CN101875007B - Preparation method of titanium dioxide and boron-doped diamond compounded photoelectric-synergetic electrode - Google Patents

Preparation method of titanium dioxide and boron-doped diamond compounded photoelectric-synergetic electrode Download PDF

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CN101875007B
CN101875007B CN2009100832628A CN200910083262A CN101875007B CN 101875007 B CN101875007 B CN 101875007B CN 2009100832628 A CN2009100832628 A CN 2009100832628A CN 200910083262 A CN200910083262 A CN 200910083262A CN 101875007 B CN101875007 B CN 101875007B
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tio
photoelectric
synergetic
dewaters
boron
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CN101875007A (en
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赵天艺
王景明
江雷
程天宇
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Institute of Chemistry CAS
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Abstract

The invention belongs to the field of photoelectric-synergetic electrodes, in particular to a preparation method of a titanium dioxide and boron-doped diamond compounded photoelectric-synergetic electrode. In the method, the boron-doped diamond is deposited on the surface of a TiO2 surface in a chemical vapor mode to prepare the titanium dioxide and boron-doped diamond compounded photoelectric-synergetic electrode. The photoelectric-synergetic electrode has good photoelectric-synergetic effects, such as better photoelectric conversion efficiency (about 3 percent), and the current intensity is increased by about 50 percent after illumination than that before illumination; and both the TiO2 and the diamond are nontoxic, have good biocompatibility and have the function of catalyzing and decomposing organic matters. The titanium dioxide and boron-doped diamond compounded photoelectric-synergetic electrode is expected to be applied to the field of photoelectric-synergetic organic matter catalysis and decomposition or used as a biologic solar cell material, and the like.

Description

The preparation method of titanium dioxide and boron-doped diamond compounded photoelectric-synergetic electrode
Technical field
The invention belongs to the photoelectric-synergetic electrode field, relate in particular to the preparation method of a kind of titanium dioxide and boron-doped diamond compounded photoelectric-synergetic electrode.
Background technology
Electrochemical oxidation technology is the novel high-level oxidation technology that latest developments are got up, because of its treatment effeciency height, easy and simple to handle, caused researcher's extensive attention with advantage such as environmental compatible.Boron-doped diamond film (BDD) have very wide electrochemical window (2.4～3.4V) and lower background current, especially show higher peroxidating current potential, therefore good Treatment of Industrial Water using value is arranged.By the doping of control boron, boron-doped diamond film shows as p type semiconductor and can conduct electricity at ambient temperature.In addition, BDD does not absorb in the ultra-violet (UV) band, therefore, and with the TiO of n type 2The boron-doped diamond film of film and p type is introduced electrode simultaneously, will improve the photocatalysis efficiency of TiO2, realizes good photoelectric-synergetic effect.
Since 1972, Fujishima and Honda delivered on the Nature magazine and have used TiO 2As light anode decomposing H under ultraviolet light illumination 2O is H 2And O 2Paper [Fujishima, A.; Honda, K.Electrochemical Photolysis of Water at a Semiconductor Electrode Nature 1972,238,37.], semiconductor catalysis has just begun from basic research to the application study New Times.TiO 2Because of its good strong oxidability, nontoxic, advantages such as good stability are in the core status that photocatalysis is studied always.But TiO 2Semiconductor only has photoresponse in the ultra-violet (UV) band, to the utilization rate less than 10% of sunshine.In addition, TiO 2The right recombination probability in light induced electron/hole higher, the hole and the electronics that are in excitation state very easily take place compound and inactivation.Therefore, in order to improve its photocatalytic activity and catalytic efficiency, a lot of methods wish to improve TiO by introducing impurity or defective 2Light absorption, improve steady-state light degraded quantum efficiency and photocatalysis usefulness, compound comprising metal ion mixing, noble metal loading, surperficial enhanced sensitivity and semiconductor.Yet, with the TiO of n type 2Actually rare with the system of the BDD hydridization of p type.In the past at the BDD electrode depositing Ti O that powers on 2Method, can make the electrode of photoelectric-synergetic, but because adamantine existence, TiO 2Cannot at high temperature anneal and control crystalline form, the character of electrode is had certain influence.
The present invention passes through at TiO 2Chemical vapour deposition (CVD) BDD is used on the surface, makes TiO 2/ BDD hybrid electrode.Its photoelectric current transformation efficiency is bigger, is fit to do novel photoelectric-synergetic catalysis material.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of titanium dioxide and boron-doped diamond compounded photoelectric-synergetic electrode.
Titanium dioxide (TiO of the present invention 2) and the preparation method of boron-doped diamond (BDD) compounded photoelectric-synergetic electrode may further comprise the steps:
(1) electro-conductive glass (ITO) being cleaned up the back dries up with nitrogen;
(2) use the method for spin-coating with TiO 2Colloidal sol is coated on the clean conductive glass that step (1) obtains, and forms TiO 2Film; Speed with 4 ℃ of per minutes is warming up to 500 ℃ then, calcines 8～10 hours;
(3) with average diameter be 50～100nm bortz powder as crystal seed by ultrasonic method be dispersed in step (2) through the calcining after the surface have TiO 2The suprabasil TiO of the electro-conductive glass of film 2On the film, then this substrate is placed on the substrate of stainless steel reaction under high pressure chamber of hot-wire chemical gas-phase deposition device, tantalum wire is positioned at the substrate top of stainless steel reaction under high pressure chamber, and substrate is heated to 450～520 ℃; Then the acetone that dewaters or the methane that dewaters are introduced reative cell as carbon source by the hydrogen bubbling, make carbon source nucleation on crystal seed, the tantalum wire Current Control is at 18A, the about 4.5V of bias voltage, nucleation time 30 minutes; Then the acetone that dewaters of borate doped trimethyl or the methane that dewaters (containing the boron element mass concentration is 0.1～0.5%) are introduced reative cell as carbon source by the hydrogen bubbling, growing diamond on the crystal seed of nucleation, the tantalum wire electric current is 22A, the about 4.5V of bias voltage, growth time 2～6 hours.In nucleation and the growth course, reacting outdoor wall provides the cooling water circulation simultaneously.
The described cleaning of step (1) is that electro-conductive glass (ITO) is ultrasonic more than 5 minutes respectively in the liquid detergent aqueous solution, ethanolic solution, acetone soln respectively.
The described TiO of step (2) 2Colloidal sol is with commercially available P25 type TiO 2Nano particle 0.6g, be dissolved in the 8g deionized water, the aqueous solution that adds the 1g mass concentration again and be 30% polyvinyl alcohol is that ratio is mixed with solution, fully stirring and ultrasonic, using centrifuge then, centrifugal (rotating speed of centrifuge is 200～1000 rev/mins, preferred 500 rev/mins) after, get supernatant liquor, obtain TiO 2Colloidal sol.
Prepared titanium dioxide of the present invention and boron-doped diamond compounded photoelectric-synergetic electrode not only have good photoelectric-synergetic effect, as photoelectric transformation efficiency (about 3%) preferably, increase (increasing about 50%) than current strength before the illumination after the illumination.And because TiO 2Be nontoxic, good biocompatibility and have the catalytic decomposition organics function with diamond, titanium dioxide that the present invention obtains and boron-doped diamond compounded photoelectric-synergetic electrode are expected to be applied in photoelectric-synergetic catalytic decomposition organic matter field, or as biologic solar cell material etc.
Description of drawings
Fig. 1. the BDD/TiO of the embodiment of the invention 1 2TiO in the compounded photoelectric-synergetic electrode 2The electromicroscopic photograph of layer.
Fig. 2. the BDD/TiO of the embodiment of the invention 1 2The electromicroscopic photograph of BDD layer in the compounded photoelectric-synergetic electrode, wherein Fig. 2 A is the enlarged drawing of Fig. 2 B.
Fig. 3. the BDD/TiO of the embodiment of the invention 1 2The cyclic voltammetry curve contrast of compounded photoelectric-synergetic electrode and common BDD electrode.
Fig. 4. the BDD/TiO of the embodiment of the invention 1 2The photoelectric current of compounded photoelectric-synergetic electrode under the different wavelengths of light irradiation.
Fig. 5. the BDD/TiO of the embodiment of the invention 1 2The current strength contrast of compounded photoelectric-synergetic electrode before and after 500nm illumination.
The specific embodiment
Embodiment 1
The cleaning of ito glass:, dry up with nitrogen with ito glass in the liquid detergent aqueous solution, ethanolic solution, acetone soln each ultrasonic 5 minutes respectively.
On ito glass, modify TiO 2Film: P25 type TiO 2Nano particle (Degussa, NipponAerisol) 0.6g, be dissolved in the 8g deionized water, polyvinyl alcohol (the PVA that adds 1g 30% (mass concentration), Mw=22000) the aqueous solution, fully stir and ultrasonic, use centrifuge centrifugal (rotating speed of centrifuge is 500 rev/mins) then after, with the method for spin-coating the supernatant liquor after centrifugal is applied on the clean ito glass.Speed with 4 ℃ of per minutes is warming up to 500 ℃, calcines 8 hours, thoroughly removes organic matter.
At TiO 2Continue deposition BDD film on the film: with hot filament CVD (HFCVD).The bortz powder that at first with average diameter is 100nm is dispersed in TiO as crystal seed by ultrasonic method 2The TiO of the ITO substrate of modified 2On the coating, then this substrate is placed on the substrate of stainless steel reaction under high pressure chamber of hot-wire chemical gas-phase deposition device, tantalum wire is positioned at the substrate top, and substrate is heated to 450～520 ℃; Then the acetone that dewaters or the methane that dewaters are introduced reative cell as carbon source by the hydrogen bubbling, make carbon source nucleation on crystal seed, the tantalum wire Current Control is at 18A, the about 4.5V of bias voltage, nucleation time 30 minutes; Then the acetone that dewaters of borate doped trimethyl or the methane that dewaters (containing the boron element mass concentration is 0.5%) are introduced reative cell as carbon source by the hydrogen bubbling, growing diamond on the crystal seed of nucleation, the tantalum wire electric current is 22A, the about 4.5V of bias voltage, growth time 4 hours.In nucleation and the growth course, reacting outdoor wall provides the cooling water circulation simultaneously.
Prepared BDD/TiO 2TiO in the compounded photoelectric-synergetic electrode 2The layer the front electromicroscopic photograph as shown in Figure 1, TiO 2The thickness of thin layer is 4.034 μ m; BDD/TiO 2In the compounded photoelectric-synergetic electrode electromicroscopic photograph of BDD layer as shown in Figure 2, wherein Fig. 2 A is the enlarged drawing of Fig. 2 B; BDD/TiO 2The cyclic voltammetry curve of compounded photoelectric-synergetic electrode and common BDD electrode contrasts as shown in Figure 3, BDD/TiO 2The photoelectric current of compounded photoelectric-synergetic electrode under different wavelengths of light irradiation as shown in Figure 4, BDD/TiO 2Composite photoelectric is done with the current strength contrast of electrode before and after 500nm illumination as shown in Figure 5.
Prepared BDD/TiO 2Compounded photoelectric-synergetic electrode is compared with common BDD electrode, and current strength obviously increases; Has good photoelectric transformation efficiency (about 3%, calculate) by Fig. 4; Current strength increases about 50% (as Fig. 3 and shown in Figure 5) before and after the illumination.
Embodiment 2
The cleaning of ito glass:, dry up with nitrogen with ito glass in the liquid detergent aqueous solution, ethanolic solution, acetone soln each ultrasonic 5 minutes respectively.
On ito glass, modify TiO 2Film: P25 type TiO 2Nano particle (Degussa, NipponAerisol) 0.6g, be dissolved in the 8g deionized water, polyvinyl alcohol (the PVA that adds 1g 30% (mass concentration), Mw=22000) the aqueous solution, fully stir and ultrasonic, use centrifuge centrifugal (rotating speed of centrifuge is 200 rev/mins) then after, with the method for spin-coating the supernatant liquor after centrifugal is applied on the clean ito glass.Speed with 4 ℃ of per minutes is warming up to 500 ℃, calcines 8 hours, thoroughly removes organic matter.
At TiO 2Continue deposition BDD film on the film: with hot filament CVD (HFCVD).The bortz powder that at first with average diameter is 50nm is dispersed in TiO as crystal seed by ultrasonic method 2The TiO of the ITO substrate of modified 2On the coating, then this substrate is placed on the substrate of stainless steel reaction under high pressure chamber of hot-wire chemical gas-phase deposition device, tantalum wire is positioned at the substrate top, and substrate is heated to 450～520 ℃; Then the acetone that dewaters or the methane that dewaters are introduced reative cell as carbon source by the hydrogen bubbling, make carbon source nucleation on crystal seed, the tantalum wire Current Control is at 18A, the about 4.5V of bias voltage, nucleation time 30 minutes; Then the acetone that dewaters of borate doped trimethyl or the methane that dewaters (containing the boron element mass concentration is 0.1%) are introduced reative cell as carbon source by the hydrogen bubbling, growing diamond on the crystal seed of nucleation, the tantalum wire electric current is 22A, the about 4.5V of bias voltage, growth time 2 hours.In nucleation and the growth course, reacting outdoor wall provides the cooling water circulation simultaneously.
Prepared BDD/TiO 2Compounded photoelectric-synergetic electrode is compared with common BDD electrode, and current strength obviously increases; Has good photoelectric transformation efficiency (about 2.7%); Current strength increases about 45% before and after the illumination.
Embodiment 3
The cleaning of ito glass: each is ultrasonic more than 5 minutes in the liquid detergent aqueous solution, ethanolic solution, acetone soln respectively with ito glass, dries up with nitrogen.
On ito glass, modify TiO 2Film: P25 type TiO 2Nano particle (Degussa, NipponAerisol) 0.6g, be dissolved in the 8g deionized water, polyvinyl alcohol (the PVA that adds 1g 30% (mass concentration), Mw=88000) the aqueous solution, fully stir and ultrasonic, use centrifuge centrifugal (rotating speed of centrifuge is 1000 rev/mins) then after, with the method for spin-coating the supernatant liquor after centrifugal is applied on the clean ito glass.Speed with 4 ℃ of per minutes is warming up to 500 ℃, calcines 10 hours, thoroughly removes organic matter.
At TiO 2Continue deposition BDD film on the film: with hot filament CVD (HFCVD).The bortz powder that at first with average diameter is 50nm is dispersed in TiO as crystal seed by ultrasonic method 2The TiO of the ITO substrate of modified 2On the coating, then this substrate is placed on the substrate of stainless steel reaction under high pressure chamber of hot-wire chemical gas-phase deposition device, tantalum wire is positioned at the substrate top, and substrate is heated to 450～520 ℃; Then the acetone that dewaters or the methane that dewaters are introduced reative cell as carbon source by the hydrogen bubbling, make carbon source nucleation on crystal seed, the tantalum wire Current Control is at 18A, the about 4.5V of bias voltage, nucleation time 30 minutes; Then the acetone that dewaters of borate doped trimethyl or the methane that dewaters (containing the boron element mass concentration is 0.5%) are introduced reative cell as carbon source by the hydrogen bubbling, growing diamond on the crystal seed of nucleation, the tantalum wire electric current is 22A, the about 4.5V of bias voltage, growth time 2 hours.In nucleation and the growth course, reacting outdoor wall provides the cooling water circulation simultaneously.
Prepared BDD/TiO 2Compounded photoelectric-synergetic electrode is compared with common BDD electrode, and current strength obviously increases; Has good photoelectric transformation efficiency (about 2.73%); Current strength increases about 45% before and after the illumination.
Embodiment 4
The cleaning of ito glass:, dry up with nitrogen with ito glass in the liquid detergent aqueous solution, ethanolic solution, acetone soln each ultrasonic 10 minutes respectively.
On ito glass, modify TiO 2Film: P25 type TiO 2Nano particle (Degussa, NipponAerisol) 0.6g, be dissolved in the 8g deionized water, polyvinyl alcohol (the PVA that adds 1g 30% (mass concentration), Mw=88000) the aqueous solution, fully stir and ultrasonic, use centrifuge centrifugal (rotating speed of centrifuge is 500 rev/mins) then after, with the method for spin-coating the supernatant liquor after centrifugal is applied on the clean ito glass.Speed with 4 ℃ of per minutes is warming up to 500 ℃, heats 10 hours, thoroughly removes organic matter.
At TiO 2Continue deposition BDD film on the film: with hot filament CVD (HFCVD).The bortz powder that at first with average diameter is 50nm is dispersed in TiO as crystal seed by ultrasonic method 2The TiO of the ITO substrate of modified 2On the coating, then this substrate is placed on the substrate of stainless steel reaction under high pressure chamber of hot-wire chemical gas-phase deposition device, tantalum wire is positioned at the substrate top, and substrate is heated to 450～520 ℃; Then the acetone that dewaters or the methane that dewaters are introduced reative cell as carbon source by the hydrogen bubbling, make carbon source nucleation on crystal seed, the tantalum wire Current Control is at 18A, the about 4.5V of bias voltage, nucleation time 30 minutes; Then the acetone that dewaters of borate doped trimethyl or the methane that dewaters (containing the boron element mass concentration is 0.5%) are introduced reative cell as carbon source by the hydrogen bubbling, growing diamond on the crystal seed of nucleation, the tantalum wire electric current is 22A, the about 4.5V of bias voltage, growth time 6 hours.In nucleation and the growth course, reacting outdoor wall provides the cooling water circulation simultaneously.
Prepared BDD/TiO 2Compounded photoelectric-synergetic electrode is compared with common BDD electrode, and current strength obviously increases; Has good photoelectric transformation efficiency (about 3%); Current strength increases about 50% before and after the illumination.

Claims (3)

1. the preparation method of titanium dioxide and boron-doped diamond compounded photoelectric-synergetic electrode is characterized in that this method may further comprise the steps:
(1) electro-conductive glass being cleaned up the back dries up with nitrogen;
(2) use the method for spin-coating with TiO 2Colloidal sol is coated on the clean conductive glass that step (1) obtains, and forms TiO 2Film; Speed with 4 ℃ of per minutes is warming up to 500 ℃ then, calcines 8～10 hours;
(3) with diameter be 50～100nm bortz powder as crystal seed by ultrasonic method be dispersed in step (2) through the calcining after the surface have TiO 2The suprabasil TiO of the electro-conductive glass of film 2On the film, then this substrate is placed on the substrate of stainless steel reaction under high pressure chamber of hot-wire chemical gas-phase deposition device, tantalum wire is positioned at the substrate top of stainless steel reaction under high pressure chamber, and substrate is heated to 450～520 ℃; Then the acetone that dewaters or the methane that dewaters are introduced reative cell as carbon source by the hydrogen bubbling, make carbon source nucleation on crystal seed, the tantalum wire Current Control is at 18A, bias voltage 4.5V, nucleation time 30 minutes; Then the acetone that dewaters of borate doped trimethyl or the methane that dewaters are introduced reative cell as carbon source by the hydrogen bubbling, growing diamond on the crystal seed of nucleation, the tantalum wire electric current is 22A, bias voltage 4.5V, growth time 2～6 hours, wherein, the boron element mass concentration that contains in the acetone that dewaters of borate doped trimethyl or the methane that dewaters is 0.1～0.5%.
2. method according to claim 1 is characterized in that: the described TiO of step (2) 2Colloidal sol is with P25 type TiO 2Nano particle 0.6g is dissolved in the 8g deionized water, and the aqueous solution that adds the 1g mass concentration again and be 30% polyvinyl alcohol is that ratio is mixed with solution, fully stirs and ultrasonic, use centrifuge centrifugal then after, get supernatant liquor, obtain TiO 2Colloidal sol, wherein, the rotating speed of centrifuge is 200～1000 rev/mins.
3. method according to claim 2 is characterized in that: the rotating speed of described centrifuge is 500 rev/mins.
CN2009100832628A 2009-04-30 2009-04-30 Preparation method of titanium dioxide and boron-doped diamond compounded photoelectric-synergetic electrode Expired - Fee Related CN101875007B (en)

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CN106623408A (en) * 2016-12-27 2017-05-10 常州大学 Electrokinetic remediation technology and method for removing heavy metal contaminated soil
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CN111676462B (en) * 2020-05-11 2021-06-25 中南大学 High-specific-surface-area patterned boron-doped diamond electrode and preparation method and application thereof

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CN1735716A (en) * 2003-05-26 2006-02-15 住友电气工业株式会社 Diamond-coated electrode and method for producing same
JP2007154262A (en) * 2005-12-06 2007-06-21 Sumitomo Electric Ind Ltd Composite substrate and production method, and electrode and electrolyzer

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1735716A (en) * 2003-05-26 2006-02-15 住友电气工业株式会社 Diamond-coated electrode and method for producing same
JP2007154262A (en) * 2005-12-06 2007-06-21 Sumitomo Electric Ind Ltd Composite substrate and production method, and electrode and electrolyzer

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