Self‐Assembled Monolayers of Cobalt and Iron Phthalocyanine Complexes on Gold Electrodes: Comparative Surface Electrochemistry and Electrocatalytic Interaction with Thiols and Thiocyanate

The self‐assembling of the octa(hydroxyethylthio)‐metallophthalocyanine {MOHETPc (M=Co and Fe)} complexes and their similar analogues, octabutylthiometallophthalocyanine {MOBTPc (M=Co and Fe)} complexes on gold electrodes are investigated. Comparative surface voltammetric insights into their distinct self‐assembling properties with respect to the passivation of Faradaic processes and surface coverages, including their solution electrochemistry, suggest different orientations and non‐cleavage of their C? S bonds. In the pH 2?9 range, the reversible [M^(III)Pc(?2)]⁺ / [M^(II)Pc(?2)] redox couples show potential shifts close to ?59 mV / pH. The gold electrodes modified with the SAMs of these species show electrocatalytic activity towards the oxidation of thiols (L ‐cysteine, homocysteine and penicillamine) and thiocyanate in acidic media with detection limits in the region of 10^?7–10^?6 mol dm^?3. These monolayers are stable and easily reproducible.     

Volcano correlations for the reactivity of surface-confined cobalt N<Subscript>4</Subscript>-macrocyclics for the electrocatalytic oxidation of 2-mercaptoacetate

We have investigated the electrocatalytic activity of several substituted and unsubstituted cobalt–phthalocyanines of substituted tetraphenyl porphyrins and of vitamin B₁₂, for the electro-oxidation of 2-mercaptoacetate, with the complexes pre-adsorbed on a pyrolytic graphite electrode. Several N4-macrocyclic were used to have a wide variety of Co(II)/(I) formal potentials. The electrocatalytic activity, measured as current at constant potential, increases with the Co(II)/(I) redox potential for porphyrins as Co–pentafluorotetraphenylporphyrin < Co–tetrasulfonatotetraphenylporphyrin < Co-2,2′,2″,2‴tetra-aminotetraphenylporphyrin and decreases for cobalt phthalocyanines as Co-3,4-octaethylhexyloxyphthalocyanine > Co–octamethoxyphthalocyanine > Co–tetranitrophthalocyanine Co–tetraaminophthalocyanine > Co–unsubstituted phthalocyanine > Co–tetrasulfonatophthalocyanine > Co–perfluorinated phthalocyanine. Vitamin B₁₂ exhibits the maximum activity. A correlation of log I (at constant potential) versus the Co(II)/(I) formal potential of the catalysts gives a volcano curve. This clearly shows that the search for better catalysts for this reaction point to those N₄-macrocyclic complexes with Co(II)/(I) formal potentials close to −0.84 V versus SCE, which correspond to an optimum situation for the interaction of the thiol with the active site. Dedicated to Prof. Dr. Teresa Iwasita on the occasion of her 65th birthday in recognition of her numerous contributions to interfacial electrochemistry.     

离子液体中硫氰根在铂电极上吸附行为的SERS研究

利用表面增强拉曼光谱(SERS)研究了室温离子液体1-丁基-3-甲基咪唑氟硼酸盐([BMIM]BF4)中SCN-在Pt电极表面的吸附行为. 研究结果表明, 离子液体中SCN-在较宽的电位范围内吸附在Pt电极上, 且SCN-的吸附方式随着电位区间的变化而变化, 在不同的电位区间内检测到了不同的Stark位移: -0.9~0.4 V约为34 cm-1/V, 对应于S端吸附; -1.6~-1.2 V约为40 cm-1/V, 该区间以N端吸附为主, 中间电位区间为吸附方式的转变区, 且Pt电极在离子液体[BMIM]BF4中的零电荷电位约为-1.1 V(vs. Pt ).     

Co-N4大环配合物分子应用于异相电催化CO2还原

利用可再生能源产生的电能催化二氧化碳还原(CO₂RR)是可持续制备碳基化学品的一种潜在途径.电催化剂是实现这个转化的关键,目前还需要深入地研究机理去优化催化剂的设计.M-N₄结构的大环配合物是一类结构明确、性能易调控的分子电催化剂,是研究结构-性能关系的理想平台.其中,金属酞菁在异相电催化CO₂RR中展现出较好的催化性能,受到广泛关注.而其它M-N₄结构大环配合物(如金属卟啉、金属咔咯)在异相电催化CO₂RR中报道较少,且催化性能一般.本文对比研究了酞菁钴(CoPc)、四苯基卟啉钴(CoTPP)和三苯基咔咯钴(CoTPC)三种分子异相电催化CO₂RR的性能,揭示制约金属卟啉和金属咔咯分子应用于异相体系的原因,并提出改进方法.首先采用碳纳米管(CNT)复合的方法对三种分子进行了研究.结果表明,只有CoPc能够与CNT形成性能优异的复合电催化剂,而CoTPP和CoTPC复合电催化剂几乎不具备活性.这是因为这两种分子具有扭曲的苯环导致分子与CNT作用力弱,在复合物里面只有很少的分子锚定在CNT上.本文采用直接滴涂法制备三种分子与CNT物理混合电极,并研究了分子载量对催化性能的影响.结果表明,在1.08×10^-8molcm^-2低分子载量时,CoTPP+CNT和Co TPC+CNT样品基本无活性,它们的电催化活性随着分子载量的提升而显著增加.在5.4×10^-7molcm^-2的高载量时,CoTPC+CNT和CoTPP+CNT样品在-0.67 V(相对可逆氢电极,下同)的电位下分别展现出14.0和7.61 mA cm^-2的CO分电流密度,是1.08×10^-8 molcm^-2载量样品的8.7和7.9倍.这说明对于Co TPP和CoTPC分子,可以通过加大载量来增加与CNT作用几率,从而提高电极活性.然而,基于CoPc制备的样品活性随着CoPc分子载量的增加变化不明显.这是由于在低载量下CoPc分子已经很好地与CNT相互作用,并且CNT上CoPc分子负载量是有限的,继续增大载量只会导致聚集.本文进一步发展一种聚乙烯吡啶(PVP)桥连的办法,提升CoTPP和CoTPC在低载量下的电极活性.聚乙烯链能够通过疏水作用缠绕在CNT上,同时吡啶能够与分子金属中心配位,从而为分子与CNT结合建立桥梁.当分子载量为1.08×10^-8mol cm^-2时,CoTPP+CNT/PVP在-0.67 V电位下展现出85%以上的CO法拉第效率,而且CO分电流密度达到7.84 mA cm^-2,是没有添加PVP对比样CoTPP+CNT的8倍.由此可见,分子与基底的相互作用强度对异相电催化CO₂RR的性能有重要影响.对于与基底相互作用弱的大环配合物分子可以通过大分子载量的滴涂法或引入桥连分子来提高电极性能.这些方法可以拓展到其它分子体系,有助于构建高效的异相分子电催化剂.     

Pt-WO3/C电极表面活化对乙二醇和CO氧化的作用

用丙酮和四氢呋喃混合溶液对Pt—WO3/C电极进行表面活化处理后，乙二醇在Pt—WO3/C电极上的电催化氧化活性大幅度提高．发现无论在中性溶液中还是在酸性溶液中，表面活化处理后的Pt—WO3/C电极，乙二醇的起始氧化电位负移，氧化峰电流在酸性介质中增加到表面活化处理前的3．2倍：中性介质中增加到表面处理前的4．7倍，其主要原因是表面活化处理后，一方面增加了催化剂Pt的活性表面，另一方面也促进了电极表面吸附的CO的电氧化，减少了CO对电极表面的毒化作用．     

Atomic‐Level Insight into Optimizing the Hydrogen Evolution Pathway over a Co1‐N4 Single‐Site Photocatalyst

Knowledge of the photocatalytic H₂ evolution mechanism is of great importance for designing active catalysts toward a sustainable energy supply. An atomic‐level insight, design, and fabrication of single‐site Co₁‐N₄ composite as a prototypical photocatalyst for efficient H₂ production is reported. Correlated atomic characterizations verify that atomically dispersed Co atoms are successfully grafted by covalently forming a Co₁‐N₄ structure on g‐C₃N₄ nanosheets by atomic layer deposition. Different from the conventional homolytic or heterolytic pathway, theoretical investigations reveal that the coordinated donor nitrogen increases the electron density and lowers the formation barrier of key Co hydride intermediate, thereby accelerating H–H coupling to facilitate H₂ generation. As a result, the composite photocatalyst exhibits a robust H₂ production activity up to 10.8 μmol h⁻¹, 11 times higher than that of pristine counterpart.     

Cobalt Phthalocyanine Molecular Electrode for the Electrochemical Investigation of the Release of Glutathione upon Copper‐Catalyzed Decomposition of S‐Nitrosoglutathione

Decomposition of S‐nitrosoglutathione (GSNO) in phosphate buffer solution at physiological pH 7.4 in the presence of cuprous ion as a catalyst and sodium borohydride as a reducing agent is analyzed by observing the transient apparition of reduced glutathione GSH through its electrooxidation. Transient formation of GSH, upon decomposition of 1 mM GSNO in presence of 0.025 mM Cu(NO₃)₂ and 1 mM NaBH₄ was detected by using an ordinary pyrolytic graphite electrode modified with an adsorbed monolayer of cobalt phthalocyanine at 0 V vs. SCE.     

Electrocatalytic Activity of Nanohybrids Based on Carbon Nanomaterials and MFe2O4 (M=Co,Mn) towards the Reduction of Hydrogen Peroxide

We report the advantages of hybrid nanomaterials prepared with electrogenerated ferrites (MFe₂O₄; M: Co, Mn) and multi‐walled carbon nanotubes (MWCNTs) or thermally reduced graphene oxide (TRGO) on the electro‐reduction of hydrogen peroxide. Glassy carbon electrodes (GCE) modified with these hybrid nanomaterials dispersed in Nafion/isopropanol demonstrated a clear synergism on the catalytic reduction of reduction of hydrogen peroxide at pH 13.00. The intimate interaction between MFe₂O₄ and carbon nanomaterials allowed a better electronic transfer and a facilitated regeneration of M²⁺ at the carbon nanomaterials, reducing the charge transfer resistances for hydrogen peroxide reduction and increasing the sensitivities of the amperometric response.     

Binderless Solution Processed Zn Doped Co3O4 Film on FTO for Rapid and Selective Non‐enzymatic Glucose Detection

A simple solution based deposition process has been used to fabricate Zn doped Co₃O₄ electrode as an electrocatalyst for non‐enzymatic oxidation of glucose. XRD, HRTEM, SEM, EELS, AFM, EIS was used to characterise the electrode. The addition of Zn as dopant on Co₃O₄ resulted in enhanced electrochemical performance of Zn:Co₃O₄ material compared to pristine Co₃O₄ due to increased charge transferability. The as prepared electrode showed fast response (<7 s) time, good sensitivity (193 μA mM⁻¹ cm⁻²) in the linear range of 5 μM–0.62 mM, good selectivity towards glucose at a relatively lower applied potential of +0.52 V in 0.1 M NaOH solution. A detection limit of ∼2 μM was measured for the Zn:Co₃O₄ electrode. The applied fabrication method resulted in good inter and intra electrode reproducibility as was shown by the lower relative standard deviation values (R.S.D). The electrode retained 70 % of initial current response after 30 days. Although the as prepared Zn:Co₃O₄ electrodes did not result in highest reported sensitivity, and lowest limit of detection; the ease of fabrication and scalability of production, good inter and intra electrode reproducibility makes it a potential candidate for commercial application as glucose sensor.     

Enhanced Electrocatalytic Activity of Dual Template Based Pt/Cu‐zeolite A/Graphene for Methanol Electrooxidation

A novel Pt/Cu‐zeolite A/graphene based electrocatalyst was successfully prepared by chemical reduction method for methanol electrooxidation. Graphite oxide and Cu functionalized zeolite A were simultaneously reduced by NaBH₄ to prepare Cu‐zeolite A/graphene support which was used to deposit Pt nanoparticles. The nanostructure and composition of as‐prepared Pt/Cu‐zeolite A/graphene composites were characterized by X‐ray diffractometer, X‐ray fluorescence, Fourier transform infrared spectrometer and scanning electron microscopy. The electrocatalytic properties of Pt/Cu‐zeolite A/graphene modified electrode for methanol oxidation were investigated by cyclic voltammetry and chronoamperometry in 0.10 mol/L H₂SO₄ + 0.50 mol/L CH₃OH solution. Compared with Pt/zeolite A/graphene electrode and Pt/graphene electrode, Pt/Cu‐zeolite A/graphene based electrode exhibited obviously enhanced current and higher electrocatalytic activity for methanol electrooxidation. The increased electrocatalytic activity was attributed to the presence of zeolite A and reduced graphene oxide based dual template, which significantly increased the effective electrode surface and facilitated the diffusion of analytes into the electroactive catalyst.     

Electrocatalytic Oxidation of Cysteine at a CoSalophen/ n‐(butyl)4SiW12O40 Carbon Paste Electrode

In the present study, a novel mixture consisting of N,N′‐bis(salicylidene)‐1,2‐phenylenediamino cobalt (CoSalophen, CoSal) complex and (n‐butyl)₄SiW₁₂O₄₀ (SiW₁₂), have been used to chemically modify a carbon paste electrode (CPE) for sensitive determination of cysteine (CySH). The electrocatalytic effect of the newly developed modified CPE towards oxidation of CySH was evaluated by comparing cyclic and differential pulse voltammograms in the presence of cysteine at bare, CoSal, SiW₁₂ and CoSal/SiW₁₂ modified CPE. The differential pulse voltammetry method was applied as a sensitive method for quantitative detection of CySH trace amounts, the experimental conditions being optimized in order to evaluate the best analytical parameters of the sensor. Reproducibility and stability studies were also performed and the sensor was applied for the determination of CySH in a pharmaceutical sample and in human blood serum and urine samples.     

Electrocatalytic Activity of Asymmetrical Cobalt Phthalocyanines in the Presence of N Doped Graphene Quantum Dots: The Push‐pull Effects of Substituents

A series of Co phthalocyanine (CoPc) derivatives and their respective nitrogen doped graphene quantum dot conjugates were used as catalysts towards the electrooxidation of hydrazine. Using a glassy carbon electrode as a support for the electrocatalysts, through cyclic voltammetry and chronoamperometry, the effects of combining the CoPcs with the nitrogen doped graphene quantum dots (NGQDs) were studied. The general observations made were that the NGQDs improve the catalytic activity of the CoPcs in both the π‐π stacked and covalently linked conjugates by increasing the sensitivities and lowering the limits of detection with values as low as 0.43 μM being recorded.     

RuP2‐Based Catalysts with Platinum‐like Activity and Higher Durability for the Hydrogen Evolution Reaction at All pH Values

Highly active, stable, and cheap Pt‐free catalysts for the hydrogen evolution reaction (HER) are under increasing demand for future energy conversion systems. However, developing HER electrocatalysts with Pt‐like activity that can function at all pH values still remains as a great challenge. Herein, based on our theoretical predictions, we design and synthesize a novel N,P dual‐doped carbon‐encapsulated ruthenium diphosphide (RuP₂@NPC) nanoparticle electrocatalyst for HER. Electrochemical tests reveal that, compared with the Pt/C catalyst, RuP₂@NPC not only has Pt‐like HER activity with small overpotentials at 10 mA cm⁻² (38 mV in 0.5 m H₂SO₄, 57 mV in 1.0 m PBS and 52 mV in 1.0 m KOH), but demonstrates superior stability at all pH values, as well as 100 % Faradaic yields. Therefore, this work adds to the growing family of transition‐metal phosphides/heteroatom‐doped carbon heterostructures with advanced performance in HER.     

Ion‐Selective Electrodes for Thiocyanate Based on the Dinuclear Zinc(II) Complex of a Bis‐N,O‐bidentate Schiff Base

An ion selective electrode based on the dinuclear complex formed by two zinc(II) ions and two molecules of the bis‐N,O‐bidentate Schiff base 2,2′‐[methylenebis(4,1‐phenylenenitrilomethylidyne)]bisphenol exhibits thiocyanate selectivity with a good discrimination of nitrite, nitrate, and azide. The selectivities of electrode membranes with various compositions indicate that this potentiometric selectivity is based on the formation of a 1 : 1 complex between the thiocyanate anion and the dinuclear ionophore. The 2 : 1 ratio of thiocyanate ions and the dinuclear ionophore that results from higher ratios of cationic sites and ionophore worsens the selectivity, suggesting that binding of a thiocyanate to both zinc(II) centers of the dinuclear ionophore is not favorable. Interestingly, the selectivity patterns of these electrodes differ radically from that of a highly sulfate selective electrode based on a compound reported previously to be the analogous mononuclear 1 : 1 complex of zinc(II) and the same Schiff base. It is suggested that the previously reported 1 : 1 complex with zinc(II) may indeed have been a polymer of the same elemental composition.     

Self‐assembly of p‐Aminothiophenol on Gold Surface: Application for Impedimetric and Potentiometric Sensing of Cobalt (II) Ions – A Comparative Study

Cobalt, despite an essential biological element, imposes threat to humans when exposed to high concentration or even to low concentration for long term which demands the development of highly sensitive and selective analytical methods for its trace analysis. In the present work, self‐assembly of p‐aminothiophenol (p‐ATP) on gold surface (Au?ATP SAM) was carried out and for the first time, applied as a platform for impedimetric and potentiometric sensing of Co²⁺. Au?ATP SAM was characterized using electrochemical techniques: cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), in the presence of two redox probes: [Fe(CN)₆]^3?/4? and [Ru(NH₃)₆]^2+/3+ to evaluate associated passivating behaviour. Au?ATP SAM completely blocked [Fe(CN)₆]^3?/4? as compared to [Ru(NH₃)₆]^2+/3+ which may be attributed to inner‐sphere and outer‐sphere ET mechanisms, respectively. Au?ATP SAM was found to exhibit excellent sensitivity towards Co²⁺ in a wider concentration range from 1.0×10^?12 M to 1.0×10^?5 M (r²=0.963) at pH 5.5 with a detection limit of 6.0×10^?13 M and superior selectivity. Further, carbon paste electrode (CPE) was prepared by incorporating p‐ATP bound gold nanoparticles and explored for potentiometric sensing of Co²⁺ which exhibited Nernstian slope of 29.2±0.2 mV/dec in linear concentration range of 1.0×10^?6 M–1.0×10^?1 M (r²=0.971) with a detection limit of 8.0×10^?7 M. The proposed sensors were successfully applied for estimation of Co²⁺ content in water samples.     

Self‐Templating Synthesis of Hollow Co3O4 Microtube Arrays for Highly Efficient Water Electrolysis

In spite of recent advances in the synthesis of hollow micro/nanostructures, the fabrication of three‐dimensional electrodes on the basis of these structures remains a major challenge. Herein, we develop an electrochemical sacrificial‐template strategy to fabricate hollow Co₃O₄ microtube arrays with hierarchical porosity. The resultant unique structures and integrated electrode configurations impart enhanced mass transfer and electron mobility, ensuring high activity and stability in catalyzing oxygen and hydrogen evolution reactions. Impressively, the apparent performance can rival that of state‐of‐the‐art noble‐metal and transition‐metal electrocatalysts. Furthermore, this bifunctional electrode can be used for highly efficient overall water splitting, even competing with the integrated performance of Pt/C and IrO₂/C.     

Boosting the Energy Density of Carbon‐Based Aqueous Supercapacitors by Optimizing the Surface Charge

The voltage of carbon‐based aqueous supercapacitors is limited by the water splitting reaction occurring in one electrode, generally resulting in the promising but unused potential range of the other electrode. Exploiting this unused potential range provides the possibility for further boosting their energy density. An efficient surface charge control strategy was developed to remarkably enhance the energy density of multiscale porous carbon (MSPC) based aqueous symmetric supercapacitors (SSCs) by controllably tuning the operating potential range of MSPC electrodes. The operating voltage of the SSCs with neutral electrolyte was significantly expanded from 1.4 V to 1.8 V after simple adjustment, enabling the energy density of the optimized SSCs reached twice as much as the original. Such a facile strategy was also demonstrated for the aqueous SSCs with acidic and alkaline electrolytes, and is believed to bring insight in the design of aqueous supercapacitors.     

Electrodeposition of Cobalt Oxide Nanostructure on the Glassy Carbon Electrode for Electrocatalytic Determination of para‐Nitrophenol

Cobalt oxide nanostructure (CoO_xNS) deposited on the glassy carbon (GC) electrode surface is proposed as a novel electrocatalytic system for the reduction of para‐Nitrophenol. Cyclic voltammetry, electrochemical impedance spectroscopy, atomic force microscopy and scanning electron microscopy were used for characterization of deposited CoO_xNS. CoO_xNS deposited by cycling at positive potentials (0 to +1.3 V) show less charge‐transfer resistance (Rct) and more catalytic activity for the electroreduction of p‐nitrophenol compared to those CoO_xNS obtained by scanning the applied potential throughout a negative V range. The GC/CoO_xNS electrode showed good electrocatalytic activity toward the reduction of p‐nitrophenol at different pH values.