Synthesis,characterizations, and electrochemical studies of ZnO/reduced graphene oxide nanohybrids for supercapacitor application

Herein the present article reports the fabrication of ZnO/reduced graphene oxide (ZnG) nanohybrid following a reduction-based process using a non-hazardous material, i.e., ascorbic acid. The morphology, structure, and bonding in the nanohybrid were analyzed using different techniques. Atomic force microscopy and scanning electron microscopy images show spherical particles of ZnO distributed over reduced graphene oxide (rGO). The X-ray diffraction analysis gives calculated values of crystallite size for ZnO as 15.62 nm. The successful incorporation of ZnO nanoparticles into rGO was confirmed using energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy analyses. The electrochemical studies were performed using an electrolyte (0.5 M H₂SO₄). The calculated value of specific capacitance for the nanohybrid was 345 Fg^-1, which was found to be almost double as compared to that of rGO, which is having a value of only 190.5 Fg^-1 at the same scan rate. The nanohybrid also showed excellent capacitance retention after 1,000 cycles.     

阳极氧化/GCD新工艺法制备镍基超级电容器薄膜电极

采用磷酸阳极氧化法在金属镍表面形成阳极氧化复合膜,在1 mol·L^-1氢氧化钾溶液中进行大电流密度恒流充放电(GCD)处理, 使基体表面形成一层多孔纳米花瓣状膜. 采用扫描电镜(SEM), X射线光电子能谱(XPS), X射线衍射(XRD)仪, 对膜的形貌、组成和结构进行了表征, 使用电化学工作站、电池寿命测试仪对该膜的电容特性进行了测试. 结果表明, 所制氧化膜由三维多孔纳米花瓣状的NiO、α-Ni(OH)₂和β-Ni(OH)₂构成, 该膜具有优异的电容特性, 其在电流密度为6.7 A·g^-1时,比电容量达1509 F·g^-1, 而当电流密度为66.7 A·g^-1时,比电容量为1120 F·g^-1 (为6.7A·g^-1时的74%).在电流密度为66.7 A·g^-1时, 经过2000次循环测试后比电容量基本保持不变.     

Characterizations of nickel mesh and nickel foam current collectors for supercapacitor application

Nickel (Ni) current collectors having a three-dimensional and porous structure are considered attractive contestants for high-efficiency supercapacitors. Therefore, Ni current collectors have a unique architecture and outstanding electrochemical properties. This study reports the effect of electrochemical characterizations on the electrochemical behavior and physical properties of Ni mesh and Ni foam. Cyclic voltammetry (CV) and galvanostatic charge discharge (GCD) are used to examine the electrochemical properties and life span of the Ni mesh and Ni foam as a current collector in a supercapacitor application. Structural and microstructural characterizations are performed to verify the formation of an oxide layer after 1000 cycles of CV analysis. Results show that Ni foam can increase the yield electrochemical performance of the supercapacitor. Ni foam present better efficiency (35 F g⁻¹) compared to the Ni mesh (12 F g⁻¹) at 10 mV s⁻¹ scan rate by using 2 mg imaginary mass of active material. This result shows that Ni foam has good electrochemical performance and reversibility, higher pseudocapacitance, weaker polarization, and enhance rotating performance as to Ni mesh. The porous structure of Ni foam is in control for improving of the electrochemical properties, therefore, the electrochemical region was increased and shortened ion diffusion. Structural analysis shows that Ni mesh and Ni foam are oxidized after the electrochemical analysis and transformed to nickel oxide hydroxide (NiOOH). Higher specific surface area between the electrode and electrolyte leads to excellent electrochemical and pseudocapacitive performance of the Ni foam compared to the Ni mesh, even if the materials of current collectors are the same. Hence, the physical structure of the current collectors have a critical part in improving the energy density of the supercapacitor.     

碳布负载氢氧化镍电极材料的合成及其电容性能分析——推荐一个综合化学实验

作为超级电容器的电极材料,Ni(OH)₂具有理论比电容高、来源丰富、环境友好等优点,但较低的电导率影响了其实际性能。解决该问题的一种有效方法是在碳布导电基底上原位生长Ni(OH)₂薄膜。以此为基础设计综合化学实验,通过Ni(OH)₂/碳布薄膜电极的制备、表征及电化学性能测试,使学生进一步理解化学平衡原理在材料合成中的应用,了解材料的基本表征方法,掌握循环伏安法、恒流充放电法等电化学分析方法在实际测试中的运用与解析,从而达到巩固电化学理论知识、培养学生的实验技能、提高学生综合实验能力的目的。本实验的开展还可以帮助学生了解储能领域的科技前沿,激发学生的科研兴趣,培养学生的科研创新意识,适合在大学化学实验中推广应用。     

Electrochemical behavior of PbO2/PbSO4 electrode in the presence of surfactants in electrolyte

The electrochemical behavior of PbO₂/PbSO₄ electrode is investigated in 4.5 M H₂SO₄ in presence of three surfactants, Sodium Dodecyl Sulfate (SDS), Cetyltrimethylammonium bromide (CTAB) and Sodium tripolyphosphate (STPP), using cyclic voltametry, electrochemical spectroscopy impedance and galvanostatic discharge as techniques. The micro morphology of the surface of the modified PbO₂ electrodes is examined by scanning electron microscopy. The results show that SDS and CTAB when added in the electrolyte could refine the coating particles and change the roughness of the surface of the electrode leading to a thin film of PbO₂ with amorphous character. In addition, SDS and CTAB shift the hydrogen evolution potential towards more negative values, improve the discharge capacity of the anodic layer and accelerate the charge transfer. Under cathodic polarization, CTAB presents the lowest value of the charge transfer resistance R_ct. In the contrary, STPP shifts the oxygen evolution potential towards more positive values, passivates the surface of the electrode and inhibits completely the reaction of PbO₂ formation.     

Amperometric determination of paracetomol by a surface modified cobalt hexacyanoferrate graphite wax composite electrode

A stable electro active thin film of cobalt hexacyanoferrate (CoHCF) was deposited on the surface of an amine adsorbed graphite wax composite electrode using a simple method. Cyclic voltammetric experiments showed two pairs of well defined peaks for this CoHCF modified electrode which exhibited excellent electrocatalytic property for the oxidation of paracetomol at a reduced overpotential of 100 mV and over a concentration range of 3.33 × 10⁻⁶ to 1.0 × 10⁻³ M with a slope of 0.208 μA/μM with good sensitivity. The influence of the supporting electrolyte on peak current and peak potential were also obtained in addition with effects of common interference (e.g., ascorbic acid) on the response of the modified electrode. Various parameters that influence the electrochemical behavior of the modified electrode were optimized by varying scan rates and pH. Electrochemical impedance spectroscopy studies suggested that the electrode reaction of the CoHCF film is mainly controlled by transport of counter ion. The immobilized CoHCF maintained its redox activity showing a surface controlled electrode reaction with the electron transfer rate constant (K_s) of 0.94 s⁻¹ and charge transfer coefficient of 0.42. Hydrodynamic and chronoamperometric studies were done to explore the utility of the modified electrode in dynamic systems. The results of the differential pulse voltammetry (DPV) using the modified electrode was applied for the determination of paracetomol in commercially available tablets. The results obtained reveal that the electrode under study could be used as an effective sensor for online monitoring of paracetomol.     

Electrochemical behavior of dopamine at a quercetin-SAM-modified gold electrode and analytical application

A stable quercetin–thioglycolic acid-modified gold electrode (Qu–TCA/Au) was prepared as a self-assembled monolayer (SAM) and its electrochemical behavior was investigated by electrochemical methods. In 0.05-M phosphate buffer solution (pH 7.0) quercetin exhibits quasi-reversible signals at the Qu–TCA/Au electrode. The stability of the quercetin-modified gold electrode is very good. The quercetin self-assembled monolayer is an effective mediator for the oxidation of dopamine, which was investigated by cyclic voltammetry and differential pulse voltammetry. Ascorbic acid does not interfere with determination of dopamine at an electrode modified with a mixture of quercetin–thioglycolic acid and quercetin–11-mercaptoundecanoic acid. This modification allows dopamine to be determined in the presence of ascorbic acid in the range from 3×10^–5 to 3×10^–4 M. The detection limit is 1×10^–6 M. Scanning electrochemical microscopy (SECM) was employed to study the electrochemical performances of the modified gold electrode indicating different feedback modes at differently modified surfaces.     

磷酸可待因在Nafion修饰玻碳电极上的伏安行为研究及测定

用循环伏安法和微分脉冲吸附伏安法对磷酸可待因在Nafion修饰玻碳电极上的伏安行为进行了研究。结果表明在 0 .1mol/LHCl底液中 ,磷酸可待因在 + 1 .0 6V处 (vs.SCE)产生一良好的氧化峰 ,磷酸可待因浓度在 5 .0× 1 0 - 7～2 .5× 1 0 - 5mol/L范围内与峰电流呈线性关系 ,检出限为 1 .3× 1 0 - 7mol/L。并分别对其单方药和复方药制剂进行了测定     

Theoretical study on the electrochemical behavior of norepinephrine at Nafion multi-walled carbon nanotubes modified pyrolytic graphite electrode

DFT-B3LYP/6-31G (d, p) and HF/6-31G (d, p) calculations are performed for deoxidized norepinephrineat (NP(R)) and its oxidized form (NP(O)). The electrochemistry of norepinephrineat (NP) was studied by cyclic voltammetry (CV) at a pyrolytic graphite electrode modified by Nafion multi-walled carbon nanotubes (MWNTs) in phosphate buffers at pH 6.0, showing that the standard electrode potential of half reaction for NP(O), H+/NP(R) is 0.75l V. This experimental standard electrode potential of half reaction is consistent with that calculated using the energies of solvation and sum of electronic and thermal free energies of NP(R) and NP(O). The frontier orbital theory and Mülliken charges of molecular explain the electrochemical behavior of CV at modified electrode well. The singlet vertical excited states for NP(R) and NP(O) are also discussed.     

Electrochemical synthesis of polypyrrole/polyimide conducting composite using a polyamic acid precursor

Conducting polymer/poly(amic acid) composites were synthesized by casting poly(amic acid) (PAAc)film onto the surface of stainless steel followed by electrochemical deposition of polypyrrole. Polypyrrole/polyimide (PPy/PI) composites were also formed by preimidizing the polyamic acid film prior to electrodeposition of PPy. The electrical resistance of the bottom side of PPy/PAAc composite (2.3 Ω cm) was lower than that of the PPy/PI composite (6.4 Ω cm), the thickness of the matrix was the same. A PI matrix was used for electropolymerization of pyrrole. The electrodeposition was investigated by using different current densities. IR spectroscopy revealed interactions between the PAAc and PPy in the composite.     

The Mediation Effect of a Polyaniline-Coated Electrode on the Reduction of Iron (III) Ions

The mediation effect of polyaniline-coated platinum electrodes on the reduction of iron(III) ions was studied by the cyclic voltammetry and rotating disk electrode methods. The rate constants of the cross reaction between iron(III) ions and polyaniline (PA) were found to depend upon the amount of PA coated on the electrode. On the basis of the rate constants the PA-coated electrode mediates the reduction of iron(III) ion efficiently and behaves as well as a metallic electrode.     

Pt/PAn/Ti电极的制备及对甲醛的电催化氧化

通过循环伏安的电化学方法在金属钛基体上先后进行苯胺的聚合和金属铂的电化学沉积,得到以金属钛为基体的聚苯胺载铂电极(Pt/PAn/Ti),并通过扫描电镜和循环伏安法对该电极进行了表征。通过研究甲醛在该电极上的电催化氧化行为,考察了载铂量对甲醛氧化效果的影响及PAn在电催化氧化甲醛的过程中所起的作用。结果表明,载铂量与甲醛的氧化有一定的关系,PAn的存在使得铂微粒分散程度更好,有效面积更大,与相同铂沉积量的Pt/Ti电极相比,甲醛在其上的正向扫描氧化峰电流密度增加了2.3倍,电位负移了40mV;反向扫描氧化峰电流密度增加了5倍,电位负移了30mV。同时,PAn的存在也增强了电极的抗中毒能力。     

单层碳纳米管修饰电极上盐酸曲普利啶的电化学行为及其应用研究

应用循环伏安法研究了盐酸曲普利啶在碳纳米管修饰电极上的电化学行为.结果表明:在0.1 mol/L磷酸盐缓冲溶液(pH 6.9)中,盐酸曲普利啶产生一灵敏的氧化峰,其峰电位为0.81 V(vs.Ag/AgCl),峰电流与盐酸曲普利啶在1.0×10-6～1.3×10-4 mol/L浓度范围内呈线性关系,检出限为5.0×10-7mol/L,已用于片剂中盐酸曲普利啶的测定.     

Construction and application of an electrochemical sensor based on graphene-MXene nanocomposites for baicalin detectionEI北大核心CSCD

Redox graphene-MXene(rGO-MXene) nanocomposites were prepared by ion polymerization and used to construct a highly sensitive electrochemical sensor for baicalin(BA) detection. The synergistic effect of rGO and MXene increased the specific surface area and electron transport capacity of the electrode, and significantly enhanced the electrochemical response of BA. The cyclic voltammetry and differential pulse voltammetry were used to investigate the electrochemical behavior of BA on the sensor. Under the optimal conditions, the peak current exhibited a good linear relationship with BA concentration in the range of 0. 05-10 μmol / L, and the limit of detection was as low as 28 nmol / L. The method was applied to analyze traditional Chinese medicine preparations containing baicalin, such as Qingkailing Capsule and Sanhuang Tablets with good accuracy and spiked recovery. The results were highly consistent with those of high performance liquid chromatography, providing a technical means for the rapid and sensitive detection of traditional Chinese medicine preparations. © 2022, Youke Publishing Co.,Ltd. All rights reserved.     

Time-derivative cyclic voltabsorptometry for voltammetric characterization of catechin film on a carbon-paste electrode: one voltammogram becomes four

Using (+)-catechin electrodeposited on a carbon-paste electrode as a model system, we have demonstrated the usefulness of the time-derivative cyclic voltabsorptometry for voltammetric characterization of the deposited films, in the case when not only the deposited species but also the same ones in free solution participated in redox processes. A long-optical-path thin-layer cell was used for the voltabsorptometric measurements. The potential-dependent absorption signals were monitored for catechin at 252 and 279 nm in B-R buffer electrolytes with pH = 1.8. The combination of voltabsorptometry with voltammetry enabled one measured cyclic voltammogram to become four, which were attributed to catechin and its oxidized state, in free solution or in deposited state, respectively. The surface coverage of the electrode was evaluated from the cyclic voltammograms obtained for the deposited catechin, which decreased with the increasing scan rate. Also, the deposited species was found to make a major contribution to the total voltammetric current, especially at higher scan rates.     

Highly scalable and low cost binder free electrode of Zinc modified NiO nanofoam for dual role of supercapacitor and its free radical scavenging activity

In this study, pristine nickel oxide (NiO) and Zinc modified NiO nanofoams were prepared by green approach using camellia sinensis leaves extract. Pristine nickel oxide and Zn²⁺ modified NiO nanofoam were characterized by XRD, FTIR, FL, UV and FESEM. FE-SEM micrographs were clearly shows that the synthesised porous nanofoam with spherical shaped were constant distribution. The as prepared foam electrodes showed excellent supercapacitive behaviour with increase in specific capacitance with decrease in scan rate. The maximum specific capacitance 1530, 1706 and 1847Fg^-1 was obtained at scan rate of 10 mVs^-1 for increasing the Zn concentrations. After 3,000 cycles at 1 A g⁻¹, the cyclic stability remains excellent at 88.1% of the initial capacitance. Moreover, the as-prepared asymmetric supercapacitor exhibits a high energy density of 30.6 W h·kg⁻¹ at power density of 398 W kg⁻¹. This study is expected to provide new insights into exploring the potential mechanism of catalyst action. These findings show that Zinc @ NiO nanofoam could be a potentially useful electrode material for energy storage devices.     

An insight to the filtration mechanism of Pb(II) at the surface of a clay ceramic membrane through its preconcentration at the surface of a graphite/clay composite working electrode

The use of cyclic voltammetry (CV) and linear scan anodic stripping voltammetry (LSASV) to predict the selectivity of microfiltration ceramic membranes made from a lump of local clay towards Pb(II) ions filtration is described. The membranes were characterized by different techniques followed by CV analysis of the Fe(CN)₆^3-/Fe(CN)₆^4- redox couple and Pb(II) on bare graphite, raw clay, and clay-modified carbon paste electrode (clay-modified CPE). The effect of clay loading in the range of 1–10 % (w/w) on the electrodes is studied, where an enhanced peak current is observed for 5 % w/w clay. Moreover, a decrease in the peak current can be seen for bare graphite electrodes, suggesting that the clay mineral had played a substantial role in the sieving of heavy metal ions through the ceramic membrane. The electroactive surface area of 5% w/w raw clay towards Fe(II) ions was found to be in the order of 3.07 × 10^-2 cm² and higher than 5% w/w clay sintered to 1000 °C and bare graphite. CV analysis shows that both, 5 % w/w raw clay and 5 % w/w clay sintered to 1000 °C exhibited high peak currents towards Pb(II) ions. The mobility of the Pb(II) ions is found to increase when 5% w/w clay sintered to 1000 °C is utilized as membrane/electrode, leading to an increase in the amount of reduced Pb(II) ions on the surfaces of the clay membranes/electrodes. The study suggests successful filtration of Pb(II) ions through the proposed membrane/electrode and a much better accumulation than Fe(II) at the surface of the membrane/electrode before being subjected to filtration.     

聚磺胺嘧啶修饰电极伏安法测定对乙酰氨基酚

利用循环伏安法制备了聚磺胺嘧啶修饰电极, 研究了对乙酰氨基酚在该修饰电极上的电化学行为. 该电极对对乙酰氨基酚有较强的电催化作用. 在pH 9.0的PBS缓冲溶液中, 用循环伏安法和差分脉冲伏安法在该电极上测定了对乙酰氨基酚, 其线性范围分别为4.0×10-6～3.0×10-4 mol/L和2.0×10-7～1.0×10-5 mol/L, 检出限分别为9.0×10-7 mol/L和8.0×10-8 mol/L.     

Electrocatalytic response of dopamine at a dl-homocysteine self-assembled gold electrode

The gold electrode self-assembled with the homocysteine monolayer (Hcy/Au) is demonstrated to catalyze the electrochemical response of dopamine (DA) by cyclic voltammetry. A pair of well-defined redox waves was obtained and the calculated standard rate constant (k_s) is 2.1×10⁻² cm/s at the self-assembled electrode. The reduction peak of DA can be used to determine the concentration of DA in presence of ascorbic acid (AA) owing to the Hcy/Au also catalyzing the electrochemical oxidation of AA.     

Facile Preparation of α‐Zirconium Phosphate/Polyaniline Hybrid Film for Detecting Potassium Ion in a Wide Linear Range

A novel α‐zirconium phosphate/polyaniline (α‐ZrP/PANI) hybrid film used as K⁺ ion sensor was fabricated on carbon paper by electrochemical method. Mechanisms of film formation and detection of K⁺ ions were also proposed. The exfoliated α‐ZrP was mixed with PANI and deposited on carbon paper. The resultant α‐ZrP/PANI film exhibited a good current response to K⁺ ion with different concentrations. It also showed a wide logarithmic linear response in detecting K⁺ ions in the ranges of 10^?8–10^?4 M and 10^?4–10^?2 M, respectively. The results can be attributed to the synergetic effect of α‐ZrP and PANI.