Amine axial ligand-coordinated cobalt phthalocyanine-based catalyst for flow-type membraneless hydrogen peroxide fuel cell or enzymatic biofuel cell

In this study,an amine-coordinated cobalt phthalocyanine(CoPc)-based anodic catalyst was fabricated by a facile process,to enhance the performance of hydrogen peroxide fuel cells(HPFCs) and enzymatic biofuel cells(EBCs).For this purpose,polyethyleneimine(PEI) was added onto the reduced graphene oxide and CoPc composite(RGO/CoPc) to create abundant NH2 axial ligand groups,for anchoring the Co core within the CoPc.Owing to the PEI addition,the onset potential of the hydrogen peroxide oxidation reaction was shifted by 0.13 V in the negative direction(0.02 V) and the current density was improved by 1.92 times(1.297 mA cm^(-2)),compared to those for RGO/CoPc(0.15 V and 0.676 mA cm^(-2),respectively),due to the formation of donor-acceptor dyads and the prevention of CoPc from leaching out.The biocatalyst using glucose oxidase(GOx)([RGO/CoPc]/PEI/GOx) showed a better onset potential and catalytic activity(0.15 V and 318.7 μA cm^(-2)) than comparable structures,as well as significantly improved operational durability and long-term stability.This is also attributed to PEI,which created a favorable microenvironment for the enzyme.The maximum power densities(MPDs) and open-circuit voltages(OCVs) obtained for HPFCs and EBCs using the suggested catalyst were 105.2±1.3 μW cm^(-2)(0.317±0.003 V) and 25.4±0.9 μW cm^(-2)(0.283±0.007 V),respectively.This shows that the amine axial ligand effectively improves the performance of the actual driving HPFCs and EBCs.

A Glucose-Responsive Enzymatic Electrode on Carbon Nanodots for Glucose Biosensor and Glucose/Air Biofuel Cell

In this study, an enzymatic electrode for glucose biosensing and bioanode of glucose/air biofuel cell has been fabricated by immobilizing poly (methylene green) (polyMG) for electrocatalytic NADH oxidation and NAD+-dependent glucose dehydrogenase (GDH) for oxidizing glucose on carbon nanodots (CNDs). The polyMG-CNDscomposites obtained by electro-polymerization of dye MG molecules adsorbed on CNDs display excellent electrocatalytic activity toward NADH electro-oxidation at a low overpotential of ca. -0.10 V (vs. Ag/AgCl) and the integrated enzymatic electrode shows fast response to glucose electrooxidation. Using the fabricated GDH-based enzymatic electrode, a glucose biosensor was constructed and exhibits a wide linear dynamic range from 0 to 8 mM, a low detection limit of 0.02 μM (S/N = 3), and fast response time (ca. 4 s) under the optimized conditions. The developed glucose biosensor was used to detect glucose content in human blood with satisfactory results. The fabricated GDH-based enzymatic electrode was also employed as bioanode to assembly a glucose/air biofuel cell with the laccase-CNDs/GC as the biocathode. The maximum power density delivered by the assembled glucose/air biofuel cell reaches 3.1 μW·cm-2 at a cell voltage of 0.22 V in real sample fruit juice. The present study demonstrates that potential applications of GDH-based CNDs electrode in analytical and biomedical measurements.

Uniform ordered mesoporous ZnCo2O4 nanospheres for super-sensitive enzyme-free H2O2 biosensing and glucose biofuel cell applications

Uniform, ordered mesoporous ZnCo2O4 （meso-ZnCo2O4） nanospheres were successfully synthesized using a sacrificing template method. The meso-ZnCo2O4 nanospheres were used for the first time for H2O2 biosensing and in glucose biofuel cells （GBFCs） as an enzyme mimic. The meso-ZnCo2O4 nanospheres not only exhibited excellent catalytic performance in the H2O2 sensor, achieving a high sensitivity （658.92 μA.mM-1.cm-2） and low detection limit （0.3 nM at signal-to-noise ratio （S/N） = 3）, but also performed as an excellent cathode material in GBFCs, resulting in an open circuit voltage of 0.83 V, maximum power density of 0.32 mW.cm-2, and limiting current density of 1.32 mA.cm-2. The preeminent catalytic abilities to H2O2 and glucose may be associated with the large specific surface area of the mesoporous structure in addition to the intrinsic catalytic activity of ZnCo2O4. These significant findings provide a successful basis for developing methods for the supersensitive detection of H2O2 and enriching catalytic materials for biofuel cells.

Preparation of Close-Packed Silver Nanoparticles on Graphene to Improve the Enzyme Immobilization and Electron Transfer at Electrode in Glucose/O2 Biofuel Cell

In this study, chemical reduced graphene-silver nanoparticles hybrid （AgNPs@CR-GO） with close-packed AgNPs structure was used as a conductive matrix to adsorb enzyme and facilitate the electron transfer between im- mobilized enzyme and electrode. A facile route to prepare AgNPs@CR-GO was designed involving in β-cyclodextrin （β-CD） as reducing and stabilizing agent. The morphologies of AgNPs were regulated and controlled by various experimental factors. To fabricate the bioelectrode, AgNPs@CR-GO was modified on glassy carbon electrode followed by immobilization of glucose oxidase （GOx） or laccase. It was demonstrated by electrochemical testing that the electrode with close-packed AgNPs provided high GOx loading （Г=4.80 × 10^- l0 mol·cm^-2） and fast electron transfer rate （ks=5.76 s^-1）. By employing GOx based-electrode as anode and laccase based-electrode as cathode, the assembled enzymatic biofuel cell exhibited a maximum power density of 77.437 μW·cm^-2 and an open-circuit voltage of 0.705 V.

The direct use of enzymatic biofuel cells as functional bioelectronics

Enzymatic biofuel cells (EBFCs) are a subgroup of fuel cells that use enzymes as catalysts. EBFCs that utilizephysiological substrates such as glucose or lactate are of great interest as implantable or wearable power sourcesto activate medical devices. This contribution introduces the working principles of EBFCs and summarizes recentprogress in EBFC-enabled biosensors, pulse generators, and therapy. Biosensors with self-powered characteristicenjoy high selectivity, leading to potential “instrument-free” or “expensive-instrument-free” measurement.Autonomous pulse generation is based on the hybrid of EBFC and supercapacitor, which is promising for theapplication in medical related electrostimulation. By providing the direct electrical stimulation, or controllablyreleasing drug, EBFCs can also be used for self-powered therapeutic system. The further combination of self-powered sensing and treating enables EBFC as a possible platform of diagnostics and therapeutics. Future efforts can be focused on resolving the limited power density and lifetime of EBFC.

Live microalgal cells modified by L-cys/Au@carbon dots/bilirubin oxidase layers for enhanced oxygen reduction in a membrane-less biofuel cell

Electrochemical oxygen reduced reaction(ORR)is a critical element in clean energy development.Despite efforts to enhance gas transfer to the reaction interface,the low solubility of O_(2)molecules and slow diffusion rate in liquid electrolyte is still a significant challenge.Herein,we design an artificial outer membrane on microalgal cells,which consists of a carbon dots/bilirubin oxidase(CDs/BOD)ORR catalyst layer and a L-cystine/Au nanoporous O_(2)supply layer.O_(2)generated by photosynthesis from microalgal cells then can be directly transported to the CDs/BOD catalytic interfaces,overcoming the sluggish gas transfer in the electrolyte.Thus,the cathode constructed by the fabricated microalgal cells realizes an ORR current density of 655.2μA/cm^(2) with fast ORR kinetics,which is 2.68 times higher than that of a BOD cathode fed with pure O_(2).A membrane-less glucose/O_(2)biofuel cell is further developed using the hybrid artificial cells as the cathode,and the power density is 2.39 times higher than that of a BOD cathode biofuel cell in O_(2)saturated solution.This biomimetic design supplies O_(2)directly to the carbon dots/BOD catalyst layer from the microalgae membrane through a nanoporous L-cys/Au layer,providing an alternative solution for the transfer barrier of O_(2)in the electrolyte.

汗液发电:原理、器件结构及应用

可穿戴设备作为一种新兴科技产品,已在健康监测、人机交互和航天航空等领域展现出巨大的应用潜力。然而,大多数可穿戴设备的能源供给方式仍采用传统的纽扣电池或锂电池组供电,此类电池刚性大、体积臃肿、储能量有限、寿命短,严重限制了可穿戴设备的应用及推广。人体排汗的连续性以及汗液中包含了大量的电解质和代谢物,使得汗液成为可穿戴器件持续能源供给的潜在来源。汗液电池是一种利用人体汗液作为燃料进行供电的新型技术,具有轻薄柔软、反应条件温和、生物相容性高、可穿戴等优点。本综述旨在全面总结汗液电池的工作原理、材料特性、器件结构与最新进展,以期为柔性汗液电池的发展提供参考。

Anthraquinone Derivative Chiral Schiff Base Copper（Ⅱ） Complexes for Enzyme Type Bio-Fuel Cell Mediators

Electrochemically, laccase, a family of multi-copper oxidase, has specificity for performing not only one-electron oxidation of phenolic-related compounds but also four-electron reduction of oxygen, which is expected to be a cathode of biofuel ceils. We have prepared three amino-acid derivatives （for enhancing affinity to laccase） and one control （just for determining redox behavior of ligands and Cu（II/I）） copper（lI） complexes 0-3 having phenolic-related ligands involving anthraquinone moiety. Enhancing current density of electron transfer between the cathode （composed of electron conducting materials such as Nation and carbon nanotube） and laccase could be observed for all 1-3 acting as good mediators according to （spectro）electrochemical results.

Effect of the protection layer formed by cross-linked gelatin on the stability and performance of glucose and oxygen fuel cells

A glucose oxidation catalyst comprising carbon nanotube,tetrathiafulvalene(TTF),gelatin,glutaraldehyde(GA)and glucose oxidase(GOx)(CNT/[TTF-GOx]/Gelatin+GA)is suggested to enhance the reactivity of glucose oxidation reaction(GOR),and the performance and stability of enzymatic biofuel cells(EBCs)using this catalyst.In this catalyst,TTF is used as mediator to transfer electron effectively,while GA is crosslinked to gelatin to form non-soluble network.The structure prevents the dissolution of gelatin from aqueous electrolyte and reduces the leaching-out of GOx and TTF molecules.To confirm the crosslinking effect of GA and gelatin,Fourier-transform infrared spectroscopy(FT-IR)and electrochemical evaluations are utilized.According to FT-IR analysis,it was observed that the amide I peak shifted after crosslinking.This is evidence showing the appropriate network formation and the reactivity of CNT/[TTFGOx]/Gelatin+GA is well preserved even after multiple potential cycling.In addition,its GOx activity is regularly monitored for one month and the measurements prove that the structure prevents the leaching out of GOx molecules.Based on that,EBC using the anodic catalyst shows excellent performances,such as open circuit voltage of 0.75 V and maximum power density of 184μW/cm^(2).

Transgenic woody plants for biofuel

Transgenic trees as a new source for biofuel have brought a great interest in tree biotechnology. Genetically modifying forest trees for ethanol production have advantages in technical challenges, costs, environmental concerns, and financial problems over some of crops. Genetic engineering of forest trees can be used to reduce the level of lignin, to produce the fast-growing trees, to develop trees with higher cellulose, and to allow the trees to be grown more widely. Trees can establish themselves in the field with less care of farmers, compared to most of crops. Transgenic crops as a new source for biofuel have been recently reviewed in several reviews. Here, we overview transgenic woody plants as a new source for biofuel including genetically modified woody plants and environment; main focus of woody plants genetic modifications; solar to chemical energy transfer; cellulose biosynthesis; lignin biosynthesis; and cellulosic ethanol as biofuel.

Current-Voltage Modeling of the Enzymatic Glucose Fuel Cells

Enzymatic fuel cells produce electrical power by oxidation of renewable energy sources. An enzymatic glucose biofuel cell uses glucose as fuel and enzymes as biocatalyst, to convert biochemical energy into electrical energy. The applications which need low electrical voltages and low currents have much of the interest in developing enzymatic fuel cells. An analytical modelling of an enzymatic fuel cell should be used, while developing fuel cell, to estimate its various parameters, to attain the highest power value. In this paper an analytical model for enzymatic glucose membraneless fuel cell with direct electron transfer was developed. The adequacy of the model was estimated by comparison with fuel cells parameters. The electrical characteristics of fuel cells are interpreted using this model, based on theoretical consideration of ions transportation in solution. The influence of the hydrogen ions, glucose and enzyme concentration and also a thickness of enzyme layer on electrical parameters of a fuel cell were investigated. The electrical parameters such as a current, a voltage, a power were calculated by the model, for various parameters of the fuel cells. The model aimed to predict a hydrogen ions current, an electrical voltage and an electrical power in enzymatic fuel cell with direct electron transfer. The model reveals that increasing the rates of hydrogen ions generation and consumption leads to higher value of current, voltage and power.

Physical Modeling of the Enzymatic Glucose-Fuelled Fuel Cells

An enzymatic glucose biofuel cell uses glucose as fuel and enzymes as biocatalyst, to transform biochemical energy into electrical energy. An analytical modelling of an enzymatic biofuel cell should be used, while developing fuel cell, to estimate its various enzymatic parameters, to obtain the highest voltage feasibly. The analytical model was developed, and the open circuit voltage (OCV) calculated by the model for various parameters of the fuel cell is in agreement with the experimental results. The OCV is interpreted by using this model, based on theoretical consideration of ions transportation in the solution. The generation and consumptions of the ions near the electrodes were defined in the model by exponential approximations, with different depletion coefficients. The model reveals that increasing the rates of hydrogen ions generation and (or) consumption by enzyme or chemical reactions leads to a higher value of OCV. The model points that the OCV is saturated with a glucose concentration and increased logarithmically with a surface enzyme concentration. Hence, a low glucose concentration is sufficient to obtain adequate OCV, on the one hand, but it can be increased by increasing electrode surface porosity, on the other hand. This model can be expanded to include time and close circuit voltage.

基于石墨烯/金纳米粒子/碳化钛复合材料构建双室酶生物燃料电池自供能葡萄糖生物传感器

基于酶生物燃料电池(EBFCs)构建的自供能电化学传感装置具有结构简单、易于小型化及无需外部电源等优势,在生物传感、环境监测和临床诊断等领域具有潜在的应用前景.本文利用石墨烯/金纳米粒子/碳化钛(rGO/AuNPs/Ti_(3)C_(2))纳米复合材料修饰玻碳电极(rGO/AuNPs/Ti_(3)C_(2)/GCE)作为EBFCs阴极,在其表面进一步固定葡萄糖氧化酶(GOx),制得EBFCs生物阳极,进而通过组装EBFCs生物阳极和阴极构建了双室酶生物燃料电池自供能葡萄糖生物传感器(EBFCs-SPGB).当阳极室存在目标物葡萄糖时,生物阳极表面固定的GOx发生酶促反应,催化葡萄糖产生电子并经外电路到达阴极,导致阴极表面Fe(CN)_(6)^(3-)发生还原反应,从而产生电化学响应信号.rGO/AuNPs/Ti_(3)C_(2)纳米复合材料具有优异的导电性、生物相容性和大的比表面积,其协同效应可显著提高GOx负载量和有效促进电子在电极表面的传递.构建的EBFCs-SPGB最大功率输出信号与葡萄糖浓度在0.3~10 mmol/L范围内呈良好的线性关系,检出限为0.1 mmol/L(S/N=3),可用于人体血清样本中葡萄糖浓度的检测分析.

基于新型纳米多孔碳复合材料的生物燃料电池研究

本论文采用金属有机框架(MOFs)制备了新型纳米结构多壁碳纳米管(MWCNT)(MWNTs@MOFs-C碳复合材料)作为高性能生物燃料电池(BFC)的电极载体。分别用黄素腺嘌呤二核苷酸型葡萄糖脱氢酶(FAD-GDH)为生物阳极和漆酶为生物阴极,锇配合物作为电子介体组装了MWNTs@MOFs-C碳复合材料生物燃料电池。得到基于MWNTs@MOFs-C碳复合材料的葡萄糖/O_(2)生物燃料电池较高的最大功率密度0.51±0.03 mW·cm^(-2)和开路电压0.61 V。而生物燃料电池一周后能保持原功率密度的57%。我们的发现将为以MWNTs@MOFs-C碳复合材料作为电极载体开发更高效的BFC开辟一条途径。

漆酶在酶生物燃料电池中的应用进展

漆酶作为一种绿色、可再生和理想的能源资源,在生物燃料电池中具有广阔的应用前景和较大的商业价值。与传统的石化燃料电池相比,生物燃料电池是一类绿色环保电池。生物燃料电池包括微生物燃料电池(MFC)、酶生物燃料电池(EBFC)和混合生物燃料电池(HFC),其中EBFC备受研究者关注。鉴于漆酶具有高氧化还原电位及环境友好性,它已成为EBFC的首选阴极生物催化剂。简要综述了MFC、EBFC和HFC的基本特性,全面总结了漆酶生物燃料电池(LFC)在电化学领域的研究进展及应用价值,旨在为开发稳定、高性能的新型LFC奠定理论基础。

酶燃料电池的研究进展

酶燃料电池原料来源广泛、生物相容性好、在常温常压和中性溶液环境中工作、可以用多种天然有机物作为燃料,是一种可再生的绿色能源,可作为微型电子装置来提供电能。通过介绍酶燃料电池发展及其应用,对当前酶燃料电池发展所遇到的瓶颈及挑战进行系统分析、总结。目前,针对所得酶燃料电池的能量密度较小,且输出功率较低,未能满足商业化的要求等限制因素,仍然需要进行大量研究,本文综述了酶燃料电池发展中存在的瓶颈,为今后为酶燃料电池的研究提供一点帮助。

酶生物燃料电池

综述了酶生物燃料电池的研究进展,特别是近年来在电池结构、性能以及电池的正极和负极研究等方面的成果。详细介绍了酶燃料电池中酶电极的制备方法和用于酶电极修饰材料的研究现状,对酶燃料电池研究中需要解决的问题和发展方向进行了探讨。

生物燃料电池研究进展

生物燃料电池利用生物催化剂直接把化学能转化为电能,具有燃料来源广泛、反应条件温和、生物相容性好等优点。按采用催化剂的不同,可分为微生物燃料电池和酶生物燃料电池。简述了生物燃料电池的工作原理,综述了其最新的研究进展。微生物燃料电池发展的新方向主要是无介体微生物燃料电池的研究和高活性微生物的选用;而酶生物燃料电池的研究,集中在寻找固定酶的新方法,发展体积更小的无介体酶生物燃料电池,以及与太阳电池相结合等方面。对生物燃料电池未来的发展方向进行了展望。

生物燃料电池

简介了生物燃料电池的概念和工作原理 ,回顾了生物燃料电池的发展历史。对 80年代后两种生物燃料电池———微生物燃料电池和酶燃料电池的研究动态分别进行了总结 ,并对目前存在的主要问题进行了分析。阐述了当前研究的发展方向 ,预计随着燃料电池研究热潮的再度兴起和生物技术的高速发展 。