CN111569896A - BiVO4-Ni/Co3O4Synthesis method of heterojunction and application of heterojunction to photoelectrolysis water - Google Patents

BiVO4-Ni/Co3O4Synthesis method of heterojunction and application of heterojunction to photoelectrolysis water Download PDF

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CN111569896A
CN111569896A CN202010423004.6A CN202010423004A CN111569896A CN 111569896 A CN111569896 A CN 111569896A CN 202010423004 A CN202010423004 A CN 202010423004A CN 111569896 A CN111569896 A CN 111569896A
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范伟强
俞立豪
白红叶
高杨
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Abstract

The invention belongs to the technical field of nano composite materials, and relates to BiVO4‑Ni/Co3O4The heterogeneous combination method comprises growing a layer of BiOI nanoparticles on FTO substrate by electrodeposition, dropping vanadyl acetylacetonate solution on FTO surface, and calcining at high temperature to obtain bismuth vanadate (BiVO)4) Placing FTO obliquely on the surface of a substrate containing Co (NO) by continuous ion adsorption reaction3)2·6H2O、Ni(NO3)2·6H2O、C6H12N4、CH4N2O and NH4F, hydrothermal reaction at 120-200 ℃ in deionized water solutionTaking out the mixture for 2-5 h, washing the mixture with deionized water, annealing the mixture for 1.5-3 h at 300-500 ℃, and naturally cooling the mixture to room temperature to obtain the product. The invention also uses the prepared heterojunction as a photoelectrode to be applied to photoelectrochemical hydrolysis reaction. The method utilizes a simple electrodeposition method and a hydrothermal method, has simple operation and good repeatability, uses low material cost, has large reserve and no toxicity, and meets the environment-friendly requirement; the prepared material can obviously reduce the interface reaction potential barrier, effectively inhibit the charge recombination of a solid-liquid interface, accelerate the water oxidation reaction kinetics, and improve the photocurrent density, thereby better utilizing the solar energy.

Description

BiVO4-Ni/Co3O4异质结的合成方法及其应用于光电解水Synthesis of BiVO4-Ni/Co3O4 Heterojunction and Its Application in Photoelectrolysis of Water

技术领域technical field

本发明属于纳米复合材料合成技术领域，涉及异质结合成，尤其涉及一种BiVO4-Ni/Co3O4异质结合成方法及其应用于光电解水。The invention belongs to the technical field of nano-composite material synthesis, and relates to heterogeneous combination, in particular to a method for heterogeneous combination of BiVO 4 -Ni/Co 3 O 4 and its application to photo-electrolyzed water.

背景技术Background technique

有效利用太阳能一直备受关注，由于化石燃料的枯竭，且带来的严重污染迫使人类不得不寻求新的清洁能源。利用太阳光分解水产生氢气是一项非常好的策略，能满足未来清洁能源的需求。The effective use of solar energy has always attracted attention. Due to the depletion of fossil fuels and the serious pollution caused, human beings have to seek new and clean energy. Using sunlight to split water to produce hydrogen is an excellent strategy to meet future clean energy needs.

近年来，以BiVO4为代表的铋系半导体在光电化学分解水领域被广泛应用。由于它的成本低、化学性质稳定、带隙窄(2.4eV)等优点受到研究者的青睐。但是，纯BiVO4由于低的电荷分离效率和缓慢的水氧化动力学导致光电流密度的低下，限制了理论上的光电化学分解水产氢效率。In recent years, bismuth-based semiconductors represented by BiVO 4 have been widely used in the field of photoelectrochemical water splitting. It is favored by researchers due to its low cost, stable chemical properties, and narrow band gap (2.4 eV). However, pure BiVO4 limits the theoretical photoelectrochemical water splitting efficiency for hydrogen production due to low charge separation efficiency and slow water oxidation kinetics resulting in low photocurrent density.

为进一步开发BiVO4的光电催化性能，异质结构建、形貌调控、界面工程和元素掺杂等策略被研究和利用。Co基材料由于成本低廉、储量大、功能性强一直被研究。作为窄带系的p型半导体Co3O4(2.07eV)，能和BiVO4耦合形成BiVO4-Ni/Co3O4的p-n异质结，加快电子-空穴分离效率，提升光电化学分解水的性能。Ni元素的引入则进一步提高导电性。Ni/Co3O4析氧助催化剂能够降低过电位，显著改善水氧化动力学。To further develop the photoelectric catalytic performance of BiVO 4 , strategies such as heterostructure construction, morphology control, interface engineering, and element doping have been studied and utilized. Co-based materials have been studied because of their low cost, large reserves and strong functionality. As a narrow-band p-type semiconductor Co 3 O 4 (2.07eV), it can couple with BiVO 4 to form a BiVO 4 -Ni/Co 3 O 4 pn heterojunction, accelerate the electron-hole separation efficiency, and improve photoelectrochemical water splitting performance. The introduction of Ni element further improves the conductivity. The Ni/Co 3 O 4 oxygen evolution cocatalyst can reduce the overpotential and significantly improve the water oxidation kinetics.

发明内容SUMMARY OF THE INVENTION

针对上述现有技术中存在的不足，本发明的目的是提供一种BiVO4-Ni/Co3O4异质结材料的合成方法。In view of the above-mentioned deficiencies in the prior art, the purpose of the present invention is to provide a method for synthesizing a BiVO 4 -Ni/Co 3 O 4 heterojunction material.

本发明首先采用经典的恒电压电沉积，在FTO表面制备BiVO4，FTO依次用无水乙醇、丙酮、水进行超声处理，烘干备用；再选取Co(NO3)2·6H2O、Ni(NO3)2·6H2O、C6H12N4、尿素(CH4N2O)和NH4F等试剂配制成混合溶液，用水热法，将密闭的反应釜置于180℃的高温烘箱中反应，取出并用大量去离子水冲洗，置于马弗炉高温退火，最终得到目标产物BiVO4-Ni/Co3O4。In the present invention, the classical constant voltage electrodeposition is used to prepare BiVO 4 on the surface of the FTO, and the FTO is ultrasonically treated with absolute ethanol, acetone and water in turn, and dried for later use; and then Co(NO 3 ) 2 ·6H 2 O, Ni (NO 3 ) 2 ·6H 2 O, C 6 H 12 N 4 , urea (CH 4 N 2 O) and NH 4 F and other reagents were prepared into a mixed solution, and the closed reaction kettle was placed in a 180° C. The reaction was carried out in a high temperature oven, taken out and rinsed with a large amount of deionized water, placed in a muffle furnace for high temperature annealing, and finally the target product BiVO 4 -Ni/Co 3 O 4 was obtained.

一种BiVO4-Ni/Co3O4异质结的合成方法，按照下列步骤进行:A kind of synthetic method of BiVO 4 -Ni/Co 3 O 4 heterojunction, carry out according to the following steps:

A、配制0.4mol/L的KI溶液，加入Bi(NO3)3·5H2O得混合水溶液，Bi(NO3)3的浓度为0.04mol/L，以硝酸调节pH至1～3，优选1.7，倒入对苯醌的乙醇溶液，搅拌10～20min，得到BiOI前驱体溶液，其中所述混合水溶液与对苯醌的乙醇溶液的体积比为5:1～5:3，优选5:2；所述对苯醌的乙醇溶液的浓度为0.23mol/L；A. Prepare 0.4 mol/L KI solution, add Bi(NO 3 ) 3 ·5H 2 O to obtain a mixed aqueous solution, the concentration of Bi(NO 3 ) 3 is 0.04 mol/L, adjust the pH to 1～3 with nitric acid, preferably 1.7, pour the ethanolic solution of p-benzoquinone, stir for 10～20min, obtain BiOI precursor solution, wherein the volume ratio of the mixed aqueous solution and the ethanolic solution of p-benzoquinone is 5:1～5:3, preferably 5:2 ; The concentration of the ethanolic solution of described p-benzoquinone is 0.23mol/L;

B、前驱体溶液置于三电极***，以FTO为工作电极、Pt丝为对电极、Ag/AgCl为参比电极，-0.1Vvs Ag/AgCl的偏压下电沉积3～6min，优选5min，在FTO表面形成均匀的暗红色BiOI薄膜，用离子水洗涤FTO，室温干燥；B. The precursor solution was placed in a three-electrode system, with FTO as the working electrode, Pt wire as the counter electrode, and Ag/AgCl as the reference electrode, and electrodeposited under the bias voltage of -0.1Vvs Ag/AgCl for 3 to 6 minutes, preferably 5 minutes, A uniform dark red BiOI film was formed on the surface of FTO, the FTO was washed with ionized water, and dried at room temperature;

C、向BiOI薄膜表面滴加0.2mol/L乙酰丙酮氧钒水溶液，将FTO于300～600℃煅烧退火1.5～3h，优选450℃退火2h，取出自然冷却至室温，用NaOH溶液浸泡去除表面多余的V2O5，去离子水洗净、干燥获得FTO基片生长有BiVO4光阳极；C. Add 0.2mol/L vanadyl acetylacetonate aqueous solution dropwise to the surface of the BiOI film, calcine and anneal the FTO at 300～600℃ for 1.5～3h, preferably anneal at 450℃ for 2h, take out and cool to room temperature naturally, soak in NaOH solution to remove excess surface of V 2 O 5 , washed with deionized water and dried to obtain FTO substrate with BiVO 4 photoanode grown;

D、向去离子水中加入Co(NO3)2·6H2O、Ni(NO3)2·6H2O、C6H12N4、CH4N2O和NH4F，超声搅拌均匀为混合溶液，其中所述Co(NO3)2·6H2O：Ni(NO3)2·6H2O：C6H12N4：CH4N2O：NH4F：去离子水为固液比0.5～5mM：2.5mM：6mM：0.36g：0.195g：50mL，优选2.5mM：2.5mM：6mM：0.36g：0.195g：50mL；D. Add Co(NO 3 ) 2 .6H 2 O, Ni(NO 3 ) 2 .6H 2 O, C 6 H 12 N 4 , CH 4 N 2 O and NH 4 F to deionized water, and ultrasonically stir evenly to Mixed solution, wherein the Co(NO 3 ) 2 ·6H 2 O: Ni(NO 3 ) 2 ·6H 2 O: C 6 H 12 N 4 : CH 4 N 2 O: NH 4 F: deionized water is solid Liquid ratio 0.5-5mM: 2.5mM: 6mM: 0.36g: 0.195g: 50mL, preferably 2.5mM: 2.5mM: 6mM: 0.36g: 0.195g: 50mL;

E、将上述混合溶液倒入水热反应釜中至体积60％处，所制得的FTO基片生长有BiVO4光阳极倾斜放置，反应温度120～200℃，加热2～5h，优选180℃加热3h，自然冷却至室温，取出用去离子水洗净，高温退火300～500℃，退火时间1.5～3h，优选400℃高温退火2h，自然冷却至室温，即得。E. Pour the above mixed solution into the hydrothermal reaction kettle to 60% of the volume, the prepared FTO substrate is grown with BiVO 4 photoanode is inclined and placed, the reaction temperature is 120～200 ℃, heated for 2～5h, preferably 180 ℃ Heating for 3 hours, cooling to room temperature naturally, taking out and washing with deionized water, annealing at high temperature at 300-500°C for 1.5-3 hours, preferably annealing at 400°C for 2 hours, and cooling to room temperature naturally.

本发明所使用的FTO，需预处理，即依次用无水乙醇、丙酮、水进行超声处理，烘干后备用。The FTO used in the present invention needs to be pretreated, that is, ultrasonically treated with absolute ethanol, acetone and water in sequence, and dried for later use.

本发明所合成的复合电极的物相、结构以及性能表征由X-射线衍射仪测定。The phase, structure and performance characterization of the composite electrode synthesized in the present invention are determined by X-ray diffractometer.

本发明的另一个目的在于，将异质结材料作为工作电极应用于光电化学水解反应。Another object of the present invention is to use the heterojunction material as a working electrode for photoelectrochemical hydrolysis.

BiVO4-Ni/Co3O4异质结光电极在氙灯光源照射下光电流测试步骤如下：The photocurrent test steps of BiVO 4 -Ni/Co 3 O 4 heterojunction photoelectrode under xenon lamp illumination are as follows:

在CHI 852C型电化学工作站下进行，电解槽里加入0.5mol/L的硫酸钠(Na2SO4)作为电解液，氯化银电极作为参比电极，铂电极作为对电极，BiVO4-Ni/Co3O4异质结材料作为工作电极，进行I–V特性曲线的扫描。It was carried out under the CHI 852C electrochemical workstation. 0.5mol/L sodium sulfate (Na 2 SO 4 ) was added to the electrolytic cell as the electrolyte, the silver chloride electrode was used as the reference electrode, the platinum electrode was used as the counter electrode, and BiVO 4 -Ni The /Co 3 O 4 heterojunction material was used as the working electrode to scan the I–V characteristic curve.

使用配备有单色器的太阳光模拟器，在入射光范围为300-540nm以及1.23VRHE偏压下，测定异质结光阳极的光电转换效率(IPCE)。Using a solar simulator equipped with a monochromator, the photoelectric conversion efficiency (IPCE) of the heterojunction photoanode was determined under an incident light range of 300-540 nm and a RHE bias of 1.23 V.

有益效果beneficial effect

本发明利用简单的电沉积法和水热合成法制备出了BiVO4-Ni/Co3O4异质结光电极，该材料具有良好的化学稳定性和光电化学性能好的优点，显著降低界面反应势垒，有效抑制固液界面电荷复合，加快水氧化反应动力学，提高光电流密度从而更好的利用太阳能。本发明操作简单，重复性好，且所用材料成本低，储量大，无毒性，符合环境友好要求。In the present invention, the BiVO 4 -Ni/Co 3 O 4 heterojunction photoelectrode is prepared by a simple electrodeposition method and a hydrothermal synthesis method, and the material has the advantages of good chemical stability and good photoelectrochemical performance, and significantly reduces the interface The reaction barrier can effectively inhibit the charge recombination at the solid-liquid interface, accelerate the kinetics of water oxidation reaction, and improve the photocurrent density to better utilize solar energy. The invention has the advantages of simple operation, good repeatability, low cost of used materials, large reserves, non-toxicity, and meets the requirements of environmental friendliness.

附图说明Description of drawings

图1.BiVO4、BiVO4/Co3O4和BiVO4-Ni/Co3O4样品的X-射线粉末衍射图谱。Figure 1. X-ray powder diffraction patterns of BiVO 4 , BiVO 4 /Co 3 O 4 and BiVO 4 -Ni/Co 3 O 4 samples.

图2.在光照和黑暗下BiVO4、BiVO4/Co3O4和BiVO4-Ni/Co3O4的I–V特性曲线图，实线和虚线分别对应光电流和暗电流。Figure 2. I–V characteristic curves of BiVO 4 , BiVO 4 /Co 3 O 4 and BiVO 4 -Ni/Co 3 O 4 under light and dark conditions, the solid and dashed lines correspond to the photocurrent and dark current, respectively.

图3.异质结光阳极的光电转换效率(IPCE)。Figure 3. Photoelectric conversion efficiency (IPCE) of heterojunction photoanode.

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BiVO4-Ni/Co3O4异质结的合成方法，按照下列步骤进行:A kind of synthetic method of BiVO 4 -Ni/Co 3 O 4 heterojunction, carry out according to the following steps:

A、FTO基片上BiVO4光阳极，所述的在FTO基片上制备出BiVO4光阳极的步骤为:(1)先用50mL的去离子水溶解3.32g KI，然后，将0.9701g Bi(NO3)3·5H2O加入上述溶液搅拌10min，滴加硝酸调节pH至1.0，形成稳定的混合溶液A；A, BiVO 4 photoanode on the FTO substrate, the described step of preparing BiVO 4 photoanode on the FTO substrate is: (1) first dissolve 3.32g KI with 50mL deionized water, then, 0.9701g Bi(NO 3 ) 3.5H 2 O was added to the above solution and stirred for 10 min, and nitric acid was added dropwise to adjust the pH to 1.0 to form a stable mixed solution A;

(2)用20mL无水乙醇溶解0.4972g对苯醌，将烧杯密封搅拌10min，得到溶液B；(2) dissolve 0.4972g p-benzoquinone with 20mL absolute ethanol, seal and stir the beaker for 10min to obtain solution B;

(3)B溶液缓慢加入上述A溶液中并搅拌10min，形成BiOI的前驱体溶液C；(3) B solution is slowly added to above-mentioned A solution and stirred for 10min to form the precursor solution C of BiOI;

(4)采用三电极体系，FTO为工作电极、Pt丝为对电极、Ag/AgCl为参比电极。在-0.1V偏压下，电沉积3min在FTO上形成均匀的暗红色BiOI薄膜；(4) A three-electrode system was adopted, with FTO as the working electrode, Pt wire as the counter electrode, and Ag/AgCl as the reference electrode. Under -0.1V bias voltage, a uniform dark red BiOI film was formed on FTO by electrodeposition for 3min;

(5)用离子水冲洗FTO，室温干燥。BiOI膜表面再滴加定量的0.2mol/L乙酰丙酮氧钒，将BiOI置于300℃马弗炉高温退火2h，样品自然冷却至室温；(5) Rinse the FTO with ionized water and dry at room temperature. Quantitative 0.2mol/L vanadyl acetylacetonate was added dropwise to the surface of the BiOI film, the BiOI was annealed at a high temperature of 300℃ in a muffle furnace for 2h, and the sample was naturally cooled to room temperature;

(6)最后，样品浸泡于1mol/L的NaOH溶液20min，去除电极表面多余的V2O5。BiVO4样品用大量去离子水冲洗，并在室温下干燥，得到纯净的BiVO4光阳极。(6) Finally, the sample was soaked in 1 mol/L NaOH solution for 20 min to remove excess V 2 O 5 on the electrode surface. The BiVO4 samples were rinsed with plenty of deionized water and dried at room temperature to obtain a pure BiVO4 photoanode.

B、BiVO4-Ni/Co3O4光电极的制备：B. Preparation of BiVO 4 -Ni/Co 3 O 4 photoelectrode:

(1)将0.5mM Co(NO3)2·6H2O、2.5mM Ni(NO3)2·6H2O、6mM C6H12N4、0.36g尿素(CH4N2O)、0.195g NH4F依次加入50mL去离子水中，超声搅拌15min，得到混合溶液D；(1) 0.5 mM Co(NO 3 ) 2 ·6H 2 O, 2.5 mM Ni(NO 3 ) 2 ·6H 2 O, 6 mM C 6 H 12 N 4 , 0.36 g urea (CH 4 N 2 O), 0.195 g NH 4 F was added to 50 mL of deionized water in turn, and ultrasonically stirred for 15 min to obtain mixed solution D;

(2)将30mL混合溶液D加入到50mL的聚四氟乙烯内衬不锈钢反应釜，BiVO4光阳极倾斜放置于反应釜。将密闭的反应釜置于120℃的高温烘箱中反应3h，将样品取出并用大量去离子水冲洗，样品置于马弗炉400℃高温退火2h，得到目标产物BiVO4-Ni/Co3O4。(2) 30mL of mixed solution D was added to 50mL of PTFE-lined stainless steel reaction kettle, and the BiVO 4 photoanode was placed in the reaction kettle obliquely. The closed reaction kettle was placed in a high temperature oven at 120°C for 3 hours, the sample was taken out and rinsed with a large amount of deionized water, and the sample was placed in a muffle furnace for annealing at a high temperature of 400°C for 2 hours to obtain the target product BiVO 4 -Ni/Co 3 O 4 .

测定了异质结光阳极的光电转换效率(IPCE)，BiVO4-Ni/Co3O4在380nm处IPCE值达到25％。The photoelectric conversion efficiency (IPCE) of the heterojunction photoanode was measured, and the IPCE value of BiVO 4 -Ni/Co 3 O 4 reached 25% at 380 nm.

实施例2Example 2

一种BiVO4-Ni/Co3O4异质结的合成方法，按照下列步骤进行:A kind of synthetic method of BiVO 4 -Ni/Co 3 O 4 heterojunction, carry out according to the following steps:

A、FTO基片上BiVO4光阳极，所述的在FTO基片上制备出BiVO4光阳极的步骤为:(1)先用50mL的去离子水溶解3.32g KI，然后，将0.9701g Bi(NO3)3·5H2O加入上述溶液搅拌10min，滴加硝酸调节pH至1.3，形成稳定的混合溶液A；A, BiVO 4 photoanode on the FTO substrate, the described step of preparing BiVO 4 photoanode on the FTO substrate is: (1) first dissolve 3.32g KI with 50mL deionized water, then, 0.9701g Bi(NO 3 ) 3.5H 2 O was added to the above solution and stirred for 10 min, and nitric acid was added dropwise to adjust the pH to 1.3 to form a stable mixed solution A;

(2)用20mL无水乙醇溶解0.4972g对苯醌，将烧杯密封搅拌10min，得到溶液B；(2) dissolve 0.4972g p-benzoquinone with 20mL absolute ethanol, seal and stir the beaker for 10min to obtain solution B;

(3)B溶液缓慢加入上述A溶液中并搅拌10min，形成BiOI的前驱体溶液C；(3) B solution is slowly added to above-mentioned A solution and stirred for 10min to form the precursor solution C of BiOI;

(4)采用三电极体系，FTO为工作电极、Pt丝为对电极、Ag/AgCl为参比电极，在-0.1V偏压下，电沉积4min在FTO上形成均匀的暗红色BiOI薄膜；(4) A three-electrode system was used, with FTO as the working electrode, Pt wire as the counter electrode, and Ag/AgCl as the reference electrode. Under -0.1V bias, a uniform dark red BiOI film was formed on the FTO by electrodeposition for 4 minutes;

(5)用离子水冲洗FTO，室温干燥。BiOI膜表面再滴加定量的0.2mol/L乙酰丙酮氧钒，将BiOI置于400℃马弗炉高温退火2h，样品自然冷却至室温；(5) Rinse the FTO with ionized water and dry at room temperature. Quantitative 0.2mol/L vanadyl acetylacetonate was added dropwise to the surface of the BiOI film, and the BiOI was annealed at a high temperature of 400 °C in a muffle furnace for 2 hours, and the sample was naturally cooled to room temperature;

(6)样品浸泡于1mol/L的NaOH溶液20min，去除电极表面多余的V2O5，BiVO4样品用大量去离子水冲洗，并在室温下干燥，得到纯净的BiVO4光阳极。(6) The sample was soaked in 1 mol/L NaOH solution for 20 min to remove excess V 2 O 5 on the electrode surface. The BiVO 4 sample was rinsed with a large amount of deionized water and dried at room temperature to obtain a pure BiVO 4 photoanode.

B、BiVO4-Ni/Co3O4光电极的制备：B. Preparation of BiVO 4 -Ni/Co 3 O 4 photoelectrode:

(1)将1.5mM Co(NO3)2·6H2O、2.5mM Ni(NO3)2·6H2O、6mM C6H12N4、0.36g尿素(CH4N2O)、0.195g NH4F依次加入50mL去离子水中，超声搅拌15min，得到混合溶液D；(1) 1.5 mM Co(NO 3 ) 2 ·6H 2 O, 2.5 mM Ni(NO 3 ) 2 ·6H 2 O, 6 mM C 6 H 12 N 4 , 0.36 g urea (CH 4 N 2 O), 0.195 g NH 4 F was added to 50 mL of deionized water in turn, and ultrasonically stirred for 15 min to obtain mixed solution D;

(2)然后，将30mL混合溶液D加入到50mL的聚四氟乙烯内衬不锈钢反应釜，BiVO4光阳极倾斜放置于反应釜；将密闭的反应釜置于160℃的高温烘箱中反应3h，将样品取出并用大量去离子水冲洗，置于马弗炉400℃高温退火2h，得到目标产物BiVO4-Ni/Co3O4。(2) Then, 30mL of mixed solution D was added to 50mL of PTFE-lined stainless steel reaction kettle, and the BiVO 4 photoanode was placed in the reaction kettle obliquely; the closed reaction kettle was placed in a high-temperature oven at 160°C for 3h reaction, The sample was taken out, rinsed with a large amount of deionized water, and annealed at a high temperature of 400 °C for 2 h in a muffle furnace to obtain the target product BiVO 4 -Ni/Co 3 O 4 .

测定了异质结光阳极的光电转换效率(IPCE)，BiVO4-Ni/Co3O4在380nm处IPCE值达到26％。The photoelectric conversion efficiency (IPCE) of the heterojunction photoanode was measured, and the IPCE value of BiVO 4 -Ni/Co 3 O 4 reached 26% at 380 nm.

实施例3Example 3

一种BiVO4-Ni/Co3O4异质结的合成方法，按照下列步骤进行:A kind of synthetic method of BiVO 4 -Ni/Co 3 O 4 heterojunction, carry out according to the following steps:

A、FTO基片上BiVO4光阳极，所述的在FTO基片上制备出BiVO4光阳极的步骤为:(1)先用50mL的去离子水溶解3.32g KI，然后，将0.9701g Bi(NO3)3·5H2O加入上述溶液搅拌10min，滴加硝酸调节pH至1.7，形成稳定的混合溶液A；A, BiVO 4 photoanode on the FTO substrate, the described step of preparing BiVO 4 photoanode on the FTO substrate is: (1) first dissolve 3.32g KI with 50mL deionized water, then, 0.9701g Bi(NO 3 ) 3.5H 2 O was added to the above solution, stirred for 10 min, and nitric acid was added dropwise to adjust the pH to 1.7 to form a stable mixed solution A;

(2)用20mL无水乙醇溶解0.4972g对苯醌，将烧杯密封搅拌10min，得到溶液B；(2) dissolve 0.4972g p-benzoquinone with 20mL absolute ethanol, seal and stir the beaker for 10min to obtain solution B;

(3)B溶液缓慢加入上述A溶液中并搅拌10min，形成BiOI的前驱体溶液C；(3) B solution is slowly added to above-mentioned A solution and stirred for 10min to form the precursor solution C of BiOI;

(4)采用三电极体系，FTO为工作电极、Pt丝为对电极、Ag/AgCl为参比电极，在-0.1V偏压下，电沉积5min在FTO上形成均匀的暗红色BiOI薄膜；(4) A three-electrode system was used, with FTO as the working electrode, Pt wire as the counter electrode, and Ag/AgCl as the reference electrode. Under -0.1V bias, a uniform dark red BiOI film was formed on the FTO by electrodeposition for 5 minutes;

(5)用离子水冲洗FTO，室温干燥，BiOI膜表面再滴加定量的0.2mol/L乙酰丙酮氧钒，将BiOI置于450℃马弗炉高温退火2h，样品自然冷却至室温；(5) Rinse the FTO with ionized water, dry at room temperature, add a quantitative amount of 0.2mol/L vanadyl acetylacetonate dropwise to the surface of the BiOI film, place the BiOI in a 450°C muffle furnace for high temperature annealing for 2h, and cool the sample to room temperature naturally;

(6)样品浸泡于1mol/L的NaOH溶液20min，去除电极表面多余的V2O5，BiVO4样品用大量去离子水冲洗，并在室温下干燥，得到纯净的BiVO4光阳极。(6) The sample was soaked in 1 mol/L NaOH solution for 20 min to remove excess V 2 O 5 on the electrode surface. The BiVO 4 sample was rinsed with a large amount of deionized water and dried at room temperature to obtain a pure BiVO 4 photoanode.

B、BiVO4-Ni/Co3O4光电极的制备：B. Preparation of BiVO 4 -Ni/Co 3 O 4 photoelectrode:

(1)将2.5mM Co(NO3)2·6H2O、2.5mM Ni(NO3)2·6H2O、6mM C6H12N4、0.36g尿素(CH4N2O)、0.195g NH4F依次加入50mL去离子水中，超声搅拌15min，得到混合溶液D；(1) 2.5 mM Co(NO 3 ) 2 ·6H 2 O, 2.5 mM Ni(NO 3 ) 2 ·6H 2 O, 6 mM C 6 H 12 N 4 , 0.36 g urea (CH 4 N 2 O), 0.195 g NH 4 F was added to 50 mL of deionized water in turn, and ultrasonically stirred for 15 min to obtain mixed solution D;

(2)将30mL混合溶液D加入到50mL的聚四氟乙烯内衬不锈钢反应釜，BiVO4光阳极倾斜放置于反应釜，将密闭的反应釜置于180℃的高温烘箱中反应3h，取出并用大量去离子水冲洗，置于马弗炉400℃高温退火2h，得到目标产物BiVO4-Ni/Co3O4。(2) 30mL of mixed solution D was added to 50mL of PTFE-lined stainless steel reaction kettle, BiVO 4 photoanode was placed in the reaction kettle obliquely, and the closed reaction kettle was placed in a high temperature oven at 180°C for 3h reaction, taken out and used Rinse with a large amount of deionized water, and place it in a muffle furnace for annealing at a high temperature of 400 °C for 2 h to obtain the target product BiVO 4 -Ni/Co 3 O 4 .

测定了异质结光阳极的光电转换效率(IPCE)，BiVO4-Ni/Co3O4在380nm处IPCE值达到27％。The photoelectric conversion efficiency (IPCE) of the heterojunction photoanode was measured, and the IPCE value of BiVO 4 -Ni/Co 3 O 4 reached 27% at 380 nm.

实施例4Example 4

一种BiVO4-Ni/Co3O4异质结的合成方法，按照下列步骤进行:A kind of synthetic method of BiVO 4 -Ni/Co 3 O 4 heterojunction, carry out according to the following steps:

A、FTO基片上BiVO4光阳极，所述的在FTO基片上制备出BiVO4光阳极的步骤为:(1)先用50mL的去离子水溶解3.32g KI，将0.9701g Bi(NO3)3·5H2O加入上述溶液搅拌10min，滴加硝酸调节pH至2.5，形成稳定的混合溶液A；A, BiVO 4 photoanode on the FTO substrate, the described steps of preparing BiVO 4 photoanode on the FTO substrate are: (1) first dissolve 3.32g KI with 50mL deionized water, and 0.9701g Bi(NO 3 ) 3. 5H 2 O was added to the above solution and stirred for 10 min, and nitric acid was added dropwise to adjust the pH to 2.5 to form a stable mixed solution A;

(2)用20mL无水乙醇溶解0.4972g对苯醌，将烧杯密封搅拌10min，得到溶液B；(2) dissolve 0.4972g p-benzoquinone with 20mL absolute ethanol, seal and stir the beaker for 10min to obtain solution B;

(3)B溶液缓慢加入上述A溶液中并搅拌10min，形成BiOI的前驱体溶液C；(3) B solution is slowly added to above-mentioned A solution and stirred for 10min to form the precursor solution C of BiOI;

(4)采用三电极体系，FTO为工作电极、Pt丝为对电极、Ag/AgCl为参比电极，在-0.1V偏压下，电沉积5.5min在FTO上形成均匀的暗红色BiOI薄膜；(4) Using a three-electrode system, FTO as the working electrode, Pt wire as the counter electrode, and Ag/AgCl as the reference electrode, under -0.1V bias, electrodeposited for 5.5min to form a uniform dark red BiOI film on FTO;

(5)用离子水冲洗FTO，室温干燥，BiOI膜表面再滴加定量的0.2mol/L乙酰丙酮氧钒，将BiOI置于500℃马弗炉高温退火2h，样品自然冷却至室温；(5) Rinse the FTO with ionized water, dry at room temperature, add a quantitative amount of 0.2mol/L vanadyl acetylacetonate dropwise to the surface of the BiOI film, place the BiOI in a 500°C muffle furnace for high temperature annealing for 2h, and cool the sample to room temperature naturally;

(6)样品浸泡于1mol/L的NaOH溶液20min，去除电极表面多余的V2O5，BiVO4样品用大量去离子水冲洗，并在室温下干燥，得到纯净的BiVO4光阳极。(6) The sample was soaked in 1 mol/L NaOH solution for 20 min to remove excess V 2 O 5 on the electrode surface. The BiVO 4 sample was rinsed with a large amount of deionized water and dried at room temperature to obtain a pure BiVO 4 photoanode.

B、BiVO4-Ni/Co3O4光电极的制备：B. Preparation of BiVO 4 -Ni/Co 3 O 4 photoelectrode:

(1)将3.5mM Co(NO3)2·6H2O、2.5mM Ni(NO3)2·6H2O、6mM C6H12N4、0.36g尿素(CH4N2O)、0.195g NH4F依次加入50mL去离子水中，超声搅拌15min，得到混合溶液D；(1) 3.5 mM Co(NO 3 ) 2 .6H 2 O, 2.5 mM Ni(NO 3 ) 2 .6H 2 O, 6 mM C 6 H 12 N 4 , 0.36 g urea (CH 4 N 2 O), 0.195 g NH 4 F was added to 50 mL of deionized water in turn, and ultrasonically stirred for 15 min to obtain mixed solution D;

(2)将30mL混合溶液D加入到50mL的聚四氟乙烯内衬不锈钢反应釜，BiVO4光阳极倾斜放置于反应釜，密闭的反应釜置于190℃的高温烘箱中反应3h，将样品取出并用大量去离子水冲洗，样品置于马弗炉400℃高温退火2h，得到目标产物BiVO4-Ni/Co3O4。(2) 30mL of mixed solution D was added to 50mL of PTFE-lined stainless steel reaction kettle, BiVO 4 photoanode was placed in the reaction kettle obliquely, and the closed reaction kettle was placed in a high temperature oven at 190°C for 3h reaction, and the sample was taken out And rinsed with a large amount of deionized water, the sample was placed in a muffle furnace for annealing at a high temperature of 400 ℃ for 2 hours, and the target product BiVO 4 -Ni/Co 3 O 4 was obtained.

测定了异质结光阳极的光电转换效率(IPCE)，BiVO4-Ni/Co3O4在380nm处IPCE值达到25.5％。The photoelectric conversion efficiency (IPCE) of the heterojunction photoanode was measured, and the IPCE value of BiVO 4 -Ni/Co 3 O 4 reached 25.5% at 380 nm.

实施例5Example 5

一种BiVO4-Ni/Co3O4异质结的合成方法，按照下列步骤进行:A kind of synthetic method of BiVO 4 -Ni/Co 3 O 4 heterojunction, carry out according to the following steps:

A、FTO基片上BiVO4光阳极，所述的在FTO基片上制备出BiVO4光阳极的步骤为:(1)先用50mL的去离子水溶解3.32g KI，将0.9701g Bi(NO3)3·5H2O加入上述溶液搅拌10min，滴加硝酸调节pH至3.0，形成稳定的混合溶液A；A, BiVO 4 photoanode on the FTO substrate, the described steps of preparing BiVO 4 photoanode on the FTO substrate are: (1) first dissolve 3.32g KI with 50mL deionized water, and 0.9701g Bi(NO 3 ) 3. 5H 2 O was added to the above solution and stirred for 10 min, and nitric acid was added dropwise to adjust the pH to 3.0 to form a stable mixed solution A;

(2)用20mL无水乙醇溶解0.4972g对苯醌，将烧杯密封搅拌10min，得到溶液B；(2) dissolve 0.4972g p-benzoquinone with 20mL absolute ethanol, seal and stir the beaker for 10min to obtain solution B;

(3)B溶液缓慢加入上述A溶液中并搅拌10min，形成BiOI的前驱体溶液C；(3) B solution is slowly added to above-mentioned A solution and stirred for 10min to form the precursor solution C of BiOI;

(4)采用三电极体系，FTO为工作电极、Pt丝为对电极、Ag/AgCl为参比电极，在-0.1V偏压下，电沉积6min在FTO上形成均匀的暗红色BiOI薄膜；(4) Using a three-electrode system, FTO as the working electrode, Pt wire as the counter electrode, and Ag/AgCl as the reference electrode, under -0.1V bias, electrodeposited for 6 minutes to form a uniform dark red BiOI film on FTO;

(5)用离子水冲洗FTO，室温干燥，BiOI膜表面再滴加定量的0.2mol/L乙酰丙酮氧钒，将BiOI置于600℃马弗炉高温退火2h，样品自然冷却至室温；(5) Rinse the FTO with ionized water, dry at room temperature, add a quantitative amount of 0.2mol/L vanadyl acetylacetonate dropwise to the surface of the BiOI film, place the BiOI in a 600°C muffle furnace for high temperature annealing for 2h, and cool the sample to room temperature naturally;

(6)样品浸泡于1mol/L的NaOH溶液20min，去除电极表面多余的V2O5，BiVO4样品用大量去离子水冲洗，并在室温下干燥，得到纯净的BiVO4光阳极。(6) The sample was soaked in 1 mol/L NaOH solution for 20 min to remove excess V 2 O 5 on the electrode surface. The BiVO 4 sample was rinsed with a large amount of deionized water and dried at room temperature to obtain a pure BiVO 4 photoanode.

B、BiVO4-Ni/Co3O4光电极的制备：B. Preparation of BiVO 4 -Ni/Co 3 O 4 photoelectrode:

(1)将5mM Co(NO3)2·6H2O、2.5mM Ni(NO3)2·6H2O、6mM C6H12N4、0.36g尿素(CH4N2O)、0.195g NH4F依次加入50mL去离子水中，超声搅拌15min，得到混合溶液D；(1) 5 mM Co(NO 3 ) 2 .6H 2 O, 2.5 mM Ni(NO 3 ) 2 .6H 2 O, 6 mM C 6 H 12 N 4 , 0.36 g urea (CH 4 N 2 O), 0.195 g NH 4 F was successively added to 50 mL of deionized water, and ultrasonically stirred for 15 min to obtain mixed solution D;

(2)将30mL混合溶液D加入到50mL的聚四氟乙烯内衬不锈钢反应釜，BiVO4光阳极倾斜放置于反应釜，密闭的反应釜置于200℃的高温烘箱中反应3h，样品取出并用大量去离子水冲洗，样品置于马弗炉400℃高温退火2h，得到目标产物BiVO4-Ni/Co3O4。(2) 30mL of mixed solution D was added to 50mL of PTFE-lined stainless steel reaction kettle, BiVO 4 photoanode was placed in the reaction kettle obliquely, the closed reaction kettle was placed in a high temperature oven at 200°C for 3h reaction, the sample was taken out and used A large amount of deionized water was rinsed, and the sample was placed in a muffle furnace for annealing at a high temperature of 400 °C for 2 h to obtain the target product BiVO 4 -Ni/Co 3 O 4 .

测定了异质结光阳极的光电转换效率(IPCE)，BiVO4-Ni/Co3O4在380nm处IPCE值达到26％。The photoelectric conversion efficiency (IPCE) of the heterojunction photoanode was measured, and the IPCE value of BiVO 4 -Ni/Co 3 O 4 reached 26% at 380 nm.

图1中位于18.3°、28.1°和29.9°的特征衍射峰分别对应于BiVO4的(011)、(121)和(040)晶面(JCPDS卡片号为14-0688)，证明BiVO4的成功制备；位于36.8°的单一衍射峰被指定为Co3O4的(311)晶面衍射(JCPDS卡片号为42-1467)，表明Co3O4被成功合成。The characteristic diffraction peaks located at 18.3°, 28.1° and 29.9° in Figure 1 correspond to the (011), (121) and (040) crystal planes of BiVO 4 (JCPDS card number 14-0688), respectively, proving the success of BiVO 4 Preparation; a single diffraction peak at 36.8° was assigned to (311) plane diffraction of Co 3 O 4 (JCPDS Card No. 42-1467), indicating that Co 3 O 4 was successfully synthesized.

图2中可以看出所有样品的暗电流基本上都为零,而其光电流都不同程度提高，其中效果最好的是BiVO4-Ni/Co3O4,说明BiVO4-Ni/Co3O4的光电化学性能是最好的。BiVO4-Ni/Co3O4在1.23VRHE偏压下光电流密度达到2.23mA/cm2，它是原始BiVO4的4.4倍。It can be seen from Fig. 2 that the dark current of all samples is basically zero, and the photocurrent is improved to varying degrees. Among them, BiVO 4 -Ni/Co 3 O 4 has the best effect, indicating that BiVO 4 -Ni/Co 3 The photoelectrochemical performance of O4 is the best. BiVO 4 -Ni/Co 3 O 4 achieves a photocurrent density of 2.23 mA/cm 2 under 1.23V RHE bias, which is 4.4 times that of pristine BiVO 4 .

图3中BiVO4-Ni/Co3O4光吸收强度明显强于原始BiVO4。与BiVO4(5％)相比，BiVO4-Ni/Co3O4在380nm处IPCE值达到27％，约是前者的5倍。这说明是Ni/Co3O4析氧催化剂在半导体/电解质界面抑制界面电荷重组，降低水氧化反应势垒，提升了效率。The optical absorption intensity of BiVO 4 -Ni/Co 3 O 4 in Fig. 3 is obviously stronger than that of pristine BiVO 4 . Compared with BiVO 4 (5%), BiVO 4 -Ni/Co 3 O 4 achieves an IPCE value of 27% at 380 nm, which is about 5 times that of the former. This indicates that the Ni/Co 3 O 4 oxygen evolution catalyst inhibits the recombination of interfacial charges at the semiconductor/electrolyte interface, reduces the water oxidation reaction barrier, and improves the efficiency.

以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。The above descriptions are only the embodiments of the present invention, and are not intended to limit the scope of the patent of the present invention. Any equivalent structure or equivalent process transformation made by the description of the present invention, or directly or indirectly applied in other related technical fields, are the same as The principles are included in the scope of patent protection of the present invention.

Claims (9)

1.BiVO4-Ni/Co3O4The synthesis method of the heterojunction is characterized by comprising the following steps:
A. preparing 0.4mol/L KI solution, adding Bi (NO)3)3·5H2O to obtain a mixed aqueous solution, Bi (NO)3)3Adjusting the pH value to 1-3 with nitric acid, pouring an ethanol solution of p-benzoquinone, and stirring for 10-20 min to obtain a BiOI precursor solution, wherein the volume ratio of the mixed aqueous solution to the ethanol solution of p-benzoquinone is 5: 1-5: 3; the concentration of the ethanol solution of the p-benzoquinone is 0.23 mol/L;
B. placing the precursor solution in a three-electrode system, performing electrodeposition for 3-6 min under the bias of-0.1 Vvs Ag/AgCl by taking FTO as a working electrode, Pt filaments as a counter electrode and Ag/AgCl as a reference electrode, forming a uniform dark red BiOI film on the surface of the FTO, washing the FTO with ionized water, and drying at room temperature;
C. dropwise adding 0.2mol/L vanadyl acetylacetonate aqueous solution on the surface of the BiOI film, calcining and annealing FTO at 300-600 ℃ for 1.5-3 h, and taking outNaturally cooling to room temperature, soaking in NaOH solution to remove excessive V on the surface2O5Cleaning with deionized water, and drying to obtain FTO substrate with BiVO4A photo-anode;
D. adding Co (NO) to deionized water3)2·6H2O、Ni(NO3)2·6H2O、C6H12N4、CH4N2O and NH4F, ultrasonically stirring uniformly to obtain a mixed solution, wherein the Co (NO) is3)2·6H2O：Ni(NO3)2·6H2O：C6H12N4：CH4N2O：NH4F: deionized water in a solid-to-liquid ratio of 0.5-5 mM: 2.5 mM: 6 mM: 0.36 g: 0.195 g: 50 mL;
E. pouring the mixed solution into a hydrothermal reaction kettle to 60% of the volume, and growing BiVO on the prepared FTO substrate4And (3) placing the photoanode obliquely, heating for 2-5 h at the reaction temperature of 120-200 ℃, naturally cooling to room temperature, taking out, washing with deionized water, annealing at the high temperature of 300-500 ℃ for 1.5-3 h, and naturally cooling to room temperature to obtain the photoanode.
2. BiVO according to claim 14-Ni/Co3O4The synthesis method of the heterojunction is characterized in that: the pH was adjusted to 1.7 with nitric acid as described in step A.
3. BiVO according to claim 14-Ni/Co3O4The synthesis method of the heterojunction is characterized in that: the volume ratio of the mixed aqueous solution to the ethanol solution of the p-benzoquinone in the step A is 5: 2.
4. BiVO according to claim 14-Ni/Co3O4The synthesis method of the heterojunction is characterized in that: electrodeposition was carried out for 5min under the bias of-0.1 Vvs Ag/AgCl described in step B.
5. BiVO according to claim 14-Ni/Co3O4Heterogeneous natureThe synthesis method of the junction is characterized in that: in the step C, the FTO is calcined and annealed at 450 ℃ for 2 h.
6. BiVO according to claim 14-Ni/Co3O4The synthesis method of the heterojunction is characterized in that: co (NO) as described in step C3)2·6H2O：Ni(NO3)2·6H2O：C6H12N4：CH4N2O：NH4F: deionized water at a solid-to-liquid ratio of 2.5 mM: 2.5 mM: 6 mM: 0.36 g: 0.195 g: 50 mL.
7. BiVO according to claim 14-Ni/Co3O4The synthesis method of the heterojunction is characterized in that: d, pouring the mixed solution into a hydrothermal reaction kettle to 60% of the volume, wherein BiVO grows on the prepared FTO substrate4The photo-anode is obliquely placed, the reaction temperature is 180 ℃, and the heating is carried out for 3 hours.
8. BiVO according to claim 14-Ni/Co3O4The synthesis method of the heterojunction is characterized in that: and D, annealing at 400 ℃ for 2 h.
9. BiVO synthesized according to any one of claims 1 to 84-Ni/Co3O4Use of a heterojunction, characterized in that: the electrode is used as a working electrode for photoelectrochemical hydrolysis reaction.
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CN113398944A (en) * 2021-05-24 2021-09-17 苏州科技大学 Composite material of bismuth vanadate surface modified nickel cobaltate spinel and preparation and application thereof
CN113403642A (en) * 2021-05-24 2021-09-17 江苏大学 BiVO4/Co1-XPreparation method and application of S composite photoelectrode
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CN114411175A (en) * 2022-01-24 2022-04-29 江苏大学 Preparation method and application of amorphous metal oxide modified p-BiVO4 composite heterojunction
CN115261869A (en) * 2022-08-03 2022-11-01 中国石油大学(北京) A kind of preparation method and application of bismuth vanadate-based photogenerated cathodic protective coating

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