Scanning Droplet Cell for Chemoselective Patterning through Local Electroactivation of Protected Quinone Monolayers

A reagentless strategy for template‐free patterning of uniformly inert surfaces is suggested. A layer of p‐hydroquinone (HQ) protected by the tert‐butyldimethylsilyl (TBDMS) group is electrografted onto glassy carbon electrodes. Chemoselective activation is performed through electrochemically controlled cleavage of the TBDMS group, which yields the redox‐active surface‐confined quinone moieties. The latter are shown to undergo electrochemically induced Michael addition, which serves for subsequent functionalization of the electrode surface. Patterning of the TBDMS–quinone‐modified surface is accomplished by using selective localized cleavage of the protecting group. State‐of‐the‐art direct‐mode scanning electrochemical microscopy (SECM) patterning fails to yield the anticipated interfacial reaction; however, the electrochemical scanning droplet cell (SDC) is capable of conducting the localized chemoselective reaction. In a small area, dictated by the dimensions of the droplet, electrochemically induced cleavage of the protecting group can be performed locally to give rise to arrays of active quinone spots. Upon deprotection, the redox signals, attributed to the hydroquinone/benzoquinone couple, provide the first direct evidence for chemoselective electrochemical patterning of sensitive functionalities. Subsequent SECM studies of the resulting modified areas demonstrate spatial control of the proposed patterning technique.     

基于DNA-甲苯胺蓝生物聚合离子膜的多环有机物电化学传感器的研究

利用DNA与小分子之间的相互作用,以DNA/壳聚糖生物聚合离子膜固定电活性小分子,制备了DNA-甲苯胺蓝/壳聚糖聚合离子复合膜修饰电极,并利用多环有机物与染料分子对DNA特异结合的竞争关系,构筑了多环有机物非试剂添加型DNA电化学生物传感器。以盐酸四环素为模式分子,利用循环伏安法和方波伏安法研究了该修饰电极的电化学特性以及该电极对盐酸四环素的电化学响应,结果表明,DNA和甲苯胺蓝成功地固定在电极表面,电极表面的甲苯胺蓝保持了很好的电化学活性。利用紫外-可见分光光度法研究了电极对盐酸四环素响应的作用机理。该传感器的线性范围为2.5~100μmol·L-1。     

含2,6-二(甲基苯并咪唑)吡啶钴、镨配合物的合成、结构、电化学性质和理论计算研究

以2,6-二(甲基苯并咪唑)吡啶和2,2′-联吡啶为配体,合成了一个钴的配合物[Co(mbzimpy)(bipy)Cl]Cl O4·1.3H2O(1)和一个镨的配合物[Pr(mbzimpy)2(NO3)2]Cl O4·2CH3COCH3(2),(mbzimpy=2,6-bis(methylbenzimidazol-2-yl)pyridine,bipy=2,2′-bipyridine)并利用单晶衍射对其结构进行了表征。还对配合物1和2的荧光和电化学性质进行了研究。晶体结构中C-H…O氢键和π-π芳环堆积作用将每个单核分子连接成一个三维的空间结构。配合物1的TD-DFT理论计算的结果表明:实验得到的紫外谱图和理论计算的紫外谱图较好地吻合。通过循环伏安图可以了解金属中心的氧化和还原电子对。在不同偶极矩的溶剂中研究其荧光性能。     

非标记凝血酶阵列电化学适体传感器的研究

基于自制的集成化三阵列金膜电极,构建了一个简单、灵敏、非标记的凝血酶阵列电化学适体传感器。以聚乙烯不干胶掩膜版法结合金属溅射沉积技术,在FR-4玻璃纤维板上制作了由3个金膜工作电极、1个大面积金膜对电极和1个厚膜Ag/AgCl参比电极构成的集成化金膜阵列电极系统。以集成化金膜阵列电极作为基础电极,采用巯基自组装技术将带巯基的凝血酶适体固定在3个金工作电极表面,巯基己醇封闭后获得三阵列凝血酶适体传感器,以电活性物质铁氰化钾作为电化学探针,基于凝血酶适体和凝血酶结合前后铁氰化钾在电极表面传质的不同导致电流变化进行凝血酶的测定。采用方波脉冲伏安法,铁氰化钾氧化峰电流的变化值与凝血酶浓度在 1.52~63 nmol/L范围内呈良好的线性关系,检出限(S/N=3)为0.92 nmol/L。     

TiO_2/12-磷钨杂多酸/金复合纳米材料的制备及电化学性能

采用水热法制备TiO2纳米管(TNTs),然后以12-磷钨杂多酸(PTA)作为交联剂,运用光催化方法在TiO2纳米管表面负载金纳米颗粒(GNPs),从而得到新型复合纳米材料——TNTs-PTA-GNPs;借助傅立叶变换红外光谱仪,X射线衍射仪和透射电子显微镜分析了新型复合纳米材料的结构及形貌,并利用循环伏安法测试了其电化学性能.结果表明,GNPs均匀分布在TNTs表面,从而大幅度改善纳米材料的导电性;但复合纳米材料中无游离的金纳米颗粒.与此同时,TNTs-PTA-GNPs纳米材料具有良好的生物相容性,且可促进酶与电极之间的直接电子转移.     

Electrochemical Phase Evolution of Metal-Based Pre-Catalysts for High-Rate Polysulfide Conversion

In situ evolution of electrocatalysts is of paramount importance in defining catalytic reactions. Catalysts for aprotic electrochemistry such as lithium–sulfur (Li-S) batteries are the cornerstone to enhance intrinsically sluggish reaction kinetics but the true active phases are often controversial. Herein, we reveal the electrochemical phase evolution of metal-based pre-catalysts (Co₄N) in working Li-S batteries that renders highly active electrocatalysts (CoS_x). Electrochemical cycling induces the transformation from single-crystalline Co₄N to polycrystalline CoS_x that are rich in active sites. This transformation propels all-phase polysulfide-involving reactions. Consequently, Co₄N enables stable operation of high-rate (10 C, 16.7 mA cm⁻²) and electrolyte-starved (4.7 μL mg_S⁻¹) Li-S batteries. The general concept of electrochemically induced sulfurization is verified by thermodynamic energetics for most of low-valence metal compounds.     

ZIF-Induced d-Band Modification in a Bimetallic Nanocatalyst: Achieving Over 44 % Efficiency in the Ambient Nitrogen Reduction Reaction

The electrochemical nitrogen reduction reaction (NRR) offers a sustainable solution towards ammonia production but suffers poor reaction performance owing to preferential catalyst–H formation and the consequential hydrogen evolution reaction (HER). Now, the Pt/Au electrocatalyst d-band structure is electronically modified using zeolitic imidazole framework (ZIF) to achieve a Faradaic efficiency (FE) of >44 % with high ammonia yield rate of >161 μg mg_cat⁻¹ h⁻¹ under ambient conditions. The strategy lowers electrocatalyst d-band position to weaken H adsorption and concurrently creates electron-deficient sites to kinetically drive NRR by promoting catalyst–N₂ interaction. The ZIF coating on the electrocatalyst doubles as a hydrophobic layer to suppress HER, further improving FE by >44-fold compared to without ZIF (ca. 1 %). The Pt/Au-N_ZIF interaction is key to enable strong N₂ adsorption over H atom.     

Surface-Plasmonic-Field-Induced Photoredox Catalysis and Mediated Electron Transfer for Washing-Free DNA Detection

Distance-dependent electromagnetic radiation and electron transfer have been commonly employed in washing-free fluorescence and electrochemical bioassays, respectively. In this study, we combined the two distance-dependent phenomena for sensitive washing-free DNA detection. A distance-dependent surface plasmonic field induces rapid photoredox catalysis of surface-bound catalytic labels, and distance-dependent mediated electron transfer allows for rapid electron transfer from the surface-bound labels to the electrode. An optimal system consists of a chemically reversible acceptor (Ru(NH₃)₆³⁺), a chemically reversible photoredox catalyst (eosin Y), and a chemically irreversible donor (triethanolamine). Side reactions with O₂ do not significantly decrease the efficiency of photoredox catalysis. Energy transfer quenching between the electrode and the label can be lowered by increasing the distance between them. Washing-free DNA detection had a detection limit of approximately 0.3 nm in buffer and 0.4 nm in serum without a washing step.     

A Universal Graphene Quantum Dot Tethering Design Strategy to Synthesize Single-Atom Catalysts

A general graphene quantum dot-tethering design strategy to synthesize single-atom catalysts (SACs) is presented. The strategy is applicable to different metals (Cr, Mn, Fe, Co, Ni, Cu, and Zn) and supports (0D carbon nanosphere, 1D carbon nanotube, 2D graphene nanosheet, and 3D graphite foam) with the metal loading of 3.0–4.5 wt %. The direct transmission electron microscopy imaging and X-ray absorption spectra analyses confirm the atomic dispersed metal in carbon supports. Our study reveals that the abundant oxygenated groups for complexing metal ions and the rich defective sites for incorporating nitrogen are essential to realize the synthesis of SACs. Furthermore, the carbon nanotube supported Ni SACs exhibits high electrocatalytic activity for CO₂ reduction with nearly 100 % CO selectivity. This universal strategy is expected to open up new research avenues to produce SACs for diverse electrocatalytic applications.     

Unveiling the Promotion of Surface-Adsorbed Chalcogenate on the Electrocatalytic Oxygen Evolution Reaction

Transition metal chalcogenides (TMCs) are efficient oxygen evolution reaction (OER) pre-electrocatalysts, and will in situ transform into metal (oxy)hydroxides under OER condition. However, the role of chalcogen is not fully elucidated after oxidation and severe leaching. Here we present the vital promotion of surface-adsorbed chalcogenates on the OER activity. Taking NiSe₂ as an example, in situ Raman spectroscopy revealed the oxidation of Se-Se to selenites (SeO₃²⁻) then to selenates (SeO₄²⁻). Combining the severe Se leaching and the strong signal of selenates, it is assumed that the selenates are rich on the surface and play significant roles. As expected, adding selenites to the electrolyte of Ni(OH)₂ dramatically enhance its OER activity. And sulfates also exhibit the similar effect, suggesting the promotion of surface-adsorbed chalcogenates on OER is universal. Our findings offer unique insight into the transformation mechanism of materials during electrolysis.