基于层状二硫化钼纳米片比色检测亚锡离子

在醋酸/醋酸钠缓冲溶液(pH=4.5)中, 亚锡离子对层状二硫化钼(MoS₂)纳米片催化过氧化氢(H₂O₂)氧化邻苯二胺(OPD)的显色反应有很强的抑制作用, 据此构建了一种检测亚锡离子的比色传感器. 实验结果表明, 与不加MoS₂纳米片的OPD/H₂O₂比色传感体系相比, MoS₂/OPD/H₂O₂体系检测亚锡离子的灵敏度显著提高, 线性范围变宽. 在优化的条件下, MoS₂/OPD/H₂O₂传感体系检测亚锡离子的线性范围为0.02~3.0 μmol/L, 检出限为8 nmol/L (S/N=3). 该传感体系对检测亚锡离子具有高的选择性, 可用于湖水中亚锡离子的检测.     

水热法制备Bi2O3纳米片及其电化学性能的研究

以Bi(NO₃)₃和氨水为原料、水溶性淀粉为分散剂, 采用水热法制备了Bi₂O₃纳米片, 用X射线衍射(XRD)、扫描电子显微技术(SEM)和氮气吸附-脱附等对材料进行了表征. 结果表明Bi₂O₃纳米片厚度分布比较窄, 比表面积达到9.26 m²/g. 同时, 采用循环伏安法和充放电仪测试了Bi₂O₃纳米片的电化学性能, 结果显示其具有一定的电化学活性.     

沉积于含硼金属有机框架的Pt(Ⅱ)通过抑制分解来增强光催化H2O2的产生(英文)

H₂O₂作为一种重要的化工资源越来越受到关注,它不仅是环境友好的氧化剂,而且是很有应用前景的新型液体燃料.目前生产H₂O₂主要采用蒽醌法,该方法存在能耗高、副产物有毒等缺点.光催化合成H₂O₂因对环境友好而受到广泛关注,该合成反应中同时发生H₂O₂的生成和分解.目前光催化合成H₂O₂相关研究主要集中在H₂O₂的生成,而有关H₂O₂分解的研究较少.研究发现Pt作为助催化剂在提高光催化活性方面发挥着重要作用,但Pt价态对光催化活性的影响,特别是对H₂O₂的生成和分解的影响,尚未进行详细研究.本文将不同价态的Pt沉积在含硼金属有机骨架(UiO-67-B)上,详细研究了Pt(0),Pt(Ⅱ)和Pt(Ⅳ)在光催化产H₂O     

噻吩环掺杂氮化碳纳米片的制备及光催化性能

二次热剥离是合成二维氮化碳纳米片(CNN)的有效方法,进一步拓宽其可见光响应并优化光电转化效率是提升CNN光催化性能的有效策略。本工作采用原位聚合分子掺杂和二次热剥离相结合的方法,以2-氨基噻吩-3-甲腈为分子掺杂源,将噻吩环原位掺杂引入并稳定存在于CNN共轭杂环,制备了噻吩环掺杂的氮化碳纳米片光催化剂(CNN-Th_x)。经过二次热剥离后,产物保持二维杂化共轭聚合结构且噻吩环依然稳定掺杂于CNN共轭杂环。噻吩环掺杂引起π共轭体系进一步扩展,降低了产物禁带宽度,拓宽了可见光吸收范围,增强了光电转换效率;同时,二次热剥离协同噻吩掺杂引起更显著的n-π*跃迁,大幅提升了催化剂的光催化活性。在可见光照下对催化剂进行光解水制H₂及活化O₂制H₂O₂的性能测试。结果表明,CNN-Th_x具有显著增强的光催化还原性能,其中,CNN-Th₁₀的产氢活性达到322.8μmol·h^-1,4 h后生成H₂O     

GOx@Fe3O4-HNTs微囊反应器的构筑及多酶级联催化性能

细胞内或细胞间的微空间使得生物体内的各种酶促反应能够高效有序地进行.基于此,本文结合天然酶-纳米酶二者的优势,构筑了一种模拟体内酶促级联反应的微囊反应器.首先,以天然硅铝酸盐矿物埃洛石纳米管(HNTs)为载体,在其表面原位生成具有类辣根过氧化物酶活性的四氧化三铁(Fe₃O₄);随后,将其作为囊壁材料封装天然葡萄糖氧化酶(GOx),构筑GOx@Fe₃O₄-HNTs微囊反应器.当向体系中加入葡萄糖时,微囊反应器内的GOx先将葡萄糖转化为葡萄糖酸和过氧化氢(H₂O₂),之后H₂O₂继续被囊壁中的Fe₃O₄催化转化为羟基自由基,触发底物3,3’,5,5’-四甲基联苯胺(TMB)显色.其中,Fe₃O₄-HNTs作为囊壁材料不仅使囊内GOx免受外界环境干扰,还可与GOx构建级联催化反应体系,这种酶-纳米酶微囊化级联体系具有比天然酶系统更优...     

CuS/Ag2S纳米复合物的制备及类过氧化物酶性质

采用水热法合成了一种微球状的CuS/Ag₂S纳米复合物. 通过透射电子显微镜、 紫外-可见吸收光谱和拉曼光谱等对其形貌及光学性质进行了表征; 考察了其类过氧化物酶性质, 并通过表面增强拉曼散射原位监测了类过氧化物酶催化反应. 以3,3',5,5'-四甲基联苯胺(TMB)为底物进行显色反应, 结果表明, 在H₂O₂存在下CuS/Ag₂S 纳米复合物具有类过氧化物酶的性质, 可以将无色的TMB氧化成蓝色的oxTMB. 基于此实现了对微量H₂O₂的检测.     

多孔纳米CoFe2O4的制备及其对高氯酸铵的热分解催化性能

采用胶晶模板法制备出具有三维多孔结构的纳米CoFe₂O₄。利用X射线衍射仪(XRD)、傅里叶变换红外(FT-IR)光谱仪、扫描电镜(SEM)、透射电镜(TEM)和N₂吸附-脱附对样品的晶型和形貌结构等进行表征,采用差示扫描量热法(DSC)对比研究多孔纳米CoFe₂O₄和球形纳米CoFe₂O₄对高氯酸铵(AP)的热分解性能的影响,并考察这两种催化剂对AP催化热分解的动力学参数。结果显示,制备出的多孔纳米CoFe₂O₄样品具有典型的尖晶石结构,孔径约200 nm;比表面积明显高于40 nm球形CoFe₂O₄,达到55.646 m²·g^-1。DSC测试结果表明：多孔纳米CoFe₂O₄的加入促进了AP的热分解,最高使AP的高温分解峰温降低91.46℃,能量释放最高达1120.88 J·g^-1,是纯AP分解放热量的2.3倍;多孔纳米CoFe₂O₄具有较高的比表面积,能提高催化反应的接触面积,使AP的高温分解峰温度更低,反应活化能较小,从而表现出比球形纳米CoFe₂O₄更高的催化活性。此外,对多孔纳米CoFe₂O₄催化AP的热分解机理进行初步探索,纳米多孔催化剂对气态中间产物的作用促进了AP的热分解。     

基于二硫化钼纳米片类过氧化物酶活性比色法测定尿酸

采用一步水热法制备具有类过氧化物酶活性的MoS₂纳米片,并基于MoS₂纳米片可催化H₂O₂氧化3,3′,5,5′-四甲基联苯胺(TMB)生成蓝色氧化产物(ox-TMB)的原理,建立了测定H₂O₂浓度的分析方法。在pH 3.7、温度35℃、MoS₂浓度1.0μg/mL及孵育时间40 min的条件下, ox-TMB的吸光度随H₂O₂浓度的升高而增大。基于H₂O₂是尿酸氧化酶催化尿酸氧化的产物之一,建立了MoS₂纳米片催化H₂O₂氧化TMB间接测定尿酸的分析方法。在2.5～40μmol/L和40～100μmol/L范围内,检测体系的吸光度与尿酸浓度呈良好的分段线性关系,方法在低浓度区间的检出限为0.093μmol/L,应用于血清和尿样中尿酸的测定,回收率为92.6%～102.0%。     

层状钒青铜纳米片的制备及其锂离子电池阳极材料性能

室温下, 在水溶液中将铵根离子和水分子插入到商用V₂O₅纳米颗粒的层间, 制得了层状的钒青 铜[(NH₄)₂V₆O₁₆·H₂O]纳米片. 该纳米片的尺寸为2~10 μm, 厚度为50~250 nm. 与商用V₂O₅纳米颗粒相比, (NH₄)₂V₆O₁₆·H₂O纳米片用作锂离子电池(LIBs)的阳极材料时, 其性能得到较大提升, 包括大的可逆放电容量 (0.1 A/g时为1148 mA·h/g)、 出色的循环性能(循环70圈后在0.1 A/g时具有1002 mA·h/g的高容量)和高倍率性能(在0.1 A/g时具有1070 mA·h/g的可逆性能). 研究结果表明, (NH₄)₂V₆O₁₆·H₂O纳米片可以作为锂离子电池优良的阳极材料, 也有望应用于其它(如钠离子电池和锌离子电池等)可再充电电池.     

Al源种类对微乳液法制备固体超强酸催化剂异构化性能的影响

分别以拟薄水铝石、γ-Al₂O₃、Al₂O₃、Al(NO₃)₃·9H₂O为Al源,通过微乳液法制备了一系列Pt-S₂₈O^2-/ZrO₂-Al₂O₃催化剂,并利用XRD、FT-IR、BET、H₂-TPR等手段对其进行了表征,考察了Al源种类对Pt-S₂₈O^2-/ZrO₂-Al₂O₃固体超强酸催化剂结构和酸性的影响,并以正戊烷异构化反应为探针,考察了Al源种类对催化剂异构化性能的影响。结果表明,不同Al源制备的催化剂均能够稳定ZrO₂四方晶相,增大催化剂的比表面积;除以拟薄水铝石为Al源制备的催化剂外,其他催化剂的氧化还原性能均有所提高。以Al(NO₃)₃·9H₂O为Al源制备的催化剂具有最大的比表面积和更多的超强酸,表现出最佳的异构化性能,在反应压力2.0 MPa、氢烃物质的量比4∶1、质量空速(WHSV)1.0 h^-1、反应温度220 ℃条件下,异戊烷产率达到59.5%。     

Colorimetric Detection of Glucose Using WO3 Nanosheets as Peroxidase-mimetic Enzyme

In the present work, WO₃ nanosheets(WO₃ NSs) were prepared by a facile method at room temperature. The obtained WO₃ NSs showed peroxidase-like activity, which could catalyze 3,3',5,5'-tetramethylbenzidine(TMB) to form a blue oxidation product(ox TMB) in the presence of H₂O₂. Based on this, convenient and sensitive colorimetric methods for the detection of H₂O₂ and glucose were established. The linear ranges for detecting H₂O₂ and glucose were 1-200 μmol/L and 1-100 μmol/L, respectively. The limits of the detection of H₂O₂ and glucose were as low as 0.79 and 0.96 μmol/L, respectively. This method was also successfully applied to the detection of glucose in urine samples. The detection result was consistent with that of the value detected by the clinical method, indicating the potential in clinical diagnosis and biomedical detection.     

具有过氧化物酶活性的Imm-Fe3+-IL的制备及用于比色法测定H2O2和葡萄糖

通过溶胶-凝胶法制备的Imm-Fe³⁺-IL纳米材料具有类过氧化物酶的活性,能够催化过氧化氢(H₂O₂)快速氧化3,3′,5,5′-四甲基联苯胺(TMB)产生相应的颜色变化。 稳态动力学分析表明,Imm-Fe³⁺-IL纳米材料遵循典型的Michaelis-Menten模型和乒乓机理。 辣根过氧化物酶(HRP)相比,Imm-Fe³⁺-IL纳米材料纳米材料具有更强的亲和性。 联合葡萄糖氧化酶建立了H₂O₂和葡萄糖的比色检测方法。 结果显示:H₂O₂和葡萄糖的浓度与反应体系的吸光度呈良好的线性关系,H₂O₂的线性范围为1~200 μmol/L,葡萄糖的线性范围为10~200 μmol/L,最低检出限(LOD)分别为0.35和3.31 μmol/L。     

MOF derived Co3O4/N-doped carbon nanotubes hybrids as efficient catalysts for sensitive detection of H2O2 and glucose

Developing enzyme-free sensors with high sensitivity and selectivity for H2O2 and glucose is highly desirable for biological science.Especially,it is attractive to exploit noble-metal-free nanomaterials with large surface area and good conductivity as highly active and selective catalysts for molecular detection in enzyme-free sensors.Herein,we successfully fabricate hollow frameworks of Co3O4/N-doped carbon nanotubes(Co3O4/NCNTs)hybrids by the pyrolysis of metal-organic frameworks followed by calcination in the air.The as-prepared novel hollow Co3O4/NCNTs hybrids exhibit excellent electrochemical performance for H2O2 reduction in neutral solutions and glucose oxidation in alkaline solutions.As sensor electrode,the Co3O4/NCNTs show excellent non-enzymatic sensing ability towards H2O2 response with a sensitivity of 87.40μA(mmol/L)^-1 cm^-2,a linear range of 5.00μmol/L-11.00 mmol/L,and a detection limitation of 1μmol/L in H2O2 detection,and a good glucose detection performance with 5μmol/L.These excellent electrochemical performances endow the hollow Co3O4/NCNTs as promising alternative to enzymes in the biological applications.     

Facile synthesis of enzyme functional metal-organic framework for colorimetric detecting H2O2 and ascorbic acid

In this work,a metal-organic frameworks material MIL-88 was prepared easily using solvent-thermal method,and was first found to have catalytic activities similar to those of biological enzymes such as catalase and peroxidase.The material was characterized by XRD,SEM,TEM,EDX,FT-IR techniques and an N_2 adsorption method.It exhibited peroxidase-like activity through catalytic oxidation of the peroxidase substrate 3,3',5,5'-tetramethylbenzidine(TMB) in the presence of H_2O_2,producing a blue-colored solution.Under optimal conditions,the absorbance at 652 nm is linearly correlated with the concentration of H_2O_2 from 2.0×10~(-6) mol/L to 2.03×10~(-5) mol/L(R~2=0.981) with a detection limit of 5.62×10~(-7) mol/L(S/N=3).More importantly,a sensitive and selective method for ascorbic acid detection was developed using this material as a catalyst.The analytical method for ascorbic acid detection was observed to have a linear range from 2.57×10~(-6) mol/L to 1.01×10~(-5) mol/L(R~2=0.989) with a detection limit of 1.03×10~(-6) mol/L(S/N=3).This work suggests MOFs have advantages of preparing biomimetic catalysts and extends applications of the functional MOFs in the field of biosensor.     

Vc-Functionalized Fe3O4 Nanocomposites as Peroxidase-like Mimetics for H2O2 and Glucose Sensing

A simple and efficient colorimetric biosensing for hydrogen peroxide and glucose with peroxidase-like vitamin C(V_c) functionalized Fe₃O₄ magnetic nanoparticles(V_c/Fe₃O₄MNPs) as a catalyst is reported. Compared with Fe₃O₄ MNPs and other catalysts, V_c/Fe₃O₄ MNPs exhibited superior catalytic properties. Kinetic studies indicated that vitamin C incorporated on Fe₃O₄ MNPs improved the affinity toward H₂O₂. As low as 0.29 μmol/L H₂O₂ can be detected with a wide linear range of 0.5—100 μmol/L H₂O₂; moreover, as low as 0.288 μmol/L glucose can be detected with a linear range of 0.5—25 μmol/L glucose. The detection method was highly sensitive in sensing H₂O₂ and glucose. The robustness of V_c/Fe₃O₄ MNPs rendered them suitable for wide ranging applications.     

基于碳量子点过氧化物模拟酶的肌氨酸比色测定

以果皮为原料制备了水溶性碳量子点(CQDs), 透射电子显微镜分析表明其平均粒径为2.4 nm; 红外光谱分析证实CQDs表面富含含氧官能团. 所得CQDs可催化H₂O₂氧化3,3',5,5'-四甲基联苯胺(TMB)生成蓝色氧化产物(ox-TMB). 基于上述反应, 建立了测定H₂O₂的分析方法, 在pH=3.5, 温度40 ℃, TMB浓度为1.0 mmol/L及孵育时间15 min的条件下, 当H₂O₂浓度在5.0~100 μmol/L范围时, ox-TMB的吸光度随H₂O₂浓度的升高而线 性增强, 方法的检出限为3.0 μmol/L. 鉴于H₂O₂是肌氨酸氧化酶催化肌氨酸氧化的产物之一, 建立了CQDs催化H₂O₂氧化TMB间接测定肌氨酸的分析方法. 结果表明, 当肌氨酸浓度在0.5~350 μmol/L范围内时, 吸光度 与其浓度呈良好的线性关系, 方法的检出限为0.3 μmol/L; 将该方法应用于人体尿样的测定, 回收率为94%~99%.     

Microwave-assisted One-pot Synthesis of Ag NPs/C and Its Application in H2O2 and Glucose Detection

The facile preparation of Ag NPs/C via a one-pot strategy was carried out by microwave treatment of a mixed aqueous solution of AgNO₃ and glucose at 180℃ for 20 min without the presence of extra reducing agent. The as-synthesized Ag NPs/C showed high catalytic performance toward the reduction of H₂O₂. The H₂O₂ sensor constructed with as-synthesized Ag NPs/C exhibited a short amperometric response time of less than 2 s. The linear range was approximately (0.1-50) mmol/L(r=0.997), and the detection limit was approximately 3.3 μmol/L at a signal-to-noise ratio of 3. A glucose biosensor was fabricated by immobilizing glucose oxidase onto Ag NPs/C- modified glassy carbon electrode to detect glucose. The glucose sensor had a wide linear response range of 2-22 mmol/L(r=0.999) and a detection limit of 190 μmol/L.     

Dual-modal Colorimetric and Fluorometric Method for Glucose Detection Using MnO2 Sheets and Carbon Quantum Dots

A novel dual-modal fluorometric and colorimetric method was developed for glucose detection using MnO2 sheets and carbon quantum dots(CQDs). The glucose could be oxidized by glucose oxidase, in accompanied witli the fbnnation of H2O2 intennediate, which resulted in the decomposition of MnO2 sheets, as well as tlie MnO2 sheets(brown) changed to Mn^2+ ions(colorless), which induced the absorption of MnO2 sheet decreased and the fluorescence of CQDs increased, consequently. The linear detection ranges of glucose are 5-1000 μmol/L by fluorescent method and 5-60 μmol/L by colorimetric method. The limits of detection of these two measurements are 2.11 and 2.18 μmol/L, respectively. This method is easy to conduct, has reasonable sensitive and selectivity, and could be applied for the glucose detection in real human senim.     

Synthesis of Holey Graphitic Carbon Nitride with Highly Enhanced Photocatalytic Reduction Activity via Melamine-cyanuric Acid Precursor Route

In this work, holey graphitic carbon nitride(HCN) was prepared by one-step thermal polymerization of hydrothermal product of melamine and then loaded with Ni/MoO₂(NiMo) cocatalyst obtained by NaBH₄ reduction process. The obtained material was used for photocatalytic production of H₂ from water reduction and H₂O₂ production from O₂ reduction. The best photocatalyst(1% NiMo/HCN) exhibited a H₂ evolution rate of 8.08 μmol/h while no H₂ was detected over 1% NiMo-modifed bulk g-C₃N₄(BCN) under visible light illumination. Moreover, this rate is 1.7 times higher than that of 1% Pt-modified HCN. The 1% NiMo/HCN catalyst also exhibited the highest H₂O₂ production activity with a value of 6.13 μmol/h. Such enhancement was ascribed to the efficient charge carrier separation and migration, which were promoted by the large specific surface area and pore volume of HCN and the synergy between MoO₂ and Ni. The proposed method to obtain HCN is expected to open up new ways in development of highly-active HCN-based photocatalysts for photocatalytic reduction reactions.