CN104911629A - Synthesis method of composite electrode - Google Patents

Synthesis method of composite electrode Download PDF

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CN104911629A
CN104911629A CN201510365555.0A CN201510365555A CN104911629A CN 104911629 A CN104911629 A CN 104911629A CN 201510365555 A CN201510365555 A CN 201510365555A CN 104911629 A CN104911629 A CN 104911629A
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titanium dioxide
fto substrate
deionized water
graphene oxide
tio
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CN104911629B (en
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范伟强
余小强
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Changshu Intellectual Property Operation Center Co ltd
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Jiangsu University
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Abstract

本发明属于光电化学技术领域，特指一种复合电极的合成方法。首先利用水热合成方法在FTO基片上合成锐钛矿型二氧化钛纳米线矩阵，然后利用溶胶凝胶法在其之上继续生长晶红石型二氧化钛纳米线矩阵，随后使用旋涂法在二氧化钛(TiO2)表面合成还原氧化石墨烯薄膜，最后在此基础上通过化学沉积法沉积氧化亚铜。利用简单的水热合成，溶胶凝胶法和化学沉积法所制备的二氧化钛/还原氧化石墨烯/氧化亚铜为复合3维光电极，该材料具有良好的化学稳定性好，光电化学性能好的优点，本发明工艺简单，重复性好，且所用材料价廉易得，符合环境友好要求。b/

The invention belongs to the technical field of photoelectrochemistry, in particular to a synthesis method of a composite electrode. Firstly, the anatase titanium dioxide nanowire matrix was synthesized on the FTO substrate by hydrothermal synthesis method, and then the crystal redite titanium dioxide nanowire matrix was grown on it by the sol-gel method, and then spin-coated on titanium dioxide (TiO 2 ) Synthesize the reduced graphene oxide film on the surface, and finally deposit cuprous oxide on this basis by chemical deposition. Titanium dioxide/reduced graphene oxide/cuprous oxide prepared by simple hydrothermal synthesis, sol-gel method and chemical deposition method is a composite 3D photoelectrode. The material has good chemical stability and good photoelectrochemical performance. The invention has the advantages of simple process and good repeatability, and the materials used are cheap and easy to obtain, meeting the requirement of environmental friendliness. b/

Description

一种复合电极的合成方法A kind of synthetic method of composite electrode

技术领域 technical field

本发明属于光电化学技术领域，特指一种复合电极的合成方法。首先利用水热合成方法在FTO基片上合成锐钛矿型二氧化钛(TiO2)纳米线矩阵，然后利用溶胶凝胶法在其之上继续生长晶红石型二氧化钛(TiO2)纳米线矩阵，随后使用旋涂法在二氧化钛(TiO2)表面合成还原氧化石墨烯（RGO）薄膜，最后在此基础上通过化学沉积法沉积氧化亚铜（Cu2O）。 The invention belongs to the technical field of photoelectrochemistry, in particular to a synthesis method of a composite electrode . First, the anatase titanium dioxide (TiO 2 ) nanowire matrix was synthesized on the FTO substrate by hydrothermal synthesis method, and then the crystal redite titanium dioxide (TiO 2 ) nanowire matrix was grown on it by the sol-gel method, and then A reduced graphene oxide (RGO) film was synthesized on the surface of titanium dioxide (TiO 2 ) by spin coating method, and finally cuprous oxide (Cu 2 O) was deposited by chemical deposition on this basis.

背景技术 Background technique

随着全球能源问题的加剧，作为一个有前途的解决方案，光电化学分解水制氢，已经吸引了全世界的关注；在这个过程中，光电阳极的效率和稳定性是光电化学水解过程中的重要特征，金属氧化物半导体因具有良好的效率以及稳定性被选中作为光电化学水解中光电阳极的候选材料。 As the global energy problem intensifies, as a promising solution, photoelectrochemical water splitting to produce hydrogen has attracted worldwide attention; in this process, the efficiency and stability of the photoanode is the key factor in the photoelectrochemical hydrolysis process. Important features, metal oxide semiconductors have been selected as candidates for photoanodes in photoelectrochemical hydrolysis due to their good efficiency and stability.

二氧化钛(TiO2)是一种重要的半导体金属氧化物材料，已经被广泛研究来应用光阳极材料，由于其优异的物理和化学性质，如化学稳定性，耐光性，无毒性，和制造成本低廉。 Titanium dioxide (TiO 2 ), an important semiconducting metal oxide material, has been extensively studied for the application of photoanode materials due to its excellent physical and chemical properties, such as chemical stability, light resistance, non-toxicity, and low manufacturing cost. .

还原氧化石墨烯（RGO）是一种具有很强导电性的材料，并且具有很好的光稳定性、化学稳定性、无毒性。 Reduced graphene oxide (RGO) is a material with strong electrical conductivity, and has good photostability, chemical stability, and non-toxicity.

氧化亚铜（Cu2O）是一种典型的具有可见光响应能力的半导体金属氧化物材料，由于其较窄的带隙，可与其他材料形成很好的复合材料。 Cuprous oxide (Cu 2 O) is a typical semiconducting metal oxide material with visible-light responsiveness. Due to its narrow band gap, it can form a good composite material with other materials.

发明内容 Contents of the invention

本发明的目的在于提供一种简单的二氧化钛(TiO2)/还原氧化石墨烯（RGO）/氧化亚铜（Cu2O）复合电极的合成方法。 The purpose of the present invention is to provide a simple synthesis method of titanium dioxide (TiO 2 )/reduced graphene oxide (RGO)/cuprous oxide (Cu 2 O) composite electrode.

本发明采用低温下液相法在FTO基片上经水热反应先制备出形貌相对均一的锐钛矿型的二氧化钛(TiO2)纳米线，继而再通过溶胶凝胶法经煅烧制备出晶红石型的二氧化钛(TiO2)纳米线，然后旋涂法在二氧化钛(TiO2)纳米线表面合成一层还原氧化石墨烯（RGO）薄膜，最后通过化学沉积法在还原氧化石墨烯表面沉积氧化亚铜（Cu2O）。 In the present invention, anatase-type titanium dioxide (TiO 2 ) nanowires with relatively uniform morphology are firstly prepared by hydrothermal reaction on an FTO substrate by a liquid phase method at a low temperature, and then crystal red is prepared by calcination by a sol-gel method. Titanium dioxide (TiO 2 ) nanowires, and then synthesize a layer of reduced graphene oxide (RGO) film on the surface of titanium dioxide (TiO 2 ) nanowires by spin coating, and finally deposit suboxide on the surface of reduced graphene oxide by chemical deposition. Copper (Cu2O ) .

本复合电极的制备方法，是按照下列步骤进行: The preparation method of this compound electrode is to carry out according to the following steps:

A 将15mL的浓盐酸和15mL的去离子水放入烧杯搅拌。 A Put 15mL of concentrated hydrochloric acid and 15mL of deionized water into a beaker and stir.

B 逐滴加入0.35mL～0.7mL钛酸四正丁酯，搅拌均匀至澄清。 B Add 0.35mL ~ 0.7mL tetra-n-butyl titanate dropwise, stir well until clear.

C 将步骤B所得到的溶液转移至四氟乙烯内衬的反应釜中，在其中放入清洗过的FTO基片，升温至180℃温度下恒温6h，自然冷却，得到锐钛矿晶型TiO2纳米线。 C Transfer the solution obtained in step B to a tetrafluoroethylene-lined reaction kettle, put the cleaned FTO substrate in it, raise the temperature to 180°C for 6 hours, and cool naturally to obtain anatase crystal form TiO 2 nanowires.

D 将步骤C所得到的水热后的FTO基片取出用去离子水洗涤干净。 D The hydrothermal FTO substrate obtained in step C is taken out and washed with deionized water.

E 将1mL乙酸和50mL乙醇放入烧杯搅拌。 E Put 1mL of acetic acid and 50mL of ethanol into a beaker and stir.

F 向其中逐滴加入0.75mL钛酸四正丁酯，搅拌均匀至澄清。 F Add 0.75mL tetra-n-butyl titanate dropwise to it, stir evenly until clear.

G 将步骤D所得到的FTO基片泡入步骤F中的溶液1h。 G Soak the FTO substrate obtained in step D into the solution in step F for 1h.

H 将步骤G所得到的FTO基片自然干燥，放入马弗炉中以2℃/min的升温速率升温至450℃恒温2h，即可得到形貌均一的双层锐钛矿/晶红石二氧化钛(TiO2)纳米线。 H Dry the FTO substrate obtained in step G naturally, put it into a muffle furnace and raise the temperature to 450°C at a constant temperature of 2h at a rate of 2°C/min, and then a double-layer anatase/sphinite with uniform shape can be obtained Titanium dioxide (TiO 2 ) nanowires.

J 将步骤H所得到的FTO基片取出用去离子水洗涤干净自然干燥。 J Take out the FTO substrate obtained in step H, wash it with deionized water and dry it naturally.

K将氧化石墨烯粉末超声分散去离子水中得到氧化石墨烯溶胶。 K ultrasonically disperses graphene oxide powder in deionized water to obtain graphene oxide sol.

L 将表面制备有双层二氧化钛的FTO基片放置于旋涂仪上，将氧化石墨烯溶胶滴加到FTO基片上的双层二氧化钛表面上，旋涂3~5次。 L Place the FTO substrate prepared with double-layer titanium dioxide on the surface on a spin coater, add the graphene oxide sol dropwise onto the double-layer titanium dioxide surface on the FTO substrate, and spin-coat for 3 to 5 times.

M将经过旋涂后的FTO基片放入管式炉在氮气气氛下400℃煅烧2h。 M Put the spin-coated FTO substrate into a tube furnace and calcinate at 400°C for 2h under a nitrogen atmosphere.

O 将步骤M所得到的的FTO基片依次浸入硫酸铜和硫代硫酸钠混合溶液、去离子水、氢氧化钠溶液和去离子水；每个浸入时间10～20s，循环30～90次后取出自然干燥；即可得到形貌均一的二氧化钛(TiO2)/还原氧化石墨烯（RGO）/氧化亚铜（Cu2O）复合光电极。 O Immerse the FTO substrate obtained in step M into the mixed solution of copper sulfate and sodium thiosulfate, deionized water, sodium hydroxide solution and deionized water in sequence; each immersion time is 10-20s, after 30-90 cycles Take it out and let it dry naturally; a titanium dioxide (TiO 2 )/reduced graphene oxide (RGO)/cuprous oxide (Cu 2 O) composite photoelectrode with uniform morphology can be obtained.

进一步地，氧化石墨烯溶胶的浓度为1g/L。 Further, the concentration of graphene oxide sol is 1g/L.

进一步地，硫酸铜和硫代硫酸钠混合溶液中硫酸铜和硫代硫酸钠的浓度均为1mol/L；氢氧化钠溶液的浓度也为1mol/L。 Further, the concentrations of copper sulfate and sodium thiosulfate in the mixed solution of copper sulfate and sodium thiosulfate are both 1 mol/L; the concentration of the sodium hydroxide solution is also 1 mol/L.

本发明中的复合电极的的物相，结构以及性能表征由X-射线衍射仪，场发射扫描电镜(SEM)测定。 The phase, structure and performance characterization of the composite electrode in the present invention are measured by X-ray diffractometer and field emission scanning electron microscope (SEM).

本发明的另一个目的，是提供所制备的二氧化钛(TiO2)/还原氧化石墨烯（RGO）/氧化亚铜（Cu2O）复合电极对于光电流的应用。 Another object of the present invention is to provide the application of the prepared titanium dioxide (TiO 2 )/reduced graphene oxide (RGO)/cuprous oxide (Cu 2 O) composite electrode for photocurrent.

二氧化钛(TiO2)/还原氧化石墨烯（RGO）/氧化亚铜（Cu2O）复合电极在氙灯光源照射下光电流测试步骤如下：在CHI 852C型电化学工作站下进行，在电解槽里加入0.5mol/L的硫酸钠(Na2SO4)作为电解液，加入氯化银电极作为参比电极，加入铂电极作为对电极，二氧化钛(TiO2)/还原氧化石墨烯（RGO）/氧化亚铜（Cu2O）复合电极作为工作电极，进行循环伏安扫描。 Titanium dioxide (TiO 2 )/reduced graphene oxide (RGO)/cuprous oxide (Cu 2 O) composite electrode under the irradiation of xenon lamp light source photocurrent test steps are as follows: under the CHI 852C electrochemical workstation, add 0.5mol/L sodium sulfate (Na 2 SO 4 ) was used as electrolyte, silver chloride electrode was added as reference electrode, platinum electrode was added as counter electrode, titanium dioxide (TiO 2 )/reduced graphene oxide (RGO)/suboxide The copper (Cu 2 O) composite electrode was used as the working electrode for cyclic voltammetry scanning.

有益效果Beneficial effect

利用简单的水热合成，溶胶凝胶法和化学沉积法所制备的二氧化钛(TiO2)/还原氧化石墨烯（RGO）/氧化亚铜（Cu2O）为复合3维光电极，该材料具有良好的化学稳定性好，光电化学性能好的优点，本发明工艺简单，重复性好，且所用材料价廉易得，符合环境友好要求。 Titanium dioxide (TiO 2 )/reduced graphene oxide (RGO)/cuprous oxide (Cu 2 O) prepared by simple hydrothermal synthesis, sol-gel method and chemical deposition method is a composite 3D photoelectrode, which has The invention has the advantages of good chemical stability and good photoelectrochemical performance, and the invention has simple process and good repeatability, and the materials used are cheap and easy to obtain, meeting the requirements of environmental friendliness.

附图说明 Description of drawings

图1为二氧化钛(TiO2)/还原氧化石墨烯（RGO）/氧化亚铜（Cu2O）复合光电极的X射线衍射分析图(XRD)，X-射线衍射仪图中没有其他物质的峰存在，该图谱表明，由化学沉积法所制备的氧化亚铜(Cu2O)为纯相氧化亚铜(Cu2O)，其与标准氧化亚铜(Cu2O)卡片(06-0249)相吻合，可以证明其中TiO2/RGO/Cu2O均为纯相的。 Figure 1 is the X-ray diffraction analysis pattern (XRD) of titanium dioxide (TiO 2 )/reduced graphene oxide (RGO)/cuprous oxide (Cu 2 O) composite photoelectrode, and there are no peaks of other substances in the X-ray diffractometer figure exists, the spectrum shows that the cuprous oxide (Cu 2 O) prepared by the chemical deposition method is a pure phase cuprous oxide (Cu 2 O), which is different from the standard cuprous oxide (Cu 2 O) card (06-0249) Consistent with each other, it can be proved that TiO 2 /RGO/Cu 2 O are all in pure phase.

图2为二氧化钛(TiO2)/还原氧化石墨烯（RGO）/氧化亚铜（Cu2O）复合光电极的扫描电镜图(SEM)，测试表明，在室温下，所合成的复合电极是由纳米线形貌的二氧化钛（TiO2），还原氧化石墨烯（RGO）纳米片，氧化亚铜（Cu2O）纳米粒子/花复合形貌组成的，图2（a）为双层TiO2纳米线SEM图，（b）为双层TiO2-RGO SEM图，（c）为TiO2-Cu2O SEM图，（d）和（e）为Cu2O循环次数30次的TiO2-RGO-Cu2O SEM图，（f）和（g）分别为Cu2O循环次数60次与90次的TiO2-RGO-Cu2O SEM图，（h）为Cu2O循环次数60次的TiO2-RGO-Cu2O横截面SEM图。 Figure 2 is the scanning electron microscope (SEM) image of titanium dioxide (TiO 2 )/reduced graphene oxide (RGO)/cuprous oxide (Cu 2 O) composite photoelectrode. The test shows that at room temperature, the synthesized composite electrode is composed of Nanowire morphology composed of titanium dioxide (TiO 2 ), reduced graphene oxide (RGO) nanosheets, and cuprous oxide (Cu 2 O) nanoparticles/flowers composite morphology, Fig. 2(a) is a bilayer TiO 2 nano Line SEM image, (b) is the SEM image of double-layer TiO 2 -RGO, (c) is the SEM image of TiO 2 -Cu 2 O, (d) and (e) are the TiO 2 -RGO with 30 cycles of Cu 2 O -Cu 2 O SEM images, (f) and (g) are TiO 2 -RGO-Cu 2 O SEM images of Cu 2 O cycles of 60 and 90 times, respectively, (h) is the Cu 2 O cycle of 60 times TiO 2 -RGO-Cu 2 O cross-sectional SEM image.

图3 二氧化钛(TiO2)/还原氧化石墨烯（RGO）/氧化亚铜（Cu2O）复合光电极的循环伏安线性图，线性图谱表明负载有三种物质的复合电极性能最佳，且当Cu2O的单次浸泡时间为10s，浸泡次数为60次时性能最佳，且光电流峰值为0.1mA/cm2。 Fig.3 Cyclic voltammetry linear diagram of titanium dioxide (TiO 2 )/reduced graphene oxide (RGO)/cuprous oxide (Cu 2 O) composite photoelectrode. The single immersion time of Cu 2 O is 10s, and the performance is the best when the immersion times are 60 times, and the peak photocurrent is 0.1mA/cm 2 .

具体实施方式 Detailed ways

下面结合实施例对本发明进行详细说明，以使本领域技术人员更好地理解本发明，但本发明并不局限于以下实施例。 The present invention will be described in detail below in conjunction with the examples, so that those skilled in the art can better understand the present invention, but the present invention is not limited to the following examples.

实施例1Example 1

一种二氧化钛(TiO2)/还原氧化石墨烯（RGO）/氧化亚铜（Cu2O）复合电极的制备方法，是按照下述步骤进行： A preparation method of titanium dioxide (TiO 2 )/reduced graphene oxide (RGO)/cuprous oxide (Cu 2 O) composite electrode is carried out according to the following steps:

A 将15mL的浓盐酸和15mL的去离子水放入烧杯搅拌。 A Put 15mL of concentrated hydrochloric acid and 15mL of deionized water into a beaker and stir.

B 逐滴加入0.35mL钛酸四正丁酯，搅拌均匀至澄清。 B Add 0.35mL tetra-n-butyl titanate dropwise, stir well until clear.

C 将步骤B所得到的溶液转移至四氟乙烯内衬的反应釜中，在其中放入清洗过的FTO基片，升温至180℃温度下恒温6h，自然冷却，得到锐钛矿晶型TiO2纳米线。 C Transfer the solution obtained in step B to a tetrafluoroethylene-lined reaction kettle, put the cleaned FTO substrate in it, raise the temperature to 180°C for 6 hours, and cool naturally to obtain anatase crystal form TiO 2 nanowires.

D 将步骤C所得到的水热后的FTO基片取出用去离子水洗涤干净。 D The hydrothermal FTO substrate obtained in step C is taken out and washed with deionized water.

E 将1mL乙酸和50mL乙醇放入烧杯搅拌。 E Put 1mL of acetic acid and 50mL of ethanol into a beaker and stir.

F 向其中逐滴加入0.75mL钛酸四正丁酯，搅拌均匀至澄清。 F Add 0.75mL tetra-n-butyl titanate dropwise to it, stir evenly until clear.

G 将步骤D所得到的FTO基片泡入步骤F中的溶液1h。 G Soak the FTO substrate obtained in step D into the solution in step F for 1h.

H 将步骤G所得到的FTO基片自然干燥，放入马弗炉中以2℃/min的升温速率升温至450℃恒温2h，即可得到形貌均一的双层锐钛矿/晶红石二氧化钛(TiO2)纳米线。 H Dry the FTO substrate obtained in step G naturally, put it into a muffle furnace and raise the temperature to 450°C at a constant temperature of 2h at a rate of 2°C/min, and then a double-layer anatase/sphinite with uniform shape can be obtained Titanium dioxide (TiO 2 ) nanowires.

J 将步骤H所得到的FTO基片取出用去离子水洗涤干净自然干燥。 J Take out the FTO substrate obtained in step H, wash it with deionized water and dry it naturally.

K将氧化石墨烯粉末超声分散去离子水中得到氧化石墨烯溶胶。 K ultrasonically disperses graphene oxide powder in deionized water to obtain graphene oxide sol.

L 将表面制备有双层二氧化钛的FTO基片放置于旋涂仪上，将氧化石墨烯溶胶滴加到FTO基片上的双层二氧化钛表面上，旋涂3次。 L Place the FTO substrate prepared with double-layer titanium dioxide on the surface on a spin coater, add the graphene oxide sol dropwise onto the double-layer titanium dioxide surface on the FTO substrate, and spin-coat three times.

M将经过旋涂后的FTO基片放入管式炉在氮气气氛下400℃煅烧2h。 M Put the spin-coated FTO substrate into a tube furnace and calcinate at 400°C for 2h under a nitrogen atmosphere.

O 将步骤M所得到的的FTO基片依次浸入硫酸铜和硫代硫酸钠混合溶液、去离子水、氢氧化钠溶液和去离子水；每个浸入时间10s，循环30次后取出自然干燥；即可得到形貌均一的二氧化钛(TiO2)/还原氧化石墨烯（RGO）/氧化亚铜（Cu2O）复合光电极；氧化石墨烯溶胶的浓度为1g/L，硫酸铜和硫代硫酸钠混合溶液中硫酸铜和硫代硫酸钠的浓度均为1mol/L；氢氧化钠溶液的浓度也为1mol/L。 O immerse the FTO substrate obtained in step M into copper sulfate and sodium thiosulfate mixed solution, deionized water, sodium hydroxide solution and deionized water successively; each immersion time is 10s, and after 30 cycles, take it out and dry it naturally; A titanium dioxide (TiO 2 )/reduced graphene oxide (RGO)/cuprous oxide (Cu 2 O) composite photoelectrode with uniform morphology can be obtained; the concentration of graphene oxide sol is 1g/L, copper sulfate and thiosulfuric acid The concentrations of copper sulfate and sodium thiosulfate in the sodium mixed solution are both 1mol/L; the concentration of sodium hydroxide solution is also 1mol/L.

经过改变钛酸正丁酯的添加量可以调节TiO2的含量，以此调节TiO2纳米线的直径。 The content of TiO 2 can be adjusted by changing the addition amount of n-butyl titanate, so as to adjust the diameter of TiO 2 nanowires.

实施例2Example 2

一种二氧化钛(TiO2)/还原氧化石墨烯（RGO）/氧化亚铜（Cu2O）复合电极的制备方法，是按照下述步骤进行： A preparation method of titanium dioxide (TiO 2 )/reduced graphene oxide (RGO)/cuprous oxide (Cu 2 O) composite electrode is carried out according to the following steps:

A 将15mL的浓盐酸和15mL的去离子水放入烧杯搅拌。 A Put 15mL of concentrated hydrochloric acid and 15mL of deionized water into a beaker and stir.

B 逐滴加入0.35mL钛酸四正丁酯，搅拌均匀至澄清。 B Add 0.35mL tetra-n-butyl titanate dropwise, stir well until clear.

C 将步骤B所得到的溶液转移至四氟乙烯内衬的反应釜中，在其中放入清洗过的FTO基片，升温至180℃温度下恒温6h，自然冷却，得到锐钛矿晶型TiO2纳米线。 C Transfer the solution obtained in step B to a tetrafluoroethylene-lined reaction kettle, put the cleaned FTO substrate in it, raise the temperature to 180°C for 6 hours, and cool naturally to obtain anatase crystal form TiO 2 nanowires.

D 将步骤C所得到的水热后的FTO基片取出用去离子水洗涤干净。 D The hydrothermal FTO substrate obtained in step C is taken out and washed with deionized water.

E 将1mL乙酸和50mL乙醇放入烧杯搅拌。 E Put 1mL of acetic acid and 50mL of ethanol into a beaker and stir.

F 向其中逐滴加入0.75mL钛酸四正丁酯，搅拌均匀至澄清。 F Add 0.75mL tetra-n-butyl titanate dropwise to it, stir evenly until clear.

G 将步骤D所得到的FTO基片泡入步骤F中的溶液1h。 G Soak the FTO substrate obtained in step D into the solution in step F for 1h.

H 将步骤G所得到的FTO基片自然干燥，放入马弗炉中以2℃/min的升温速率升温至450℃恒温2h，即可得到形貌均一的双层锐钛矿/晶红石二氧化钛(TiO2)纳米线。 H Dry the FTO substrate obtained in step G naturally, put it into a muffle furnace and raise the temperature to 450°C at a constant temperature of 2h at a rate of 2°C/min, and then a double-layer anatase/sphinite with uniform shape can be obtained Titanium dioxide (TiO 2 ) nanowires.

J 将步骤H所得到的FTO基片取出用去离子水洗涤干净自然干燥。 J Take out the FTO substrate obtained in step H, wash it with deionized water and dry it naturally.

K将氧化石墨烯粉末超声分散去离子水中得到氧化石墨烯溶胶。 K ultrasonically disperses graphene oxide powder in deionized water to obtain graphene oxide sol.

L 将表面制备有双层二氧化钛的FTO基片放置于旋涂仪上，将氧化石墨烯溶胶滴加到FTO基片上的双层二氧化钛表面上，旋涂5次。 L Place the FTO substrate prepared with double-layer titanium dioxide on the surface on a spin coater, add the graphene oxide sol dropwise onto the double-layer titanium dioxide surface on the FTO substrate, and spin-coat 5 times.

M将经过旋涂后的FTO基片放入管式炉在氮气气氛下400℃煅烧2h。 M Put the spin-coated FTO substrate into a tube furnace and calcinate at 400°C for 2h under a nitrogen atmosphere.

O 将步骤M所得到的的FTO基片依次浸入硫酸铜和硫代硫酸钠混合溶液、去离子水、氢氧化钠溶液和去离子水；每个浸入时间10s，循环30次后取出自然干燥；即可得到形貌均一的二氧化钛(TiO2)/还原氧化石墨烯（RGO）/氧化亚铜（Cu2O）复合光电极。 O immerse the FTO substrate obtained in step M into copper sulfate and sodium thiosulfate mixed solution, deionized water, sodium hydroxide solution and deionized water successively; each immersion time is 10s, and after 30 cycles, take it out and dry it naturally; A titanium dioxide (TiO 2 )/reduced graphene oxide (RGO)/cuprous oxide (Cu 2 O) composite photoelectrode with uniform morphology can be obtained.

通过调节氧化石墨的旋涂次数可以调节RGO纳米片的厚度。 The thickness of RGO nanosheets can be tuned by adjusting the number of spin coatings of graphite oxide.

实施例3Example 3

A 将15mL的浓盐酸和15mL的去离子水放入烧杯搅拌。 A Put 15mL of concentrated hydrochloric acid and 15mL of deionized water into a beaker and stir.

B 逐滴加入0.35mL钛酸四正丁酯，搅拌均匀至澄清。 B Add 0.35mL tetra-n-butyl titanate dropwise, stir well until clear.

C 将步骤B所得到的溶液转移至四氟乙烯内衬的反应釜中，在其中放入清洗过的FTO基片，升温至180℃温度下恒温6h，自然冷却，得到锐钛矿晶型TiO2纳米线。 C Transfer the solution obtained in step B to a tetrafluoroethylene-lined reaction kettle, put the cleaned FTO substrate in it, raise the temperature to 180°C for 6 hours, and cool naturally to obtain anatase crystal form TiO 2 nanowires.

D 将步骤C所得到的水热后的FTO基片取出用去离子水洗涤干净。 D The hydrothermal FTO substrate obtained in step C is taken out and washed with deionized water.

E 将1mL乙酸和50mL乙醇放入烧杯搅拌。 E Put 1mL of acetic acid and 50mL of ethanol into a beaker and stir.

F 向其中逐滴加入0.75mL钛酸四正丁酯，搅拌均匀至澄清。 F Add 0.75mL tetra-n-butyl titanate dropwise to it, stir evenly until clear.

G 将步骤D所得到的FTO基片泡入步骤F中的溶液1h。 G Soak the FTO substrate obtained in step D into the solution in step F for 1h.

H 将步骤G所得到的FTO基片自然干燥，放入马弗炉中以2℃/min的升温速率升温至450℃恒温2h，即可得到形貌均一的双层锐钛矿/晶红石二氧化钛(TiO2)纳米线。 H Dry the FTO substrate obtained in step G naturally, put it into a muffle furnace and raise the temperature to 450°C at a constant temperature of 2h at a rate of 2°C/min, and then a double-layer anatase/sphinite with uniform shape can be obtained Titanium dioxide (TiO 2 ) nanowires.

J 将步骤H所得到的FTO基片取出用去离子水洗涤干净自然干燥。 J Take out the FTO substrate obtained in step H, wash it with deionized water and dry it naturally.

K将氧化石墨烯粉末超声分散去离子水中得到氧化石墨烯溶胶。 K ultrasonically disperses graphene oxide powder in deionized water to obtain graphene oxide sol.

L 将表面制备有双层二氧化钛的FTO基片放置于旋涂仪上，将氧化石墨烯溶胶滴加到FTO基片上的双层二氧化钛表面上，旋涂3次。 L Place the FTO substrate prepared with double-layer titanium dioxide on the surface on a spin coater, add the graphene oxide sol dropwise onto the double-layer titanium dioxide surface on the FTO substrate, and spin-coat three times.

M将经过旋涂后的FTO基片放入管式炉在氮气气氛下400℃煅烧2h。 M Put the spin-coated FTO substrate into a tube furnace and calcinate at 400°C for 2h under a nitrogen atmosphere.

O 将步骤M所得到的的FTO基片依次浸入硫酸铜和硫代硫酸钠混合溶液、去离子水、氢氧化钠溶液和去离子水；每个浸入时间20s，循环30次后取出自然干燥；即可得到形貌均一的二氧化钛(TiO2)/还原氧化石墨烯（RGO）/氧化亚铜（Cu2O）复合光电极。 O immerse the FTO substrate obtained in step M into copper sulfate and sodium thiosulfate mixed solution, deionized water, sodium hydroxide solution and deionized water successively; each immersion time is 20s, and after 30 cycles, take it out and dry it naturally; A titanium dioxide (TiO 2 )/reduced graphene oxide (RGO)/cuprous oxide (Cu 2 O) composite photoelectrode with uniform morphology can be obtained.

通过调节浸入时间可以调控Cu2O的含量。 The content of Cu 2 O can be regulated by adjusting the immersion time.

实施例4Example 4

一种二氧化钛(TiO2)/还原氧化石墨烯（RGO）/氧化亚铜（Cu2O）复合电极的制备方法，是按照下述步骤进行: A preparation method of titanium dioxide (TiO 2 )/reduced graphene oxide (RGO)/cuprous oxide (Cu 2 O) composite electrode is carried out according to the following steps:

A 将15mL的浓盐酸和15mL的去离子水放入烧杯搅拌。 A Put 15mL of concentrated hydrochloric acid and 15mL of deionized water into a beaker and stir.

B 逐滴加入0.35mL钛酸四正丁酯，搅拌均匀至澄清。 B Add 0.35mL tetra-n-butyl titanate dropwise, stir well until clear.

C 将步骤B所得到的溶液转移至四氟乙烯内衬的反应釜中，在其中放入清洗过的FTO基片，升温至180℃温度下恒温6h，自然冷却，得到锐钛矿晶型TiO2纳米线。 C Transfer the solution obtained in step B to a tetrafluoroethylene-lined reaction kettle, put the cleaned FTO substrate in it, raise the temperature to 180°C for 6 hours, and cool naturally to obtain anatase crystal form TiO 2 nanowires.

D 将步骤C所得到的水热后的FTO基片取出用去离子水洗涤干净。 D The hydrothermal FTO substrate obtained in step C is taken out and washed with deionized water.

E 将1mL乙酸和50mL乙醇放入烧杯搅拌。 E Put 1mL of acetic acid and 50mL of ethanol into a beaker and stir.

F 向其中逐滴加入0.75mL钛酸四正丁酯，搅拌均匀至澄清。 F Add 0.75mL tetra-n-butyl titanate dropwise to it, stir evenly until clear.

G 将步骤D所得到的FTO基片泡入步骤F中的溶液1h。 G Soak the FTO substrate obtained in step D into the solution in step F for 1h.

H 将步骤G所得到的FTO基片自然干燥，放入马弗炉中以2℃/min的升温速率升温至450℃恒温2h，即可得到形貌均一的双层锐钛矿/晶红石二氧化钛(TiO2)纳米线。 H Dry the FTO substrate obtained in step G naturally, put it into a muffle furnace and raise the temperature to 450°C at a constant temperature of 2h at a rate of 2°C/min, and then a double-layer anatase/sphinite with uniform shape can be obtained Titanium dioxide (TiO 2 ) nanowires.

J 将步骤H所得到的FTO基片取出用去离子水洗涤干净自然干燥。 J Take out the FTO substrate obtained in step H, wash it with deionized water and dry it naturally.

K将氧化石墨烯粉末超声分散去离子水中得到氧化石墨烯溶胶。 K ultrasonically disperses graphene oxide powder in deionized water to obtain graphene oxide sol.

L 将表面制备有双层二氧化钛的FTO基片放置于旋涂仪上，将氧化石墨烯溶胶滴加到FTO基片上的双层二氧化钛表面上，旋涂5次。 L Place the FTO substrate prepared with double-layer titanium dioxide on the surface on a spin coater, add the graphene oxide sol dropwise onto the double-layer titanium dioxide surface on the FTO substrate, and spin-coat 5 times.

M将经过旋涂后的FTO基片放入管式炉在氮气气氛下400℃煅烧2h。 M Put the spin-coated FTO substrate into a tube furnace and calcinate at 400°C for 2h under a nitrogen atmosphere.

O 将步骤M所得到的的FTO基片依次浸入硫酸铜和硫代硫酸钠混合溶液、去离子水、氢氧化钠溶液和去离子水；每个浸入时间10s，循环60次后取出自然干燥；即可得到形貌均一的二氧化钛(TiO2)/还原氧化石墨烯（RGO）/氧化亚铜（Cu2O）复合光电极。 O immerse the FTO substrate obtained in step M into copper sulfate and sodium thiosulfate mixed solution, deionized water, sodium hydroxide solution and deionized water successively; each immersion time is 10s, and after 60 cycles, take it out and dry it naturally; A titanium dioxide (TiO 2 )/reduced graphene oxide (RGO)/cuprous oxide (Cu 2 O) composite photoelectrode with uniform morphology can be obtained.

通过调节Cu2O的循环次(在四个烧杯各浸泡一次为一个循环数)可以调控Cu2O的含量。 The content of Cu 2 O can be regulated by adjusting the number of cycles of Cu 2 O (soaking once in each of the four beakers is one cycle).

Claims (7)

1. the synthetic method of a combined electrode, it is characterized in that: described combined electrode is that titanium dioxide/redox graphene/Red copper oxide compound 3 ties up optoelectronic pole, under employing low temperature, liquid phase method first prepares the titanium dioxide nano thread of the relatively homogeneous Detitanium-ore-type of pattern on FTO substrate through hydro-thermal reaction, then prepared the titanium dioxide nano thread of brilliant red stone-type again through calcining by sol-gel method, then spin-coating method is adopted to synthesize one deck oxidation graphene film on double-deck Detitanium-ore-type/brilliant red stone-type titanium dioxide nano thread surface that pattern is homogeneous, finally by chemical deposition at oxidation graphene film surface deposition Red copper oxide.
2. the synthetic method of a kind of combined electrode as claimed in claim 1, is characterized in that concrete steps are as follows: obtain graphene oxide colloidal sol by graphene oxide powder ultrasonic dispersion deionized water; There is the FTO substrate of double-deck Detitanium-ore-type/brilliant red stone-type titanium dioxide nano thread to be positioned on spin coating instrument surface preparation, graphene oxide colloidal sol is added drop-wise to the on-chip two-layer titanium dioxide of FTO on the surface, spin coating 3 ~ 5 times; FTO substrate after spin coating is put into tube furnace calcine in a nitrogen atmosphere; FTO substrate after calcining is immersed copper sulfate and Sulfothiorine mixing solutions, deionized water, sodium hydroxide solution and deionized water successively; Each immersion time 10 ~ 20s, circulates after 30 ~ 90 times and takes out seasoning; Pattern homogeneous titanium dioxide/redox graphene/Red copper oxide complex light electrode can be obtained.
3. the synthetic method of a kind of combined electrode as claimed in claim 2, is characterized in that: described calcining refers to 400 DEG C of calcining 2h.
4. the synthetic method of a kind of combined electrode as claimed in claim 2, is characterized in that: the concentration of graphene oxide colloidal sol is 1g/L.
5. the synthetic method of a kind of combined electrode as claimed in claim 2, is characterized in that: in copper sulfate and Sulfothiorine mixing solutions, the concentration of copper sulfate and Sulfothiorine is 1mol/L; The concentration of sodium hydroxide solution is also 1mol/L.
6. the synthetic method of a kind of combined electrode as claimed in claim 2, is characterized in that: the FTO substrate after calcining is immersed copper sulfate and Sulfothiorine mixing solutions, deionized water, sodium hydroxide solution and deionized water successively; Each immersion time 10s, circulates after 60 times and takes out seasoning.
7. as claimed in claim 1 or 2 the combined electrode prepared of preparation method in photoelectrochemistry hydrolysis reaction as the purposes of working electrode.
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