CN112973729B - TiO of rich oxygen vacancy/AuCu alloy 2 Preparation method and application of nano square sheet - Google Patents

TiO of rich oxygen vacancy/AuCu alloy 2 Preparation method and application of nano square sheet Download PDF

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CN112973729B
CN112973729B CN202110167051.3A CN202110167051A CN112973729B CN 112973729 B CN112973729 B CN 112973729B CN 202110167051 A CN202110167051 A CN 202110167051A CN 112973729 B CN112973729 B CN 112973729B
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姜德立
张乾晓
李娣
周以萌
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Jiangsu University
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Abstract

The invention belongs to the field of nano materials, and discloses TiO rich in oxygen vacancy/AuCu alloy 2 The preparation method of the nanosheet photocatalyst comprises the step of preparing TiO by a hydrothermal method 2 Preparing TiO rich in AuCu alloy by nanosheet and oil bath method 2 Nanosheet and further preparing TiO rich in oxygen vacancy/AuCu alloy through hydrogen reduction 2 Nanosheets. Ti in the vicinity of oxygen vacancy 3+ As an electron donor for photocatalytic reduction of CO 2 The reaction provides electrons; au promotes the formation of CO intermediates; cu can generate enough H to favor CO to CH 4 The conversion of (1). Surface oxygen vacancy and AuCu alloy synergy to enable TiO rich in oxygen vacancy/AuCu alloy 2 The nano-sheet photocatalyst can directionally convert CO 2 To high value-added hydrocarbons. The material can be used for photocatalytic reduction of CO 2 Preparation of CH 4 The method has important significance for the development of clean energy.

Description

TiO of rich oxygen vacancy/AuCu alloy 2 Preparation method and application of nano square sheet
Technical Field
The invention belongs to the field of nano materials, and relates to TiO 2 A method for preparing a nano square sheet, in particular to a TiO rich in oxygen vacancy/AuCu alloy 2 A nano square tablet and a preparation method and application thereof.
Technical Field
Titanium dioxide (TiO) 2 ) As a semiconductor material which is most widely researched, the semiconductor material has the characteristics of low price, stable performance, abundant reserves, no toxicity and the like, and attracts people's wide attention. However, in practical application, the forbidden band width is large (3.0-3.2 eV), and sites for regulating and controlling reaction paths are lacked, so that the solar energy utilization rate is seriously low, and the photocatalytic performance is low.
In recent years, photocatalytic systems rich in oxygen vacancies have been used for the photocatalytic reduction of CO 2 The aspect shows unique advantages. Oxygen vacancy rich TiO 2 The preparation is simple, the cost is low, and the method is a research hotspot for photocatalytic carbon dioxide emission reduction. Ti in the vicinity of oxygen vacancy 3+ Not only can be used as a strong electron donor to be CO 2 Provide a large number of electrons and can act as a trap and activate CO 2 Increasing CO, increasing the reaction sites of 2 The adsorption performance of (2) and the activation energy required by the reaction are reduced. In addition, the surface oxygen vacancy can adjust the electronic structure of the catalyst, expand the response range of incident light, promote the separation of photo-generated charges and further improve the photocatalytic activity of the catalyst. At present, researchers at home and abroad intensify photocatalytic material to reduce CO by surface oxygen vacancy 2 A series of highly effective works have been carried out in terms of performance. For example, huang et al prepared an oxygen vacancy-rich blue TiO 2 In the photocatalytic reduction of CO 2 Shows excellent performance in the process of (2). The presence of oxygen vacancies enhances the visible light absorption properties, providing a rich set of active sites. Based on these advantages, CH 4 Has a formation rate of 16.2mol g -1 ·h -1 Is simple TiO 2 9 times (G.H.Yin, X.Y.Huang, T.Y.Chen, W.ZHao, Q.Y.Bi, J.Xu, Y.F.Han, F.Q.Huang.Hydrogenic blue titanium for electronic devices: preparation, chromatography, and reaction mechanism of CO 2 Acs cat, 2018,8, 1009-1017). But in CO 2 During the reduction, various electron transfer and reaction routes occur simultaneously, for example: CO 2 2 +2H + +2e - ＝CO+ H 2 O and 2H + +2e - ＝H 2 Thus the reduction products are mainly composed of CO and H 2 Mainly comprises the following steps. This is due to Ti in the vicinity of surface oxygen vacancies 3+ Can only provide electrons for the reaction, but can not adjust CO 2 Reaction pathways and intermediates of the reduction process. Therefore, it is difficult to simultaneously realize CH by using a single surface oxygen vacancy site 4 High yield and high selectivity. Thus, the construction of highly selective oxygen vacancy-rich TiO 2 Photocatalytic systems remain a significant challenge.
The introduction of metal promoters as active sites in the photocatalytic system allows for the modulation of the reaction pathways and intermediates, thereby increasing CH 4 Yield and selectivity (r.long, y.li, y.liu, s.m.chen, x.s.zheng, c.gao, c.h.he, n.s.chen, z.m.qi, l.song, j.jiang, j.f.zhu, y.j.xiong.j.am.chem.soc.,2017,139, 4486-4492.). In particular toAu, in turn, accelerates CO formation. The proper binding energy between Cu and H is favorable for the product to move from CO to CH 4 The transformation of (3). More importantly, the accumulation of H and electrons on the Cu sites can cause severe hydrogen evolution competition reaction, and the Au (5.1 eV) with larger work function can effectively attract the electrons on the surface of the Cu (4.65 eV) with smaller work function, so that the hydrogen evolution competition reaction of the Cu sites can be inhibited. Thus, in the case of oxygen vacancy-rich TiO 2 The reaction path can be effectively and selectively adjusted by introducing the AuCu alloy on the surface, and CO is promoted 2 To CH 4 The transformation of (3).
Disclosure of Invention
The present invention is directed to TiO 2 Photocatalytic reduction of CO 2 The problem of low conversion rate and selectivity is solved by providing TiO rich in oxygen vacancy/AuCu alloy 2 A method for preparing a nano square sheet photocatalytic material. The preparation method synthesizes the TiO of the oxygen-rich vacancy/AuCu alloy by a hydrothermal method, an oil bath method and a calcination method 2 The photocatalyst prepared from the nano square sheet has better photocatalytic reduction of CO 2 Produce CH 4 Efficiency.
Thus, this patent proposes a method of forming a film on TiO 2 The method for introducing oxygen vacancies and AuCu alloy on the nano square sheet has the advantages that the grain diameter of ultrafine AuCu alloy particles is uniform, and the AuCu alloy particles can still keep the initial shape after the oxygen vacancies are introduced. And the preparation process is green and environment-friendly, and has potential application prospect in energy problems and new material synthesis.
The technical scheme of the invention is as follows:
(1) Preparation of TiO 2 Nano square sheets for later use:
sequentially adding TBOT and HF into a polytetrafluoroethylene reaction kettle according to a proportion, then reacting for 12-36 h at 100-300 ℃, repeatedly washing the obtained solid with ethanol and water, centrifuging, and baking for 12-20 h in an oven at 40-80 ℃; wherein the volume ratio of TBOT to HF is 3-7 mL: 0.6-1 mL.
(2) Preparation of TiO rich in AuCu alloy 2 Nano square sheet material, for use:
sequentially adding a certain amount of TiO into a flask 2 Adding nanometer square sheet, PVP and KBr under ultrasonic treatmentMethanol, then CuCl was added with gentle stirring 2 ·2H 2 O and HAuCl 4 ·4H 2 O, heating the whole solution in an oil bath at the temperature of 80-120 ℃ to boil, and then adding NaBH 4 Adding the mixture into the mixed solution, continuously reacting for 0.5-2 h under vigorous stirring, slowly cooling to room temperature, centrifugally separating the obtained sample, washing with distilled water and ethanol, and baking the obtained solid in an oven at 40-80 ℃ for 12-20 h.
Wherein, the TiO is 2 PVP, KBr, methanol, cuCl 2 ·2H 2 O，HAuCl 4 ·4H 2 O and NaBH 4 The dosage is respectively as follows: 80-120 mg; 30-50 mg; 100-120 mg; 50-100 mL; 8-10 mg; 2-5 mg: 5-10 mg.
(3) Preparation of oxygen vacancy-rich/AuCu alloyed TiO 2 Nano square sheet material:
TiO rich in AuCu alloy obtained in the step (2) 2 Calcining the nano square sheet for 1 to 3 hours at the temperature of between 100 and 300 ℃ in a reducing atmosphere until the TiO of the oxygen vacancy-rich/AuCu alloy 2 The temperature rise rate of the nanometer square sheet is 2-5 ℃/min.
Wherein the reducing atmosphere is a mixture of 90vol.% argon and 10vol.% hydrogen.
The TiO rich in oxygen vacancy/AuCu alloy of the invention 2 Nano square sheet for photocatalytic reduction of CO 2 Manufacture of CH 4 The use of (1).
Using X-ray diffractometer (XRD), transmission Electron Microscope (TEM) and Electron Paramagnetic Resonance (EPR) to analyze the morphology of the product, and measuring CH in a certain time period by gas chromatography 4 And production of by-products to evaluate photocatalytic reduction of CO 2 Manufacture of CH 4 Activity and selectivity.
The beneficial effects of the invention are as follows:
the invention successfully prepares CO with high activity and selectivity by adopting a hydrothermal method, an oil bath method and a calcination method for the first time 2 Conversion to CH 4 TiO of oxygen vacancy-rich/AuCu alloy 2 The preparation process of the nano square sheet catalyst has the advantages of simple process, low cost, short period, environmental friendliness and the like. Prepared byTiO of oxygen vacancy rich/AuCu alloy 2 The nanometer square sheet effectively improves the photocatalytic reduction of CO 2 Preparation of CH 4 The activity and the selectivity of the composite photocatalyst are good, the recyclable stability of the composite photocatalyst is good, and the composite photocatalyst has potential application prospects in the field of development of clean energy.
Drawings
FIG. 1a, b and c are respectively TiO 2 Nano square sheet, tiO rich in AuCu alloy 2 Nano square sheet and TiO of oxygen vacancy-rich/AuCu alloy 2 XRD diffraction pattern of nanometer square plate.
FIG. 2a, b and c are respectively TiO 2 Nano square sheet, tiO rich in AuCu alloy 2 Nano square sheet and TiO rich in oxygen vacancy/AuCu alloy 2 EPR spectrum of the nano square sheet.
FIG. 3a, b, c are TiO respectively 2 Nano square sheet, tiO rich in AuCu alloy 2 Nano square sheet and TiO rich in oxygen vacancy/AuCu alloy 2 Photocatalytic reduction of CO from nano square sheets 2 Activity and preparation of CH 4 And (4) a selectivity graph.
FIGS. 4a, b and c are TiO respectively 2 Nano square sheet, tiO rich in AuCu alloy 2 Nano square sheet and TiO of oxygen vacancy-rich/AuCu alloy 2 TEM images of nanoprisms.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Example 1
(1) Preparation of TiO 2 Nano square sheets for standby:
5mL of TBOT and 0.8mL of HF were sequentially added to the Teflon reactor. Then reacted at 200 ℃ for 24h. The resulting solid was washed repeatedly with ethanol and water and centrifuged and baked in an oven at 60 ℃ for 16h.
(2) Preparation of TiO rich in AuCu alloy 2 Nano square sheets for standby:
100mg of TiO were added to the flask in succession 2 Nanobule, 41mg PVP and 117mg KBr, and add 75mL of methanol under sonication, then add under gentle stirring8.93mg CuCl 2 ·2H 2 O and 3.45mg HAuCl 4 ·4H 2 O, the entire solution was heated to boiling in an oil bath at 100 ℃ and then 8mg of NaBH 4 Adding into the mixed solution, reacting for 1h under vigorous stirring, slowly cooling to room temperature, centrifuging the obtained sample, washing with distilled water and ethanol, and baking the obtained solid in an oven at 60 deg.C for 16h.
(3) Preparation of oxygen vacancy-rich/AuCu alloyed TiO 2 Nano square sheets:
TiO rich in AuCu alloy obtained in the step (2) 2 Calcining the nano square sheet for 2h at 200 ℃ in a reducing atmosphere until the TiO of the oxygen vacancy/AuCu alloy is enriched 2 The temperature rise rate of the nanometer square sheet is 2 ℃/min.
Example 2
The steps (2) and (3) of this example are the same as in example 1;
(1) Preparation of TiO 2 Nano square sheet material:
6mL of TBOT and 0.8mL of TBOT were sequentially added to a polytetrafluoroethylene reaction kettle and then reacted at 200 ℃ for 24 hours, and the resulting solid was repeatedly washed with ethanol and water and centrifuged and baked in an oven at 60 ℃ for 16 hours.
Example 3
The steps (1) and (3) of this example are the same as in example 1;
(2) Preparation of TiO rich in AuCu alloy 2 Nano square sheet material:
80mg of TiO was added to a 100mL flask in sequence 2 Nanobold, 41mg PVP and 117mg KBr, and 75mL of methanol was added under sonication, followed by 8.93mg CuCl with gentle stirring 2 ·2H 2 O and 2mL HAuCl 4 ·4H 2 O aqueous solution (4.2X 10) -3 M), the entire solution is heated to boiling in an oil bath at 100 ℃ and then 8mg of NaBH are added 4 Adding into the mixed solution, reacting for 1h under vigorous stirring, slowly cooling to room temperature, centrifuging the obtained sample, washing with distilled water and ethanol, and baking the obtained solid in an oven at 60 deg.C for 16h.
Example 4
The steps (1) and (3) of this example are the same as in example 1;
(2) Preparation of TiO rich in AuCu alloy 2 Nano square sheets:
100mg of TiO were added to the flask in sequence 2 Nanobubble, 41mg PVP and 117mg KBr, and 75mL of methanol was added under sonication. Then 10mg of CuCl was added with gentle stirring 2 ·2H 2 O and 3.45mg HAuCl 4 ·4H 2 O, the entire solution was heated to boiling in an oil bath at 100 ℃ and then 8mg of NaBH was added 4 Adding into the mixed solution, reacting for 1h under vigorous stirring, slowly cooling to room temperature, centrifuging the obtained sample, washing with distilled water and ethanol, and baking the obtained solid in an oven at 60 deg.C for 16h.
Example 5
The steps (1) and (2) of this example are the same as in example 1;
(3) TiO of oxygen vacancy rich/AuCu alloy 2 Nano square sheets:
TiO rich in AuCu alloy obtained in the step (2) 2 Calcining the nano square sheet at 500 ℃ for 2h in reducing atmosphere to obtain TiO rich in oxygen vacancy/AuCu alloy 2 The temperature rise rate of the nano square sheet is 2 ℃/min.
Examples TiO of oxygen vacancy-rich/AuCu alloy 2 Characterization and analysis of nano-square plate photocatalyst
FIG. 1a, b and c are respectively TiO 2 Nano square sheet, tiO rich in AuCu alloy 2 Nano square sheet and TiO of oxygen vacancy-rich/AuCu alloy 2 XRD diffraction pattern of nanometer square plate. From the figure, it can be seen that the patterns belong to typical anatase diffraction peaks, and no other phases and impurities are found, indicating that the introduction of oxygen vacancies and alloys does not affect TiO 2 The main crystal structure of (1). No diffraction peak was observed for the AuCu alloy, indicating that the AuCu alloy exists in the form of ultrafine nanoparticles.
FIG. 2a, b and c are respectively TiO 2 Nano square sheet, tiO rich in AuCu alloy 2 Nano square sheet and TiO of oxygen vacancy-rich/AuCu alloy 2 EPR spectrum of the nano square sheet. It is apparent that Ti before the reintroduction of oxygen vacancies is presentO 2 Nano square sheet and TiO rich in AuCu alloy 2 The nanoplanar plates have no obvious EPR peak. And TiO of oxygen vacancy-rich/AuCu alloy 2 The nano square sheet has obvious EPR peak at g =2.002, which shows that the nano square sheet is in the TiO rich in AuCu alloy 2 Oxygen vacancies are successfully introduced into the nano square sheet.
FIG. 3a, b, c are TiO respectively 2 Nano square sheet, tiO rich in AuCu alloy 2 Nano square sheet and TiO of oxygen vacancy-rich/AuCu alloy 2 Photocatalytic reduction of CO from nanosquared sheets 2 Activity and preparation of CH 4 And (4) a selectivity graph. It can be seen that pure TiO 2 The nano square sheet has no proper adsorption sites and electron donors, and can be used for photocatalytic reduction of CO 2 And CH 4 All of them are poor. And rich in TiO of AuCu alloy 2 Nano square sheet photocatalytic reduction of CO 2 The activity of (a) is enhanced since Au accelerates CO formation. The proper binding energy between Cu and H is favorable for the product to move from CO to CH 4 The transformation of (3). But not enough electrons to promote the reaction, CH 4 Yield (12.10. Mu. Mol. G) -1 ) And selectivity (77.50%) improvement was not significant. TiO of oxygen vacancy/AuCu-rich alloy obtained after oxygen vacancy is introduced 2 The nanometer square sheet realizes the synergy of AuCu alloy and oxygen vacancy, CH 4 The yield of (a) is improved to 22.47 mu mol g -1 The selectivity is improved to 90.55 percent.
FIG. 4a, b, c are TiO respectively 2 Nano square sheet, tiO rich in AuCu alloy 2 Nano square sheet and TiO of oxygen vacancy-rich/AuCu alloy 2 TEM images of nanoplatelets. From a picture, it can be seen that TiO is successfully synthesized 2 A nano square sheet. FIG. b shows the success in TiO 2 The surface of the nano square sheet is introduced with the AuCu alloy. In the figure c, it can be seen that TiO is introduced after oxygen vacancy is introduced 2 The morphology of the AuCu nanoparticles on the surface of the nano square plate is not obviously changed.

Claims (6)

1. TiO of rich oxygen vacancy/AuCu alloy 2 The preparation method of the nano square sheet is characterized by comprising the following steps of:
(1) Preparation of TiO 2 Nano square sheets for later use;
(2) Preparation of TiO rich in AuCu alloy 2 Nano square sheet material for standby:
adding a certain amount of TiO into a flask in sequence 2 Nano square sheet, PVP and KBr, dispersing into methanol under ultrasonic treatment, and adding CuCl under mild stirring 2 ·2H 2 O and HAuCl 4 ·4H 2 O, heating the whole solution in oil bath at a certain temperature to boil, and then adding NaBH 4 Adding into the mixed solution, reacting for a while under vigorous stirring, slowly cooling to room temperature, washing the obtained sample with distilled water and ethanol, centrifuging, and drying in oven to obtain TiO rich in AuCu alloy 2 A nano square sheet;
the TiO is 2 PVP, KBr, methanol, cuCl 2 ·2H 2 O，HAuCl 4 ·4H 2 O and NaBH 4 The dosage is respectively as follows: 80-120 mg; 30-50 mg; 100-120 mg; 50-100 mL; 8-10 mg; 2-5 mg: 5-10 mg;
the oil bath temperature is 80-120 ℃, and the oil bath time is 0.5-2 h;
(3) Preparation of oxygen vacancy-rich/AuCu alloyed TiO 2 Nano square sheet material:
TiO rich in AuCu alloy obtained in the step (2) 2 Calcining the nano square sheet for 1 to 3 hours at the temperature of between 100 and 300 ℃ in a reducing atmosphere to obtain the TiO rich in the oxygen vacancy/AuCu alloy 2 A nano square sheet.
2. The method of claim 1, wherein: in the step (1), tiO is prepared 2 The steps of the nano square sheet are as follows:
sequentially adding TBOT and HF into a polytetrafluoroethylene reaction kettle according to a proportion, then reacting for 12-36 h at 100-300 ℃, repeatedly washing the obtained solid with ethanol and water, centrifuging, and baking for 12-20 h in an oven at 40-80 ℃; wherein the volume ratio of TBOT to HF is 3-7 mL: 0.6-1 mL.
3. The method of claim 1, wherein: in the step (2), the drying temperature is 40-80 ℃, and the drying time is 12-20 h.
4. The method of claim 1, wherein: in the step (3), the temperature rise rate of calcination is 2-5 ℃/min.
5. The method of claim 1, wherein: in step (3), the reducing atmosphere is a mixture of 90vol.% argon and 10vol.% hydrogen.
6. TiO alloy rich in oxygen vacancy/AuCu produced by the production method according to any one of claims 1 to 5 2 Nano square sheet for photocatalytic reduction of CO 2 Preparation of CH 4 The use of (1).
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