基于纳米二氧化锆与铂微粒复合修饰玻碳电极的甲醛传感器研究

采用循环伏安法在玻碳电极表面依次电沉积纳米二氧化锆和铂微粒,制备了一种检测甲醛的新型电化学传感器。用电镜扫描对该修饰电极表面进行了表征,循环伏安法和线性扫描伏安法研究了甲醛在该修饰电极上的电催化氧化作用,优化了实验参数。结果表明,该修饰电极对甲醛有很好的电催化氧化作用,在0.1 mol/L H2SO4溶液中,甲醛的氧化峰电流与其浓度在1.0×10-6~5.0×10-3mol/L范围内呈良好线性关系,回归方程为Ip(μA)=79.95+2.005×105c(mol/L),相关系数r=0.999 3,检出限为5.0×10-7mol/L。     

A Sensitive and Selective Nitrite Detection in Water Using Graphene/Platinum Nanocomposite

A glassy carbon electrode modified with reduced graphene oxide and platinum nanocomposite film was developed simply by electrochemical method for the sensitive and selective detection of nitrite in water. The electrochemical reduction of graphene oxide (GO) efficiently eliminates oxygen‐containing functional groups. Pt nanoparticles were electrochemically and homogeneously deposited on the ErGO surface. Field emission scanning electron microscopy (FE‐SEM), Raman spectroscopy, attenuated total reflectance‐fourier transform infrared spectroscopy (ATR‐FTIR), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) were used to examine the surface morphology and electrocatalytic properties of the Pt‐ErGO nanocomposite film‐modified electrode surface. The fabricated nitrite sensor showed good electrochemical performance with two linear ranges; one from 5 to 100 µM (R²=0.9995) and the other from 100 to 1000 µM (R²=0.9972) and a detection limit of 0.22 µM. The proposed sensor was successfully applied for the detection of nitrite in tap water samples which proves performance of the Pt‐ErGO nanocomposite films.     

Photoelectrochemical Reduction of Carbon Dioxide with a Copper Graphitic Carbon Nitride Photocathode

Research on the photoreduction of CO₂ often has been dominated by the use of sacrificial reducing agents. A pathway that avoids this problem would be the development of photocathodes for CO₂ reduction that could then be coupled to a photoanodic oxygen evolution reaction. Here, we present the use of copper-substituted graphitic carbon nitride (Cu−CN) on a fluorinated tin oxide (FTO) electrode for the photoelectrochemical two-electron reduction of CO₂ to CO as a major product (>95 %) and formic acid (<5 %). The results show that at a potential of −2.5 V versus Fc\Fc⁺ the CO₂ reduction activity of Cu−CN on FTO electrode improves by 25 % upon illumination by visible light with a faradaic efficiency of nearly 100 %. Independently, X-ray photoelectron spectroscopy conclusively shows a pronounced increase in the electrical conductivity of the Cu−CN upon white light illumination under vacuum and a contactless measuring configuration. This photo-assisted charge mobility is shown to play a key role in the increased reactivity and faradaic efficiency for the reduction of CO₂.     

On the Existence and Role of Formaldehyde During Aqueous Electrochemical Reduction of Carbon Monoxide to Methanol by Cobalt Phthalocyanine

A long-time challenge in aqueous CO₂ electrochemical reduction is to catalyze the formation of products beyond carbon monoxide with selectivity. Formaldehyde is the simplest of these products and one of the most relevant due to its broad use in the industry. Paradoxically it is one of the less reported product. Such scarcity may be in part explained by difficult identification and quantification using conventional chromatography or proton nuclear magnetic resonance techniques. Likewise, indirect detection methods are usually not compatible with labelled studies for asserting product origin. Recently, the possible production of formaldehyde during electrochemical reduction of carbon monoxide to methanol at cobalt phthalocyanine molecular catalyst in basic media has been the object of contradictory reports. By applying an analytical procedure based on proton NMR along with labelled studies, we provide definitive evidence for HCHO formation. We have further identified the possible scenarios for methanol formation through formaldehyde and revealed that the formation of the intermediate and its subsequent reduction are taking place at the same single active site. These studies open a new perspective to improve selectivity toward formaldehyde formation and to develop a subsequent chemistry based on reacting it with nucleophiles.     

Preparation of Chitosan Based Scaffolds Using Supercritical Carbon Dioxide

A novel chitosan-formaldehyde porous derivative (scaffolds) was prepared by reaction of 85% deacetylated chitosan with 37% aq. formaldehyde using supercritical carbon dioxide (sc. CO₂). Prior to reaction, the chitosan hydrogel was prepared in 1% aq. acetic acid (AcOH) and formaldehyde. The prepared hydrogel was subjected to solvent exchange. The identity of the Schiff base was confirmed by Fourier transform infrared spectroscopy (FTIR). The chitosan-derivative was evaluated by thermal analysis, scanning electron microscopy, and porosimetry analysis. Overall, the sc. CO₂ assisted chitosan derivative opens new perspectives as biomedical material.     

Boosting Visible-Light Carbon Dioxide Reduction with Imidazolium-Based Ionic Liquids

Efficiently generating C₁ building blocks from environmentally friendly carbon sources, such as through photocatalytic CO₂ reduction, is essential for fostering a sustainable circular economy. The pursuit of mild catalytic activation methods has yielded powerful catalysts that can be synergistically employed alongside various reaction media to enhance overall performance. Herein, we elucidate the influence of diverse imidazolium-based ionic liquids as additives for visible-light-driven CO₂ reduction with ruthenium(II)- and rhenium(I)-bipyridine complexes. Our investigation reveals that incorporating ionic liquids into traditional solvents at concentrations below 10 % can markedly boost CO production while suppressing H₂ generation. The best results were obtained for the highly basic ionic liquid [C₂mim][OAc], resulting in a substantial rise in CO formation from 0.3 μmol/h to 5.4 μmol/h and an increase in turnover number from 3 to 59. This study underscores the cooperative influence of imidazolium-based ionic liquids on CO₂ photoreduction while circumventing their use as primary solvents, thus offering a promising avenue for sustainable chemical synthesis.     

Amperometric Glucose Biosensor Based on Pt‐Pd Nanoparticles Supported by Reduced Graphene Oxide and Integrated with Glucose Oxidase

A novel glucose biosensor was developed based on the immobilization of glucose oxidase (GOx) on reduced graphene oxide incorporated with electrochemically deposited platinum and palladium nanoparticles (PtPdNPs). Reduced graphene oxide (RGO) was more hybridized by chemical and heat treatment. Bimetallic nanoparticles were deposited electrochemically on the RGO surface for potential application of the Pd? Pt alloy in biosensor preparation. The as‐prepared hybrid electrode exhibited high electrocatalytic activities toward H₂O₂, with a wide linear response range from 0.5 to 8 mM (R²=0.997) and high sensitivity of 814×10^?6 A/mMcm². Furthermore, glucose oxidase with active material was integrated by a simple casting method on the RGO/PdPtNPs surface. The as‐prepared biosensor showed good amperometric response to glucose in the linear range from 2 mM to 12 mM, with a sensitivity of 24×10^?6 A/mMcm², a low detection limit of 0.001 mM, and a short response time (5 s). Moreover, the effect of interference materials, reproducibility and the stability of the sensor were also investigated.     

A Stable and Conductive Metallophthalocyanine Framework for Electrocatalytic Carbon Dioxide Reduction in Water

Transformation of carbon dioxide to high value‐added chemicals becomes a significant challenge for clean energy studies. Here a stable and conductive covalent organic framework was developed for electrocatalytic carbon dioxide reduction to carbon monoxide in aqueous solution. The cobalt(II) phthalocyanine catalysts are topologically connected via robust phenazine linkage into a two‐dimensional tetragonal framework that is stable under boiling water, acid, or base conditions. The 2D lattice enables full π conjugation along x and y directions as well as π conduction along the z axis across the π columns. With these structural features, the electrocatalytic framework exhibits a faradaic efficiency of 96 %, an exceptional turnover number up to 320 000, and a long‐term turnover frequency of 11 412 hour^?1, which is a 32‐fold improvement over molecular catalyst. The combination of catalytic activity, selectivity, efficiency, and durability is desirable for clean energy production.     

In-Situ Electrodeposition of Rhodium nanoparticles Anchored on Reduced Graphene Oxide nanosheets as an Efficient Oxygen Reduction Electrocatalyst

A simple, versatile, and cost-effective one-pot electrochemical deposition is used to fabricate rhodium (Rh) nanoparticles decorated surface of reduced graphene oxide (rGO) functionalized glassy carbon electrode (GCE) for oxygen reduction reaction (ORR) in alkaline media. The chemical and physical structure of the sample is probed via transmission electron microscopy, rotating disk electrode (RDE), X-ray photoelectron spectroscopy, linear sweep voltammetry, and Raman spectroscopy. The synergistic effects between the unique properties of Rh nanoparticles and rGO creates such innovative hybrid that exhibits a catalytic activity comparable to that of the commercial platinum electrocatalyst (Pt/C). As a result, the as-electrodeposited Rh@rGO hybrid exhibits outstanding ORR activity in alkaline media, as evidenced by a larger diffusion-limited current, greater positive onset potential, much better stability and methanol tolerance than Pt/C under the same conditions.     

二氧化锆/石墨烯复合材料对亚硝酸盐的电化学传感研究

制备了一种二氧化锆/还原氧化石墨烯(ZrO2NPs/rGO)复合材料修饰电极的亚硝酸盐电化学传感器,并成功用于亚硝酸盐的检测.采用循环伏安法和电流-时间曲线考察了修饰电极的电化学行为.实验结果表明,ZrO2NPs/rGO复合材料修饰电极对亚硝酸盐具有良好的电流响应.在最优实验条件下,电流-时间曲线中的电流响应信号与亚硝酸盐浓度在3.0×10Symbolm@@_7～1.0×10Symbolm@@_6 mol/L和1.0×10Symbolm@@_6～6.0×10Symbolm@@_6 mol/L的范围内呈良好的线性关系,检测限为1.0×10Symbolm@@_7 mol/L(S/N 3).该传感器灵敏性高、稳定性和重现性好.使用此传感器检测实际样品香肠中的亚硝酸盐的回收率为93.7％～110.4％,相对标准偏差为1.6％～2.1％.     

Cu2O/CuO Electrocatalyst for Electrochemical Reduction of Carbon Dioxide to Methanol

Herein, we report the controlled and direct fabrication of Cu₂O/CuO thin film on the conductive nickel foam using electrodeposition route for the electrochemical reduction of carbon dioxide (CO₂) to methanol. The electrocatalytic reduction was performed in CO₂ saturated aqueous solution consisting of KHCO₃, pyridine and HCl at room temperature. CO₂ reduction was carried out at a constant potential of −1.3 V for 120 min to study the electrochemical performance of the prepared electrocatalysts. Cu₂O/CuO shows better electrocatalytic activity with highest current density of 46 mA/cm². The prepared catalyst can be an efficient and selective electrode for the production of methanol.     

Electrochemical Reduction of Carbon Dioxide to Methanol on Hierarchical Pd/SnO2 Nanosheets with Abundant Pd–O–Sn Interfaces

Electrochemical conversion of CO₂ into fuels using electricity generated from renewable sources helps to create an artificial carbon cycle. However, the low efficiency and poor stability hinder the practical use of most conventional electrocatalysts. In this work, a 2D hierarchical Pd/SnO₂ structure, ultrathin Pd nanosheets partially capped by SnO₂ nanoparticles, is designed to enable multi‐electron transfer for selective electroreduction of CO₂ into CH₃OH. Such a structure design not only enhances the adsorption of CO₂ on SnO₂, but also weakens the binding strength of CO on Pd due to the as‐built Pd–O–Sn interfaces, which is demonstrated to be critical to improve the electrocatalytic selectivity and stability of Pd catalysts. This work provides a new strategy to improve electrochemical performance of metal‐based catalysts by creating metal oxide interfaces for selective electroreduction of CO₂.     

电化学二氧化碳还原中的铜基催化剂

由于不断增加的二氧化碳排放导致全球变暖,且能源短缺等问题日益恶化,将二氧化碳电化学还原为高附加值化学品和燃料引起了极大的兴趣,设计高效催化剂对实现二氧化碳的高效选择性转化具有重要意义. 在所探索的各种催化剂中,铜基催化剂具有良好的开发潜力,可用于烃类生产. 本文综述了铜基电化学二氧化碳转化材料的最新进展. 分别从尺寸结构到不同形式（合金、氧化物）的铜基催化剂,以及分子催化剂等方面展开,重点讨论铜基催化剂上二氧化碳电解还原的反应机理. 最后,对未来高效铜基催化剂的设计提出展望,以促进二氧化碳转化的可持续发展.     

Pt-Mo电极上CO、甲醛和甲醇的电催化氧化-微分电化学质谱研究

利用微分电化学质谱（DEMS）研究了Mo修饰的Pt电极上CO、甲醛和甲醇的电催 化氧化,证实了Mo(IV)是催化活性样品,而且它只对弱吸附CO的氧化起催化作用, 对强吸附CO的氧化没有催化活性。在低于0.4 V的电位下,吸附在Pt电极上的Mo结 甲醇和甲醛的催化氧化是通过弱吸附CO的氧化路径进行的。     

还原氧化石墨烯-多壁碳纳米管复合膜负载金纳米粒子修饰玻碳电极检测双酚A

以水合肼为还原剂,采用均相还原法制备还原氧化石墨烯-多壁碳纳米管复合材料(rGO-MWCNTs),通过滴涂法将其修饰到玻碳电极(GCE)表面.以此复合材料为载体,采用电化学方法制备了金纳米粒子-还原氧化石墨烯-多壁碳纳米管复合膜修饰电极(AuNPs-rGO-MWCNTs/GCE).通过扫描电镜(SEM)、EDS能谱技术和电化学方法对此电极进行了表征.研究了双酚A在修饰电极上的电化学行为.结果表明,此电极对双酚A的电极过程具有良好的电化学活性,在0.10 mol/L PBS溶液(pH 7.0)中,微分脉冲伏安法测定双酚A的线性范围为5.0 × 10-9~1.0 × 10-7 mol/L和1.0 × 10-7~2.0 × 10-5 mol/L,检出限为1.0 ×10-9 mol/L(S/N=3). 将此电极用于模拟水样和超市购物小票样品中双酚A含量的测定,加标回收率分别为97%~110%和98%~104%.     

Reduction of Carbon Dioxide to Formate at Low Overpotential Using a Superbase Ionic Liquid

A new low‐energy pathway is reported for the electrochemical reduction of CO₂ to formate and syngas at low overpotentials, utilizing a reactive ionic liquid as the solvent. The superbasic tetraalkyl phosphonium ionic liquid [P₆₆₆₁₄][124Triz] is able to chemisorb CO₂ through equimolar binding of CO₂ with the 1,2,4‐triazole anion. This chemisorbed CO₂ can be reduced at silver electrodes at overpotentials as low as 0.17 V, forming formate. In contrast, physically absorbed CO₂ within the same ionic liquid or in ionic liquids where chemisorption is impossible (such as [P₆₆₆₁₄][NTf₂]) undergoes reduction at significantly increased overpotentials, producing only CO as the product.     

单原子催化剂电催化还原二氧化碳研究进展

电催化CO₂还原能够在常温常压下利用电能将CO₂转化为含碳清洁能源,具有很好的应用前景。 但其应用仍受缓慢的阴极催化剂限制。众所周知,催化剂的尺寸对其活性有很大的影响,将金属催化剂减少到纳米颗粒级别,能够显著提升其暴露的活性位点数和本征活性,从而提升其催化性能。在这一思路下,如果将催化剂的尺寸降低到单原子分散级别,催化剂的活性能够得到明显提升。近几年,由于单原子分散催化剂具有特殊的微观几何结构和电子态,已经成为电催化还原CO₂领域的研究热点。在本综述中,对单原子分散催化剂在电催化还原CO₂方面的研究进行了总结和回顾,并对未来单原子分散催化剂在电催化还原CO₂领域的难点问题和进一步研究方向进行了分析和讨论。     

Partially Oxidized Palladium Nanodots for Enhanced Electrocatalytic Carbon Dioxide Reduction

Here we report a partially oxidized palladium nanodot (Pd/PdO_x) catalyst with a diameter of around 4.5 nm. In aqueous CO₂‐saturated 0.5 m KHCO₃, the catalyst displays a Faradaic efficiency (FE) of 90 % at −0.55 V vs. reversible hydrogen electrode (RHE) for carbon monoxide (CO) production, and the activity can be retained for at least 24 h. The improved catalytic activity can be attributed to the strong adsorption of CO₂^.− intermediate on the Pd/PdO_x electrode, wherein the presence of Pd²⁺ during the electroreduction reaction of CO₂ may play an important role in accelerating the carbon dioxide reduction reaction (CO₂RR). This study explores the catalytic mechanism of a partially oxidized nanostructured Pd electrocatalyst and provides new opportunities for improving the CO₂RR performance of metal systems.