bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) High Catalytic Activity for Ethanol Bioelectrooxidation at Hybrid Electrocatalysts
Authors: De Andrade Adalgisa Rodrigues , Honorio Franco Jefferson , Minteer Shelley D. 
Published: May 2020

The use of enzymes immobilized onto the surface of electrodes as the main catalyst in biological fuel cells has been extensively reported. A biofuel cell provides a means to obtain clean, renewable energy and have great potential to be used as alternative energy source for low power devices. There still a lot of important issues in the development of these device, one of them, is to obtain the maximum power density from the fuel for this is important to immobilize a group of enzymes to perform a cascade in order to maximize the fuel oxidation.
Recently, we have concentrated our goal to the develop hybrid nanomaterials with MWCNT in order to immobilize efficiently the enzymes and organic catalyst. We will report a number of approaches to combine enzymes with a recently developed TEMPO-modified linear poly(ethylenimine) (TEMPO-LPEI) coupled with carboxylate multi-walled carbon nanotubes (MWCNT-COOH) to transform ethanol, ethylene glycol into CO2. In the case of ethanol extraction of 12 electrons per molecule at a single hybrid anode has been obtained with success. This simple methodology can replace the use of enzymatic cascade (7-8 enzymes) and may improve the application in biofuel cells.
The electrochemical response of the enzyme system (MWCNT-COOH/LPEI/OxOx) at increasing concentrations of ethanol confirms the excellent activity of these hybrid bioanodes.
To confirm complete ethanol oxidation to CO2, electrolysis of ethanol was performed for using different electrode systems hybrid systems. Product analysis allowed us to correlate the increase in current with the formation of CO2 as main product. The modification of nanomaterials to obtain a large energy output form an enzymatic system will be highlighted.

Acknowledge: FAPESP (grants # 2017/20431-7 and 2014/50945-4 ), CNPq (grant (465571/2014-0) and CAPES 001. Army Research Office MURI (W911NF-14-1-0263).
(Invited) Cobalt-Based Multicomponent Electrocatalyst Generated By Melamine Thermal Polycondensation
Authors: Alonso-Vante Nicolas , Zhong Haihong 
Published: May 2020

The pivotal process and the bottleneck for electrochemical energy converting devices lies in the oxygen reduction reaction (ORR). The kinetics of this complex multi-electron charge transfer process is by two or more orders of the magnitude lower than the hydrogen reaction on Platinum. Intensive efforts have been devoted to develop earth-abundant metal elements-based materials, such as, Fe, Co, and Ni as possible alternates to Pt [1, 2]. Herein, our strategy was to develop a series of the cobalt-based electrocatalysts for ORR synthesized following various heat treatment of the chemical precursor supported on carbon Vulcan and melamine mixture. We observed that the cobalt-based active sites, nitrogen species and carbon carbonization/graphitization degree were different in the samples obtained from different annealing temperatures, which greatly influenced the electrocatalytic performances of these cobalt-based materials.
The ORR electro-catalytic performance (activity, stability and durability) were evaluated in alkaline medium. The sample annealed at 550 ˚C, showed a remarkable ORR activity, high stability, and long-term durability comparable with that of commercial 20wt% Pt/C catalyst, in alkaline medium.

Reference:

[1] H. H. Zhong, Y. Luo, S. He, P. Tang, D. Li, N. Alonso-Vante, Y. Feng, ACS Appl. Mater. Interfaces, 9, 2541 (2017).
[2] H. H. Zhong, R. Tian, X. Gong, D. Li, P. Tang, N. Alonso-Vante, Y. Feng, J. Power Sources, 361, 21 (2017).
(Invited) Photo-Induced Signal Chains at Enzyme Electrodes
Authors: Riedel Marc , Lisdat Fred 
Published: May 2020

During the last decade photoelectrochemical devices which couple biochemical reactions to light-sensitive electrodes have gained increasing research interest. These kind of light-triggered systems have the inherent advantage that an additional tool - the light - can be used to control the reactions at a sensing electrode. This allows a light-directed read-out, but can also be used to change the energetic situation on the surface resulting in advantageous potential behavior [1].
Enzymes as biocatalysts provide the advantage of a catalytic analyte conversion and specificity in this reaction. In order to couple them to light-sensitive electrodes different approaches have used.
Besides the use of co-substrates or products [2], we have been focusing on the use of mediators for this interaction [3] or the establishment of a direct electron transfer of the enzyme to the light- sensitive entity [4]. Here we report on the use of two different types of polymers for establishing the electrical contact.
In order to exploit the advantages of a high surface area we have constructed 3D electrodes which can be rather easily prepared by a template approach combined with spin coating as deposition method..Thus, the thickness of the electrode structure can be adjusted in a defined way [5,6].
In a first approach 3D TiO2 of inverse opal character has been sensitized by a conducting polymer – sulfonated polyaniline. The polymer has here two functions: It ensures the light sensitivity in the visible range and also provides an interface at which the enzyme can exchange electrons. Advantageously the current signal can be gained at rather low potential. Furthermore, the response can be tuned by the dimensions of the 3D electrode demonstrating the scalability of the approach.
As a further advancement we have used a redox polymer in order to couple FAD-dependent glucose dehydrogenase to the electrode. Here PbS QDs have been generated directly onto a 3D TiO2 electrode and characterized by TEM and photoelectrochemistry. The system allows the generation of a defined anodic photocurrent, which can be significantly enhanced by the biocatalytic conversion of glucose. Here the substrate dependent current signal starts at about -054V vs Ag/AgCl.
Such electrode systems can find application in light-triggered sensing, but also for bioenergetics since the photocatalytic process can be “feeded” by electrons from the biocatalytic conversion.
References
[1] F. Lisdat, D. Schäfer, A. Kapp, Anal. Bioanal. Chem. 405, 3739 (2013).
[2] J. Tanne, D. Schäfer, W. Khalid, W. J. Parak, F. Lisdat, Analytical Chemistry 83 (20) (2011) 7778–7785
[3] M. Riedel, N. Sabir, F. W. Scheller, W. J. Parak, F. Lisdat, Nanoscale 9, 2814 (2017).
[4] Ch. Stoll, S. Kudera, W.J. Parak, F. Lisdat,”,SMALL 2 (6) (2006) 741-743).
[5] M. Riedel, F. Lisdat, ACS Applied Materials & Interfaces, (2018), Vol. 10 (1), p. 267-277
[6] M. Riedel, W. Parak, A. Ruff, W. Schuhmann, F. Lisdat, ACS Catalysis, (2018), Vol. 8, 5212-5220
(Invited) New Ionic Liquids (ILs) for Secondary Batteries: Interplay between Structure, Electrical Response and Conductivity Mechanism
Authors: Vezzù Keti , Pagot Gioele , Negro Enrico , Di Noto Vito 
Published: May 2020

The main bottleneck towards the development of high-performing “beyond Lithium ion” batteries in the portable electronic, electric automotive, and stationary applications [1] is the lack of electrolytes that are safe, electrochemically stable, and compatible with the electrode materials [2-3].
Recently published papers demonstrated that halo-aluminate ionic liquids (ILs) can provide an appealing alternative to conventional ethereal solvent-based electrolytes due to their low volatility, negligible flammability, and excellent electrochemical performance [4-7].
Following this, an overview on recent advancements on electrolytes for secondary batteries is presented, with a particular reference to imidazolium- and pyrrolidinium-based ILs. Insights on the interplay between thermal properties, structure and conductivity of BF4
-, Cl-/AlCl3, Cl-/TiCl4, and I-/AlI3-based systems are given, thus providing an in-depth understanding of the relation existing between ion speciation, long-range charge transfer mechanism, conductivity mechanisms and electrochemical performance of this very promising class of materials.

References

[1] B. Dunn, H. Kamath, J. M. Tarascon, Science 334 (2011) 928-935.
[2] V. Di Noto, T. A. Zawodzinski, A. M. Herring, G. A. Giffin, E. Negro, S. Lavina, Int. J. Hydrogen Energy 37 (2012) 6120-6131.
[3] B. Scrosati, J. Garche, J. Power Sources 195 (2010) 2419-2430.
[4] F. Bertasi, C. Hettige, F. Sepehr, X. Bogle, G. Pagot, K. Vezzù, E. Negro, S.J. Paddison, S.G. Greenbaum, M. Vittadello, V. Di Noto. ChemSusChem. 8 (2015) 3069-3076.
[5] F. Bertasi, F. Sepehr, G. Pagot, S.J. Paddison, V. Di Noto. Adv. Funct. Mater. 2016, 26, 4860-4865.
[6] F. Bertasi, K. Vezzù, G. Nawn, G. Pagot, V. Di Noto. Electrochim. Acta. 2016, 219, 152-162.
[7] G. Pagot, F. Bertasi, K. Vezzù, F. Sepehr, X. Luo, G. Nawn, E. Negro, S.J. Paddison, V. Di Noto. Electrochim. Acta. 2017, 246, 916-923.
(Invited) Corrosion of PGM-Free Electrocatalysts for Oxygen Reduction in Fuel Cells: A Combined Experimental and Theoretical Study
Authors: Zhang Hanguang , Holby Edward F. , Martinez Ulises , Zelenay Piotr 
Published: May 2020

Achieving practical stability and durability of PGM-free catalysts, e.g., M-N-C catalysts (where M, N, and C represent a transition metal, nitrogen, and carbon, respectively), remain a great challenge for the practical application of these catalysts in polymer electrolyte fuel cell (PEFC) cathodes. A variety of degradation paths have been proposed for M-N-C catalysts, including irreversible dissolution of the M from the active site and corrosion of the C matrix.1 Both mechanisms are active areas of research but it remains difficult to de-convolute contributions from each and how these mechanisms couple to environmental conditions (temperature, pH, fuel cell humidification, reactant flow rates, etc.). It is possible that metal dissolution occurs which destabilizes the local C which is then more easily corroded. It is also possible that C corrosion occurs which destabilizes the local M binding environment leading to dissolution of M. It is further possible that free radicals generated from 2-electron ORR pathways (either on M sites or defected-C sites) subsequently attack the C support, the M, or both. Also, the mechanisms may not be directly linked. Thus, without further understanding of each mechanism, it is difficult to prescribe methods of material stabilization or even accelerated stress tests for exacerbating a given activity loss mechanism.
In this talk, combined experimental and theoretical C corrosion studies of M-N-C catalysts will be presented. This work includes operando quantification of CO2 emission by nondispersive infrared detection and inductively coupled plasma measurement of metal dissolution as a function of fuel cell conditions. Specifically, the C corrosion of M-N-C catalysts will be evaluated at different relative humidity, cell temperature and reactant stoichiometry. M-N-C catalysts with various C structure will also be compared for exploring the possible mechanism of C corrosion in PGM-free catalysts. DFT calculations of C corrosion and oxidation as a function of atomic scale structure will also be discussed for comparison with metal dissolution stability studies. Overall, we aim to decouple de-metalation and C corrosion mechanisms for activity loss in PGM-free ORR electrocatalysts in order to better mitigate such losses, thus strengthening their case as PGM replacements in fuel cell applications.
References
1. Martinez, U., Komini Babu, S., Holby, E. F. & Zelenay, P. Durability challenges and perspective in the development of PGM-free electrocatalysts for the oxygen reduction reaction. Current Opinion in Electrochemistry
9, 224-232, 2018.
Spherical MoS2/Carbon Composite with Improved Electrochemical Performance for Sodium-Ion Battery Anode
Authors: Lim Hyojun , Kim Hyeongwoo , Kim Sang-Ok , Choi Wonchang 
Published: May 2020

Lithium-ion batteries (LIBs) with high energy density and long cycle life have been widely applied as the power sources in a variety of fields from portable electronic devices to large-scale energy storage systems (ESSs). Particularly in recent years, owing to the rapid growth of global electric vehicle and ESS markets, the cost of lithium source has risen sharply and many researchers predict a lithium shortage in the near future. In this regard, sodium-ion batteries (SIBs) have recently attracted growing attention because of low price and huge natural abundance of sodium, compared to lithium. However, the larger ionic radius of sodium ion (1.02 Å) than that of lithium (0.76 Å) results in poor electrochemical behaviors, which makes it difficult to find suitable anode materials for SIBs. [1] Among many proposed anode materials for SIBs, molybdenum disulfide (MoS2) is one of promising sodium-ion host materials because of its 2D-layered structure and high theoretical capacity of 670 mA h g-1. Despite these advantages, when used as an anode for SIBs, MoS2 exhibits several problems associated with low cycling stability and poor rate performance caused by large volume change during sodium insertion and extraction and low electrical conductivity. [2] In order to solve the aforementioned drawbacks of MoS2, herein, we present a spherical-shaped MoS2/carbon (MoS2/C) composite as a high-performance anode for SIBs. The spherical MoS2/C composites were synthesized by a facile and simple in situ wet chemical method using furfural as a surfactant as well as a carbon source. The as-prepared MoS2/C composite showed uniform distribution of MoS2 particles in the mesoporous carbonaceous matrix, which not only effectively alleviates large volume variation during repeated cycling, but also ensures high electrical conductivity. Owing to these benefits of good dispersion of active materials and the introduction of multifunctional matrix, the spherical MoS2/C composite electrodes demonstrated improved electrochemical performance such as enhanced cycle stability and superior rate capability. Furthermore, we believe that our facile and effective approach to synthesize MoS2/C composites can be extended to design and develop various transition metal-chalcogenides as promising and desirable anode candidates for SIBs.
REFERENCE
[1] Y. Xiao, S. H. Lee, Y. K. Sun, Adv. Energy Mater. 2017, 7, 1601329
[2] Q. Pan, Q. Zhang, F. Zheng, Y. Liu, Y. Li, X. Ou, X. Xiong, C. Yang, M. Liu, ACS Nano 2018, 12, 12578.

Figure 1
Molecularly Imprinted Voltammetric Sensor Based on Chitosan-CNTs Decorated with AuNPs Nanocomposite for Catechol Detection
Authors: Salvo-Comino Coral , Rassas Ilhem , Minot Sylvain , Bessueille Fancois , Arab Madjib , Rodriguez-Mendez Maria Luz , Errachid Abdelhamid , Jaffrezic-Renault Nicole 
Published: May 2020

This research is based on the development of a novel, biocompatible and sensitive electrochemical imprinted sensor based on the detection of a phenolic compound, such as catechol, employing electroactive nanomaterials with the objective of improving the electron transfer between the electrode surface and the solution [1] and a natural biopolymer due to its excellent layer forming ability [2]. The development of the sensor is based on the modification of multiwalled carbon nanotubes (MWCNTs) with gold nanoparticles (AuNPs). The decorated MWCNTs have been recovered with a polymeric chitosan (CS) matrix generating a nanocomposite that contains the electroactive material inside. The polymeric matrix of CS that holds the modified MWCNTs has been electrodeposited in the presence of the phenolic compound on a boron doped diamond (BDD) electrode. The sensor surface has been structurally characterized to demonstrate the correct adsorption of the film and the correct recovery of the decorated carbon nanotubes on the BDD electrode surface. The performance as an electrochemical MIP sensor analyzed by cyclic voltammetry has offered excellent characteristics, demonstrating a high affinity to catechol with high selectivity, reproducibility, repeatability and sensitivity in the range of catechol concentrations from 0 to 1 mM. Finally, the implementation of the sensor to measure in a complex red wine sample has been carried out. The obtained results have resulted to be successful to quantify catechol in the real matrix. For these reasons, the proposed research manifests a promising and interesting way to implement an imprinting biocompatible polymers method in the development of an electrochemical sensor for phenols detection in the 4.0 industry.
[1] S. A. Zaidi, Sensors Actuators B. Chem., 2018, 265,488-497.
[2] A. Gopalan, S. Komathi, N. Muthuchamy, K. Lee, M. J. Whitcombe, L. Dhana, y G. Sai-anand, Prog. Polym. Sci., 2019 88, 1-129.

Acknowledgments: Financial support by MINECO and FEDER (RTI2018-097990-B-100 and BES-2016-077825) and the Junta de Castilla y León-FEDER (VA-275P18) is gratefully acknowledged.
Waste-Biomass-Derived Carbon As Renewable Electrode Materials for Plant Microbial Fuel Cells
Authors: Lin Fang-Yi , Liu Tzu-Yin , Chen Han-Yi 
Published: May 2020

Developing clean and sustainable energy sources is important as it deals directly with energy shortage and environmental pollution problems caused by fossil fuels. Plant microbial fuel cells (PMFCs) is a novel technology that can convert solar energy into electrical energy by the microbes at the region of rhizosphere of the plants. Without producing any harmful byproducts during the energy generation process, PMFCs seems to be a promising choice as a renewable power supply technique. Green carbon materials, utilizing agro-industrial waste as precursors, has attracted lots of interest in research recently on account of them being environmental friendly materials and mitigating bio-wastes.
To combine the advantages of PMFCs and green carbon materials, the aim of this study is to optimize the electrochemical performance of our designed PMFCs by utilizing biowaste-derived activated carbon materials as the electrode materials. The biowaste-derived activated carbon materials were characterized by Brunauer-Emmett-Teller (BET) surface area analyzer, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The electrochemical performance of PMFCs devices developed by ourselves were analyzed through linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). This study set out to examine the relationship between the properties of activated carbon and the electrochemical performance of PMFCs, expecting to develop a high power density PMFCs device.
Electrochemical Oxidation of Organic Fuels at Rotating and Flow through Electrodes
Authors: Sayadi Azam , Pickup Peter G 
Published: May 2020

Oxidation of small organic molecules (SOM) has been one of the most active targets of investigation in electrochemistry for several decades. One of the main reasons is that SOM such as formic acid, methanol, and ethanol, can be used to produce electrical power through their oxidation in fuel cells [1]. These devices have the potential to produce close to 100% energy efficiency in theory. However, practically this level of efficiency has not been achieved for SOM so far due to deficiencies such as slow and incomplete oxidation of the fuel. For enhancement of the energy efficiency, a comprehensive study of the electrocatalytic oxidation mechanisms and average number of exchanged electrons of SOM as fuels are fundamental. One of the widespread approaches for these studies is applying hydrodynamic methods due to their ability to emulate the hydrodynamic conditions of a fuel cell anode.
We have applied rotating disc voltammetry (RDV) and flow cells to study the electrocatalytic oxidation of ethanol, methanol and formic acid. Using RDV the measured current can be separated into its kinetic and mass transport components and this provides reproducible and controllable conditions for kinetic and mechanistic studies [2]. The number of electrons transferred for ethanol oxidation at room temperature was found to be ca. 3.5 [3], which agrees with literature reports of product distributions. Also, we showed that accurate kinetic currents could be obtained for formic acid oxidation using RDV [4]. One hundred percent faradaic efficiency and a diffusion coefficient in good agreement with literature values were obtained for methanol oxidation at a PtRu black catalyst using RDV [5]. Our next approach was to design a flow-through electrolysis cell in order to evaluate the reliability of findings from RDV by product analysis. The organic fuel solution passes through the working and counter electrodes in line, and the cell exhaust is collected for spectroscopic analysis by H-NMR. Also, a CO2 detector was used for real-time measurements. Despite its simple design, this flow cell can provide valuable information regarding the kinetics and stoichiometry of catalytic electrooxidation of organic fuels.
[1] G. L. Soloveichik, Beilstein, J. Nanotechnol,
5, 1399–1418 (2014).
[2] A.J. Bard, L.R. Faulkner, Electrochemical methods. Fundamentals and applications, 2nd ed. 2001, Weily, New York, (2001).
[3] A. Sayadi and P. G. Pickup, Electrochimica Acta, 215, 84-92 (2016).
[4] A. Sayadi and P. G. Pickup, Electrochimica Acta,
199, 12-17 (2016).
[5] A. Sayadi, and P. G. Pickup, Special V. G. Levich Issue of Russ. J. Electrochemistry, 53, 1183–1192 (2017).
In Situ Observations of Molecular CO2 Interaction on SnS2 Thin Film for Gas-Phase Photocatalytic CO2 Reduction Activity
Authors: Reta Tadesse Billo , Shown Indrajit , Lee Chih-Hao , Chen Kuei-Hsien , Chen Li-Chyong 
Published: May 2020

Among the several approaches, the gas phase photocatalytic conversion of CO2 to useful fuels with the help of renewable energy sources and water vapor has attracted widespread attention. In this system, the gas-solid interaction between a CO2 molecule and a solid catalyst surface is a crucial step. However, the adsorbate-catalyst surface interaction in the gas-phase of CO2 reduction system on the surface of semiconductor photocatalysts remains unaddressed.
In this report, high-quality SnS2 thin film was prepared through a chemical vapor transport process followed by controlled carbon implantation to form C-SnS2. Our material design and characterization approaches, which involve in-situ observations enabled us to correlate the adsorbate-catalyst surface interactions and their implications on photocatalytic CO2 reduction. Using in-situ dark current and in-situ Raman spectroscopy, under different gas ambient conditions, we have observed that, the C-SnS2 surface exhibited a strong affinity towards CO2 molecule and higher photon to electron conversion efficiency under light illumination. In addition, the optimized carbon implanted SnS2 sample has demonstrated more than 108 times enhancement in the CO2 conversion efficiency and about 89% product selectivity towards CH4 formation. Additional information on the mechanism of interfacial charge transfer was obtained using angle-dependent XANES, X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) analysis.
We anticipate that the adsorbate-catalyst surface interaction studies applied in this report can be extended to be used as a benchmark in design and material selection in the gas-phase CO2 photoreduction applications. We further expect that C-SnS2 with its promising photocatalytic performance and high affinity toward CO2 adsorption and activation; will inspire the development of new semiconductor photocatalysts by modifying it with metal or non-metal dopants towards CO2 conversion into useful products. The detail characterization and experimental results with the future perspective of this study will be presented.