N3敏化Ho~（3＋）离子修饰TiO2纳米晶电极的光电化学性质

研究了Ho3+离子表面修饰对TiO2纳米晶电极光电性能的影响.TiO2表面氧化钬的存在一方而降低了染料和TiO2之间的电子注入速率,而另一方面它也能够抑制电荷复合.结果表明,在TiO2纳米晶薄膜表面修饰一定厚度的HO3+离子层,在电极表面就形成了一个势垒,能够有效抑制电极表面的电荷复合,从而提高了染料敏化太阳能电池的光电压和光电转化效率.在93.1 mW·cm-2白光照射下,TiO2/Ho-0.1和TiO2/Ho-0.2(0.1和0.2分别是修饰TjO2电极的Ho3+液的浓度,单位是mol·L-1)两个电极的光电转化效率分别达到8.3%和7.6%,与TiO2电极(7.2%)比较,分别增大了15%和5%.     

镍修饰WO3膜光电化学氧化水的研究

在强碱性溶液中低电压低电流条件下在W基底上经阳极氧化得到致密WO3层,而后在酸性条件下在WO3表面经光辅助电化学还原沉积镍,所获得的复合电极具有优异的光电化学氧化水的活性和稳定性.SEM,EDX,XPS和TEM等表征表明复合电极中具有体心立方结构的W基底经阳极氧化形成了具有单斜结构的WO3层,表面修饰的镍物种以Ni(OH)2形式存在.光电化学实验表明WO3层对可见光具有良好的光响应,表面修饰镍后,光电氧化水的起始电位显著降低,电极的稳定性也得以提高.     

镍纳米粒子修饰碳糊电极直接电催化鸟嘌呤的研究

将镍纳米粒子与石蜡、石墨按照一定比例混合制备镍纳米粒子修饰碳糊电极,采用循环伏安法(CV)对修饰碳糊电极进行电化学表征,在0.1 mol/L B-R缓冲溶液(pH4.5)中研究了鸟嘌呤在该修饰电极上的电化学行为。结果表明,与裸碳糊电极相比,以掺杂法制备的镍纳米粒子修饰电极能够明显降低鸟嘌呤的过电位,增大其氧化电流,很好地催化氧化鸟嘌呤。在优化的实验条件下,鸟嘌呤在该修饰电极上的氧化峰电流与其浓度在1.0×10-5~5.0×10-4mol/L范围内呈良好的线性关系,检出限(3σ)为7.5×10-6mol/L。     

镍纳米粒子-离子液体修饰碳糊电极的制备及其对多巴胺的测定

制备了镍纳米粒子-离子液体修饰电极,在0.1 mol/L磷酸缓冲溶液(pH 6.0)中研究了多巴胺(DA)在修饰电极上的电化学行为.与裸电极相比,DA在该修饰电极上的氧化还原电位明显降低,氧化还原反应的峰电流明显增大,DA的峰电流与其浓度在2.0×10~(-8) ～1.0×10~(-4) mol/L范围内呈良好的线性关系,检出限为6.5×10~(-9) mol/L.该修饰电极对抗坏血酸具有明显的抗干扰能力.     

N3敏化Ho3+离子修饰TiO2纳米晶电极的光电化学性质

研究了Ho3+离子表面修饰对TiO2纳米晶电极光电性能的影响. TiO2表面氧化钬的存在一方面降低了染料和TiO2之间的电子注入速率, 而另一方面它也能够抑制电荷复合. 结果表明, 在TiO2纳米晶薄膜表面修饰一定厚度的Ho3+离子层, 在电极表面就形成了一个势垒, 能够有效抑制电极表面的电荷复合, 从而提高了染料敏化太阳能电池的光电压和光电转化效率. 在93.1 mW·cm-2白光照射下, TiO2/Ho-0.1 和TiO2/Ho-0.2(0.1 和0.2分别是修饰TiO2电极的Ho3+溶液的浓度, 单位是mol·L-1)两个电极的光电转化效率分别达到8.3%和7.6%, 与TiO2电极(7.2%)比较, 分别增大了15%和5%.     

电化学沉积ZnS@CdS构建光电化学传感器测定谷胱甘肽

采用电化学沉积方法制备了具有核/壳结构的ZnS@CdS复合纳米修饰电极,采用扫描电子显微镜、电化学阻抗谱及光电化学方法对其进行了表征。由于快速有效的电子跃迁和光致电子-空穴对复合的抑制,ZnS@CdS修饰电极的光电流增强。以谷胱甘肽（GSH）为模型,制备了光电化学生物传感器。方法检出限为43 nmol/L,检测范围0.1～60μmol/L。方法已用于葡萄糖注射液中加标回收检测谷胱甘肽的含量,回收率为96.0%～106.5%。     

聚乙撑二氧噻吩修饰电极的电化学行为及对抗坏血酸的电催化作用

研究了聚乙撑二氧噻吩修饰电极在水溶液中的电化学行为及对抗坏血酸的电催化作用,实验表明抗坏血酸在聚乙撑二氧噻吩修饰电极上的氧化峰电位为+0.23V,较其在铂电极上的氧化峰电位负移220mV.在1.0×10^-1～1.0×10^-1mol/L浓度范围内,峰电流和抗坏血酸的浓度有线性关系,可用于水果等样品中抗坏血酸的测定。     

ZnSe/MoO_3/TiO_2复合膜的制备及其光生阴极保护效应

针对TiO_2半导体不能有效吸收可见光,光电转换效率较低等问题,可通过对TiO_2半导体进行修饰和改性,制备TiO_2复合材料,提高其光电化学性能。因此,本工作以Ti表面制备的TiO_2纳米管膜为基础,分别应用循环伏安电沉积法和脉冲电沉积法在膜表面先后沉积MoO3和ZnSe颗粒,获得具有级联能带结构的ZnSe/MoO3/TiO_2纳米管复合膜,并将其应用于对403不锈钢(403SS)实施光生阴极保护。相较于纯TiO_2纳米管膜,紫外-可见(UV-Vis)吸收光谱和光致发光(PL)谱测试表明,ZnSe/MoO3/TiO_2复合膜的吸收边红移,在可见光区具有良好的光吸收性能,光生载流子复合得到更有效抑制。光电化学测试表明,白光照射下,处于0.5 mol·L~(-1) KOH溶液中的ZnSe/MoO3/TiO_2复合膜的光电流密度达到了同条件下纯TiO_2膜的2倍,可使与之耦连的浸泡于0.5 mol·L-1 NaCl溶液中的403SS电极电位下降470 mV,显示出良好的光生阴极保护效应。复合膜还具有一定的储能特性,在光照后又转为暗态的22.5 h内仍对403SS具有一定阴极保护作用。     

吡硫醇在单壁碳纳米管修饰电极上电化学行为的研究

研究了吡硫醇在单壁碳纳米管修饰电极上的电化学行为,提出了一种检测吡硫醇的电化学方法.在0.1 mol/L的NaAc-HAc(pH 4.0)缓冲溶液中,吡硫醇在单壁碳纳米管修饰电极上出现一灵敏的氧化峰,峰电位位于0094 V处.与裸玻碳电极相比,单壁碳纳米管修饰电极显著提高了吡硫醇的氧化峰电流.在最佳实验条件下,吡硫醇浓度在9.9×10~(-6)～5.7×10~(-4) mol/L范围内与峰电流呈良好的线性关系,检出限为2.98×10~(-7) mol/L.吡硫醇在单壁碳纳米管修饰电极上的氧化过程受吸附控制,为1电子2质子的过程.     

介孔碳修饰玻碳电极上葡萄糖氧化酶的直接电化学

使用简单的方法将葡萄糖氧化酶(GOD)固定在介孔碳(Mesoporous Carbon)修饰的玻碳电极(GCE)表面.循环伏安测试表明:修饰电极上的GOD在0.1mol/L磷酸缓冲溶液(PBS)(pH=7.1)中发生了准可逆的氧化还原反应,其克式量电位为-0.4294 V,并且该电化学反应包含有两电子两质子的传递.在氮气饱和的情况下,以羧基二茂铁作为电子传递中介体,GOD能将葡萄糖彻底催化氧化,可见介孔碳修饰电极上的GOD保持了其生物学活性.     

金属氧化物(Fe2O3, CuO,NiO)改性对TiO2纳米管阵列光电催化活性的增强效应

采用阳极氧化法和阴极电沉积法制备了Fe2O3,CuO和NiO纳米粒子改性的高度有序的TiO2纳米管(TiO2-NT)阵列.运用场发射扫描电子显微镜(FE-SEM),透射电子显微镜(TEM),X射线衍射(XRD)和紫外-可见漫反射光谱等手段对Fe2O3/TiO2-NT、CuO/TiO2-NT和NiO/TiO2-NT复合电极进行表征.以苯酚为模拟污染物,考察复合电极的光电性能.结果表明,金属氧化物(Fe2O3,CuO,NiO)纳米粒子成功沉积在TiO2-NTs的管口、内壁和管底.金属氧化物改性复合电极的光电催化活性比未改性的TiO2-NTs提高了2倍以上.Fe2O3/TiO2-NTs在可见光区显示出最高的吸收强度.以Fe2O3/TiO2-NTs为阳极处理苯酚废水,光照120min后苯酚去除率达到96%,而未改性的TiO2-NTs的苯酚去除率只有41%.此外,Fe2O3/TiO2-NTs在生成低毒中间产物方面表现出良好的性能.较高的复合电极光电催化活性主要是由于TiO2纳米管和过渡金属氧化物纳米粒子间构筑的高界面面积异质纳米结构,有效地促进了电子转移,抑制了光生电子-空穴对的复合.     

A Photoelectrochemical Biosensor Fabricated using Hierarchically Structured Gold Nanoparticle and MoS2 on Tannic Acid Templated Mesoporous TiO2

In a tannic acid assisted synthesis of mesoporous TiO₂, tannic acid was used as a cost effective and non‐toxic template for pore formation. Meanwhile, a gold nanoparticles (Au NPs) deposited TiO₂ nanocomposite was coated on an indium tin oxide electrode for the fabrication of a photoelectrochemical (PEC) biosensing system. Upon the formation of anatase structure, the electrode was coated with MoS₂ for effective visible light absorption. The mesoporous structure led to an enhanced surface area by improving Au NPs and glucose oxidase adsorption. Incorporation of Au NPs led to an enhanced photonic efficiency due to the generation of Schottky barriers. The obtained nanocomposite was used for the light‐driven, real‐time, and selective PEC glucose sensing. Under visible light irradiation, the enzyme immobilized electrodes yielded significant photocurrent improvement owing to the releasing electron donor H₂O₂. The obtained PEC biosensor demonstrated acceptable reproducibility and stability with a sensitivity of 4.42 μA mM^?1 cm^?2 and a low detection limit of 1.2 μM glucose. Also, the linear measurement range was found to be 0.004–1.75 mM glucose. The results indicated that the proposed production method of mesoporous TiO₂ will pave the way for a green chemistry based porous material production, along with the extension of the implementation of semiconductors in PEC biosensing systems.     

Formation of efficient dye-sensitized solar cells by introducing an interfacial layer of long-range ordered mesoporous TiO2 thin film

Long-range ordered cubic mesoporous TiO 2 films with 300 nm thickness were fabricated on fluorine-doped tin oxide (FTO) substrate by evaporation-induced self-assembly (EISA) process using F127 as a structure-directing agent. The prepared mesoporous TiO 2 film (Meso-TiO 2) was applied as an interfacial layer between the nanocrystalline TiO 2 film (NC-TiO 2) and the FTO electrode in the dye-sensitized solar cell (DSSC). The introduction of Meso-TiO 2 increased J sc from 12.3 to 14.5 mA/cm (2), and V oc by 55 mV, whereas there was no appreciable change in the fill factor (FF). As a result, the photovoltaic conversion efficiency ( eta) was improved by 30.0% from 5.77% to 7.48%. Notably, introduction of Meso-TiO 2 increased the transmittance of visible light through the FTO glass by 23% as a result of its excellent antireflective role. Thus the increased transmittance was a key factor in enhancing the photovoltaic conversion efficiency. In addition, the presence of interfacial Meso-TiO 2 provided excellent adhesion between the FTO and main TiO 2 layer, and suppressed the back-transport reaction by blocking direct contact between the electrolyte and FTO electrode.     

Visible light induced photoelectrochemical biosensing based on oxygen-sensitive quantum dots

A visible light induced photoelectrochemical biosensing platform based on oxygen-sensitive near-infrared quantum dots (NIR QDs) was developed for detection of glucose. The NIR QDs were synthesized in an aqueous solution, and characterized with scanning electron microscopy and X-ray photoelectron spectroscopy. The as-prepared NIR QDs were employed to construct oxygen-sensitive photoelectrochemical biosensor on a fluorine-doped tin oxide (FTO) electrode. The oxygen dependency of the photocurrent was investigated at as-prepared electrode, which demonstrated the signal of photocurrent is suppressed with the decreasing of oxygen. Coupling with the consumption of oxygen during enzymatic reaction, a photoelectrochemical strategy was proposed for the detection of substrate. Using glucose oxidase (GOx) as a model enzyme, that is, GOx was covalently attached to the surface of CdTe QDs, the resulting biosensor showed the sensitive response to glucose. Under the irradiation of visible light of a wavelength at 505 nm, the proposed photoelectrochemical method could detect glucose ranging from 0.1 mM to 11 mM with a detection limit of 0.04 mM. The photoelectrochemical biosensor showed a good performance with high upper detection limit, acceptable stability and accuracy, providing an alternative method for monitoring biomolecules and extending the application of near-infrared QDs.     

Preparation of a p-n heterojunction 2D BiOI nanosheet/1DBiPO4 nanorod composite electrode for enhanced visible light photoelectrocatalysis

In this study, a 2D BiOI nanosheet/1D BiPO₄ nanorod/fluorine-doped tin oxide (FTO) composite electrode with a p-n heterojunction structure was prepared by a two-step electrodeposition method. Field-emission scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, UV-visible diffuse reflectance spectroscopy, and electrochemical testing were used to characterize its composition, crystal morphology, and optical properties. The BiOI/BiPO₄/FTO composite electrode has higher photoelectrocatalytic (PEC) activity for the degradation of tetracycline than pure BiPO₄ and BiOI. The PEC activity of the composite was 1.98 times and 2.46 times higher than those of the BiOI/FTO and BiPO₄/FTO electrodes, respectively. The effects of the working voltage and BiOI deposition time on the degradation of tetracycline were investigated. The optimum BiOI deposition time was found to be 150 s and the optimum working voltage is 1.2 V. Trapping experiments showed that hydroxyl radicals (?OH) and superoxide radicals (?O₂^?) are the major reactive species in the PEC degradation process. The BiOI/BiPO₄/FTO composite electrode has good stability, and the tetracycline removal efficiency remains substantially unchanged after four cycles in a static system. The reason for the PEC efficiency enhancement in the BiOI/BiPO₄/FTO composite electrode is the increased visible light absorption range and the p-n heterojunction structure, which promotes the separation and migration of the photogenerated electrons and holes.     

Non-noble metal Bi/BiVO4 photoanode for surface plasmon resonance-induced photoelectrochemical biosensor of hydrogen peroxide detection

Non-noble metal for surface plasmon resonance (SPR)-induced nano-enzymatic photoelectrochemical (PEC) biosensors is a promising method for broad applications. Non-noble metal bismuth (Bi) is gradually being valued for their properties such as non-toxicity, abundant reserves, and good catalysis. Meanwhile, metallic Bi nanoparticles (NPs) have superior SPR properties similar to that of noble metal. Therefore, a non-noble metal Bi/BiVO₄ photoanode based on SPR was designed for the PEC detection of H₂O₂ in this work. The synergistic effect of BiVO₄ with suitable band gap (2.5 eV) and Bi NPs with superior SPR effectively reduces the recombination of photogenerated electrons and holes, which significantly improves the PEC activity of Bi/BiVO₄ electrode at low voltage. The in situ Bi/BiVO₄/FTO photoelectrode not only exhibits a more comprehensive linear range of 0.005–2.6 mM with a lower detection limit of 2.0 μM but also possesses excellent selectivity for the determination of H₂O₂ because the coexisting substances are difficult to be oxidized at 0 V bias voltage. The investigation of Bi/BiVO₄-based sensor has contributed to the development of non-noble metal for SPR-induced PEC biosensors.

     

核酸适配体功能化的稀土上转换纳米材料在生物检测中的应用

稀土上转换纳米材料可以吸收近红外光并发射出可见光或紫外光,在生物传感领域得到了广泛研究。核酸适配体能高特异性和高亲和性地与靶标物结合,被广泛应用于生物传感、疾病诊断等领域。将稀土上转换纳米材料与核酸适配体结合构建的检测体系,可实现对目标物灵敏、高选择性的检测。本文介绍了近几年核酸适配体功能化的稀土上转换纳米材料在生物小分子、蛋白质、核酸、病原微生物、细胞等方面的应用,并展望了其在分析检测领域的发展前景。     

Photodeposition of Ag2S quantum dots and application to photoelectrochemical cells for hydrogen production under simulated sunlight

UV light irradiation of TiO(2) (λ > 320 nm) in a mixed solution of AgNO(3) and S(8) has led to the formation of Ag(2)S quantum dots (QDs) on TiO(2), while Ag nanoparticles (NPs) are photodeposited without S(8). Photoelectrochemical measurements indicated that the Ag(2)S photodeposition proceeds via the preferential reduction of Ag(+) ions to Ag(0), followed by the chemical reaction with S(8). The application of this in situ photodeposition technique to mesoporous (mp) TiO(2) nanocrystalline films coated on fluorine-doped SnO(2) (FTO) electrodes enables formation of Ag(2)S QDs (Ag(2)S/mp-TiO(2)/FTO). Ag(2)S/mp-TiO(2)/FTO has the interband transition absorption in the whole visible region, while in the spectrum of Ag/mp-TiO(2)/FTO, a localized surface plasmon resonance absorption of Ag NPs is present centered at 490 nm. Ag(2)S QD-sensitized photoelectrochemical cells using the Ag(2)S/mp-TiO(2)/FTO and Ag/mp-TiO(2)/FTO photoanodes were fabricated. Under illumination of one sun, the Ag(2)S photoanode cell yielded H(2) at a rate of 0.8 mL·h(-1) with a total conversion efficiency of 0.29%, whereas the Ag/mp-TiO(2)/FTO photoanode is inactive.     

Surface plasmon resonance-enhanced photoelectrochemical immunoassay of prostate-specific antigen based on BiOCl-Au heterojunction

Taking advantage of the high-efficiency photocurrent response of bismuth oxychloride sensitized with gold nanoparticles (BiOCl−Au) in combination with the antigen-antibody biological recognition reaction, a convenient photoelectrochemical (PEC) immunoassay (model target: prostate-specific antigen; PSA) has been fabricated. In particular, the enhanced photocurrent response could be attributed to the enhanced optical absorption of visible light from surface plasmon resonance (SPR) effect of gold nanoparticles in the hierarchical structure of BiOCl layered. To realize the biological detection process, an immunoreaction was implemented between target PSA and alkaline phosphatase (ALP)-labeled anti-PSA antibodies. With the formation of ternary sandwich immunocomplex, the carried and loaded ALP catalysed the substrate ascorbic acid 2-phosphate (AAP) to generate ascorbic acid for increasing the photocurrent intensity of BiOCl−Au/FTO. Under optimum reaction time, the photocurrent peak intensity of BiOCl−Au/FTO increased with the increasing of target PSA concentration in the range of 0.01 ng/mL to 50 ng/mL with a limit of detection (LOD) down to 2.3 pg/mL. In the photocurrent control experiment, the photocurrent of BiOCl−Au/FTO was not only higher than that of BiOCl/FTO, but also showed greater changes in photocurrent under the same target PSA concentration. Impressively, the proposed split-type PEC immunoassay was applied to detect PSA concentration in human serum samples, giving acceptable and satisfactory accuracy compared with the gold standard PSA ELISA method.     

两种菁类染料复合敏化TiO2纳米晶电极的光电化学研究

应用光电化学方法研究了两种菁类染料Cy3和Cy5复合敏化TiO2纳米晶电极的光电化学行为. 结合两种染料的紫外-可见光谱和循环伏安曲线, 确定了Cy3和Cy5的电子基态和激发态能级位置. 结果表明两种染料的激发态能级位置能与TiO2纳米粒子导带边位置相匹配, 复合敏化可以显著提高TiO2纳米晶的光电流, 使TiO2纳米晶电极吸收波长由紫外光区红移至可见光区和近红外区. 复合敏化降低了染料Cy3在电极吸附时的聚集程度, 使其单色光的转换效率(IPCE)提高了169%, 复合敏化电极总的光电转换效率η为2.09%, 分别是Cy3和Cy5单独敏化时光电转换效率的2.069和1.229倍.