Na of graphene oxide in step 32SO4The concentration of graphene oxide is in solution 0.5mol/L。
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