bluuebunny/crossref_metadata_2025 huggingface dataset:
Aging Cell Detection Method of ESS Base on Operating Data
Authors: Lee SungEun , Choi Jin Hyeok , Park Jay
Published: December 2020

Lithium based ESS is consist of many battery cells series. Ideally, when many cells degrade at the same rate of life, safety can be maintained when operating the facility. In reality, it shows a difference in internal resistance and capacity for each cell, and it is difficult to estimate the deterioration state for each cell. So it includes a passive cell balancing function based on the BMS voltage to manage the battery, but it is not a fundamental solution. Differences in cell deterioration fundamentally degrade ESS performance and, if used excessively, may lead to fire due to a runaway temperature of the lithium battery.In this paper, proposed a method that can detect a cell with a relatively high deterioration rate among a number of cells and diagnose it step by step based on limited ESS operation data. it is possible to accumulate location information based on a maximum minimum voltage value stored every second by classifying when charging, discharging, and stopping, and extracting a statistically based deterioration cell when a lot of data is accumulated. It is intended to define the IR Ratio and monitor the risk in advance and improve the safety of the ESS when current flows and through preemptive degradation cell detection.
An Improved High-Rate Discharging Performance of “Unbalanced” LiFePO4 Cathodes with Different LiFePO4 Loadingsby a Grid-Patterned Micrometer Size-Holed Electrode Structuring
Authors: Matsumoto Futoshi , Watanabe Tatsuya , Gunji Takao , Ohsaka Takeo , Nakamura Susumu , Soma Naohiko , Ando Nobuo , Hayashi Narumi
Published: December 2020

The degradation of charging/discharging capacities in the rate-performance test of lithium iron phosphate (LFP) cathodes with different loading amounts of an active material on both sides of a current collector (i.e., “unbalanced” LFP/LFP cathodes) in a laminated cell (typically composed of anode/separator/unbalanced cathodes/separator/anode) was not observed actually at low C-rates (e.g., 0.1 C). However, the rate-performance data obtained at high C-rates (e.g., > 5 C) indicated that the imbalance of the loading amounts of an active cathode material on both sides of an Al current collector causes a significant capacity degradation. We have found that it is possible to prevent the capacity degradation observed at high C-rates by holing the unbalanced LFP/LFP cathodes in a micrometer-sized grid-patterned way (the percentages of the holed area are typically several %) using a pico-second pulsed laser: The non-holed unbalanced LFP/LFP cathodes exhibited a considerable capacity degradation at C-rates which are, for example, larger than 5C, while the holed ones showed no degradation in capacity even at high C-rates (e.g., 5-20 C). Forming micrometer-sized grid-patterned holes in the LFP/LFP cathodes leads to an improved capacity and high-rate performance of their charging/discharging processes. The improvement in the discharging performance at the holed cathodes at high C-rates can be considered to result from a facilitated transfer of Li+ ions in the discharging of the thick layer as well as the thin one through both the surface and the sidewalls (produced by forming the holes) of the LFP layer (or the LFP/current collector layers). In order to keep a high discharge capacity at high C-rates even in thick LFP layers, resulting in an improvement of the battery performance of LIBs, the optimization of the diameter of holes formed and the percentage of holed areas (i.e., opening rate) is examined now.

Fig. 1 Schematic description of high-rate discharging processes on (A) non-holed, (B) through-holed and (C) non-through-holed LFP/LFP cathodes with loading ratios of 3 at low- and high-rate discharging (e.g., at 0.1 and 10 C).

Figure 1
Mo Thio and Oxo-Thio Molecular Complexes As Water-Soluble Self-Healing Catalysts for Photocatalytic Hydrogen Evolution on 2D Materials
Authors: Taberna Pierre-Louis , Barbosa Juliana Barros , Chane Ching Jean-Yves , Balocchi Andrea , Marie Xavier , Gerber Iann
Published: December 2020

2D semiconducting nanosheets of Transition Metal Dichalcogenides are attractive materials for solar energy conversion because of their unique absorption properties. Recently, Hydrogen evolution reaction (HER) was achieved with thin 2D WSe2 nanosheets activated by well-known precious metal catalysts. Here, we propose noble-metal-free, Mo thio- and oxo-thio-complexes anchored on 2D p-WSe2 nanosheets for efficient water splitting under visible light irradiation with photocurrent density up to 2.0 mA cm-2 at -0.2 V/NHE. These Mo thio and oxo-thio- molecular complexes films represent an ideal class of catalysts, well-suited to functionalize 2D materials since they are stable in aqueous environments, cheap, environmentally benign to synthesize and process. Besides developing high electro-catalytic activity, the Mo complexe films were shown to display ability to heal surface defects. We propose that the observed healing of surface defects arises from the strong adsorption on point defects of the 2D WSe2 substrate of Mo-complexes such as (MoS4)2-, (MoOS3)2-, (Mo2S6O2)2- as shown from DFT calculations. In addition to display catalytic and healing effects, the thio-, oxo-thio Mo complexes films which spontaneously formed at well-defined pH were shown to enhance charge carrier separation and migration for the Hydrogen Evolution Reaction, thus representing an example of multicomponent passivation layer exhibiting multiple properties.
Bismuth Vanadate Encapsulated with Reduced Graphene Oxide for Hydrogen Peroxide Generation
Authors: Dhabarde Nikhil , Tian Siyu , Xiong Guoping , Misra Mano , Subramanian Vaidyanathan
Published: December 2020

Hydrogen peroxide (H2O2), a strong oxidant, is considered as a highly value-added chemical due to its diverse applications. The conventional multi-step process for H2O2 production in the industrial setting is energy intensive, using reactants of explosive nature and expensive catalysts. A photocatalytic H2O2 production, in contrast, is a sustainable and eco-friendly process, requiring mostly water, dioxygen (O2), and sunlight. The role of the photocatalyst is to provide the electron for the reduction of O2 and holes for the release of hydrogen ion in water. The main challenge with this approach is the lack of an efficient photocatalyst, which can absorb light and transfer the energy to redox reaction. Bismuth vanadate (BiVO4), a semiconductor with a low band gap energy (~2.4 eV), is known to be a promising photocatalyst. Moreover, reduced graphene oxide (RGO) is well-known for its role in promoting the separation and transport of charges, preventing the recombination of photogenerated electron−hole pairs. This study proposes a method of synthesizing a composite catalyst by functionalizing BiVO4, via the encapsulation with RGO. The catalyst synthesis is optimized by varying the amount of graphene oxide (GO) loading on BiVO4. This paper will summarize the structural, morphological, and photoelectrochemical characterization of these BiVO4-RGO catalysts. Preliminary results have indicated that the H2O2 production is enhanced by 3-fold with the presence of RGO and BiVO4 than BiVO4 alone. The role of carbon doping in improving the light trapping and charge separation, resulting in the enhancement of photocatalytic H2O2 yield, will be examined.
(Invited) Solar-Driven CO2 Reduction By Molecular-Semiconductor Hybrid Systems: Photoelectrodes and Particulate Photocatalysts
Authors: Morikawa Takeshi , Sato Shunsuke , Sekizawa Keita , Arai Takeo , Suzuki Tomiko M.
Published: December 2020

For the development of photosystem for CO2 reduction into useful energy-rich chemicals using water as an electron donor operating under sunlight irradiation, the combination of a semiconductor photosensitizer and a metal-complex catalyst is one promising approach. We previously proposed the a hybrid molecular-catalyst/semiconductor system for the visible-light driven CO2 reduction, and demonstrated particulate photocatalyst and photoelectrode systems utilizing Ru-bipyridine complexes and their polymers as catalysts contacted with semiconductors of N-doped Ta2O5[1], GaP:Zn [2], InP:Zn[2], (CuGa)0.8Zn0.4S2[3], (AgIn)0.22Zn1.56S2[3], ZnS:Ni[3], etc. (Fig. 1). As an example, the photoelectrode system demonstrated formate generation with a solar-to-chemical conversion efficiency of 4.6 % by a non-biased tablet-formed device immersed in an aqueous solution [4].

One recent topic is a visible-light-driven Z-schematic CO2 reduction using H2O as an electron donor in aqueous particulate suspension system which can be operated in a simple mixture of [Ru(4,4’-diphosphonate-2,2’-bipyridine)(CO)2Cl2] ([Ru(dpbpy)] modified (CuGa)1-xZn2xS2 (CGZS) hybrid photocatalyst as a CO2 reduction, BiVO4 photocatalyst as a water oxidation and Co-complex as an electron mediator [5]. The CO2 reduction activity was significantly dependent on the composition of CGZS, and utilization of [Ru(dpbpy)]/CGZS at x=0.7 (E
g = 2.36 eV) showed the highest Z-schematic CO2 reduction activity for CO and HCOO- production accompanying O2 generation under visible-light irradiation. The very high CO2 reduction selectivity beyond 60% under visible light irradiation as the aqueous particulate suspension suggests that particulate Z-schematic system is feasible to construct selective and efficient photocatalytic system for CO2 fixation and solar fuel generation. An electrode system using earth-abundant elements such as Mn[6], Fe[7] and Si will also be presented.[8]

- References

[1] S. Sato, T. Morikawa, et al, Angew. Chem. Int. Ed.
2010,
49, 5101-5105.

[2] S. Sato, T. Arai, T. Morikawa, et al., J. Am. Chem. Soc.,
2011,
133, 15240-15243.

[3] T. M. Suzuki, A. Kudo, T. Morikawa, Applied Catalysis B: Environ.
2018
, 224, 572–578.

[4] T. Arai, S. Sato, T. Morikawa, Energy Environ. Sci.,
201
5
,
8
, 1998-2002.

[5] T. M. Suzuki, A. Kudo, T. Morikawa, et al., Chem. Commun., 2018, 54, 10199-10202

[6] S. Sato, K.Sekizawa, et al, ACS Catal., 2018, 8, 4452-4458.

[7] T. M. Suzuki, et al., Bull. Chem. Soc. Jpn, 2018, 91, 778–786.

[8] T. Arai, et al., Chem. Commun., 2019, 55,237-240.

_

Figure 1
Use of in Situ Synchrotron Techniques to Probe the Oxidized Surface of Molybdenum Nitride Oxygen Reduction Electrocatalysis
Authors: Kreider Melissa E , Stevens Michaela Burke , Gibbons Brenna M. , Gallo Alessandro , Ievlev Anton , Mehta Apurva , Davis Ryan , King Laurie A. , Jaramillo Thomas F
Published: December 2020

The development of active and stable earth-abundant catalysts for the oxygen reduction reaction (ORR) is needed for widespread, economic development of fuel cell technologies. Designing and optimizing these non-platinum group metals is challenging, however, because they are susceptible to composition and structure changes, including dissolution, oxidation, and corrosion, both in air and under reaction conditions. To identify the active surface, and thus understand the properties that affect activity, the catalyst surface must be characterized in situ. Herein, we utilize a grazing incidence electrochemical cell to investigate in situ composition and morphology changes of a molybdenum nitride (Mo-N) thin film catalyst using grazing incidence x-ray absorption spectroscopy (GI-XAS) and x-ray reflectivity (XRR). In rotating ring disk electrode measurements, we find that the activity, selectivity, stability, and capacitance of the Mo-N catalyst is dependent on the maximum potential to which it has been exposed. Specifically, the overpotential required to reach -2 mA cm-2
geo decreases by over 90 mV when the maximum potential is increased from 0.3 to 0.8 V vs RHE (Figure 1). Because the Mo-N oxidizes rapidly in air, ex situ characterization methods including x-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry can provide only limited insight into these in situ catalyst changes. Using in situ GI-XAS measurements at applied potentials between 0.3 and 0.9 V vs RHE, however, we are able to determine that the surface of the film oxidizes and becomes more amorphous when exposed to increasingly higher potentials (Figure 1). Furthermore, the surface remains oxidized on the order of several hours when returned to “ORR relevant potentials” (< 0.6 V vs RHE), indicating that this surface-oxidized nitride is the active surface for ORR. Using in situ XRR measurements, we find that there is no change in surface roughness at potentials below 0.7 V vs RHE, but the film roughens significantly at 0.8 V vs RHE, correlating with ex situ measurements of Mo dissolution at this potential (Figure 1). We therefore conclude that the intrinsic activity of the Mo-N catalyst increases when exposed to potentials up to 0.7 V vs RHE, while above that potential activity enhancements are due to the exposure of more active sites through dissolution. The in situ electrochemical surface-sensitive x-ray characterization as used here is a promising methodology for understanding and leveraging surface dynamics to improve the performance of non-traditional catalysts.

Figure 1. RRDE measurements in O2-saturated 0.1M HClO4 at 1600 rpm and schematics illustrating how the catalyst composition and morphology change with applied potential.

Figure 1
(Invited) Liquid Phase TEM for Studying Catalysis and Electrochemistry of Nanomaterials
Authors: Park Jungwon
Published: December 2020

For the past few decades, nanomaterials of various sizes, shapes, and compositions have been synthesized and utilized in many different applications in heterogeneous catalysts and energy conversion systems. However, due to a lack of analytical tools that can characterize structural changes at the nanoscale level, many of their growth, transformations, and reactions are limitedly understood. The recent development of liquid‐phase transmission electron microscopy (TEM) is gaining attention as a new tool to directly observe chemical reactions that occur in solution. Due to its high spatial and temporal resolution, this technique is widely employed to reveal fundamental mechanisms relevant to nanomaterial chemistry. Here, the technical developments for liquid‐phase TEM are introduced. In addition, its use in in-situ liquid phase studies of the growth mechanism, 3D structures, surface reactions of heterogeneous catalytic nanoparticles will be discussed. Our in-situ observations with liquid phase TEM elucidate different types of non-classical pathway, including two-step nucleation, amorphous-to-crystalline transition, and coalescence of clusters, are involved in different conditions of catalytic nanoparticle formation. We also observe the diffraction patterns from individual heterogeneous catalytic nanoparticles as they rotate in the liquid cell, and ultimately, we are able to align and invert those images to obtain the 3D atomic structure of individual catalytic particles freely moving in liquid. Obtained 3D density maps unveil internal and surface structural features of those particles that have been either underestimated or unattainable in conventional analysis. Liquid phase TEM is further advanced to have a capability of resolving solution phase reactions of nanomaterials under in-situ electrical biasing conditions. Examples of in-situ biasing liquid TEM studies of electrochemical reactions in Li-air battery system will be also presented.
Compton Scattering Imaging for Operando Observation of Lithiation State on Commercial Lithium Battery Cells
Authors: Suzuki Kosuke , Tsuji Naruki , Orikasa Yuki , Uchimoto Yoshiharu , Sakurai Yoshiharu , Sakurai Hiroshi
Published: December 2020

X-ray Compton scattering imaging technique based on synchrotron radiation is a unique technique to observe lithiation sate in the electrode of commercial lithium battery cells under operando and in-situ conditions. The advantage of this technique is using high-energy which over 100 keV X-rays as an incident beam. High-energy X-rays allow to nondestructively observe the electrochemical reaction in the cells because high-energy X-rays have high-penetration power to the matter [1]. Moreover, by using high-energy X-rays, we can measure light elements like lithium because inelastic scattering effect (Compton effect) relatively enhanced in the interaction between photons and the matter. This talk presents our recent studies using a commercial coin-type lithium battery, which have carried out at BL08W of SPring-8, Japan [2,3]. In these studies, we have developed a method for quantifying lithium from the line-shape of Compton scattered X-ray energy spectrum which called the S-parameter method. By using the S-parameter method, we nondestructively visualized the volume expansion of the electrodes during the charge-discharge cycle and the lithium distribution depending on the cycle rate on the VL2020 coin cell. Moreover, the change of lithium concentration on both anode and cathode during the cycle was revealed in-operando and in-situ conditions. Our technique which allows to directly measure the lithiation state in-operando and in-situ condition opens a new pathway for advanced characterization of the closed electrochemical cells. In this talk, we will also introduce a newly developed Compton scattering imaging system using a two-dimensional detector instead of a previous Ge solid-state detector.

[1] M. Itou, Y. Orikasa, Y. Gogyo, K. Suzuki, H. Sakurai, Y. Uchimoto and Y. Sakurai, J. Synchrotron Rad., 22, 161-164 (2015).

[2] K. Suzuki, A. Suzuki, T. Ishikawa, M. Itou, H. Yamashige, Y. Orikasa, Y. Uchimoto, Y. Sakurai and H. Sakurai, J. Synchrotron Rad., 24, 1006-1011 (2017).

[3] K. Suzuki, R. Kanai, N. Tsuji, H. Yamashige, Y. Orikasa, Y. Uchimoto, Y. Sakurai and H. Sakurai, Condens. Matter, 3, 27 (2018).
(Keynote) Electrolyzer Development and Process Optimization: Paving the Road for Industrial Carbon-Dioxide Electroreduction
Authors: Endrodi Balazs , Kecsenovity Egon , Jones Richard , Janaky Csaba
Published: December 2020

Electrochemical reduction of CO2 is a promising method for converting a greenhouse gas into value-added products, utilizing renewable energy. Novel catalysts, electrode assemblies, and cell configurations are all necessary to achieve economically appealing performance. In this talk, I am going to present a zero gap electrolyzer cell, which converts gas phase CO2 to products without the need for any liquid catholyte. I will show how to optimize the cell components, to simultaneously provide industrially relevant performance, such as high partial current density (up to 800 mA cm-2), low cell voltage (−2.8-3.2 V), high conversion efficiency (up to 45 %), and high selectivity for CO production (over 95%).

I will also demonstrate our CO2 electrolyzer cell, where multiple layers are connected into an electrolyzer stack, thus scaling up the electrolysis process. The operation of the cell was validated using both silver nanoparticle and copper nanocube catalysts. Evenly distributing the CO2 gas among the layers (parallel connection), the operation of the cell stack was identical to the sum of multiple single-layer cells. When passing the CO2 gas through the layers one after the other (serial gas connection), the CO2 conversion efficiency was increased remarkably.

Finally, I will show how the cell can operate with pure water feed on the anode side, therefore avoiding the use of alkaline anolyte. A carefully designed activation protocol will be presented, which allows the cell to operate at high current density, using pure water feed. The effect of temperature and flow rate on the operation will also be presented. Finally, the nature of ion-transport through the anion exchange membrane as a function of the operational conditions will be discussed.
(Keynote) Molecular Electrochemical Reduction of CO2 with 2, 4 and 6 Electrons with Co Complexes at Electrodes and Photoelectrodes
Authors: Robert Marc
Published: December 2020

Reduction of carbon dioxide has as main objective the production of useful organic compounds and fuels - renewable fuels - in which solar energy would be stored. Molecular catalysts can be employed to reach this goal. They may in particular provide excellent selectivity thanks to easy tuning of the electronic properties at the metal and of the ligand second and third coordination sphere. Hybrid systems in which a robust molecular catalyst is associated to a porous carbon material conductive support or to a semi-conductive support may combine the advantages of both homogeneous and heterogeneous catalysis.

Using Co complexes (phthalocyanines and quaterpyridines), our recent results for CO2 reduction into CO but also formaldehyde and methanol at molecular cathodes (1-5) and photocathodes (6) will be discussed. These studies illustrate the synergy between electrochemical and photochemical approaches and the rich potential of molecular catalysts to generate fuels from CO2 used as a renewable feedstock

References

M. Wang, L. Chen, T-C. Lau, M. Robert, Angew. Chem. Int. Ed.
2018, 57, 7769-7773.

S. Ren, D. Joulie, D. Salvatore, K. Torbensen, M. Wang, M. Robert, C. Berlinguette, Science
2019, 365, 367-369.

M. Wang,K. Torbensen, D. Salvatore, S. Ren, D. Joulie, F. Dumoulin, D. Mendoza, B. Lassalle-Kaiser, U. Işci, C. Berlinguette, M. Robert, Nat. Commun.
2019, 10:3602.

E. Boutin, M. Wang, J. C. Lin, M. Mesnage, D. Mendoza, B. Lassalle-Kaiser, C. Hahn, T. F. Jaramillo, M. Robert, Angew. Chem. Int. Ed.
2019, 58, 16172-16176.

K. Torbensen, D. Joulie, S. Ren, D. Salvatore, M. Wang, C. Berlinguette, M. Robert, ACS Energy Letters
2020, 5, 5, 1512-1518.

P. B. Pati, E. Boutin, R. Wang, S. Diring, S. Jobic, N. Barreau, F. Odobel, M. Robert, Nat. Commun.
2020, in press.
(Keynote) Bioelectrocatalysis of Carbon Dioxide Reduction
Authors: Minteer Shelley D.
Published: December 2020

CO2 reduction has the potential to address issues related to the environment and the energy crisis. However, the reduction of CO2 is hard to achieve due to its kinetic and thermodynamic stability. Despite significant research effort, existing catalysts such as transition metals and metal complex suffer from either low selectivity and/or low CO2 conversion efficiency. Biocatalysts are an attractive alternative owing to their highly selectivity, low overpotential and mild operating conditions. A recently developed molybdenum dependent formate dehydrogenase (Mo-FDH) from Escherichia coli is a biocatalyst that is easy to obtain and has high efficiency to interconvert formate and CO2. However, the direct electron transfer of Mo-FDH is inefficient, and so far, no immobilized mediating system has been designed with Mo-FDH to support CO2 reduction. Low potential redox polymers are rare due to a limited number of mediators and stability issues. Here we developed a reductive redox polymer (cobaltocene modified poly allyl amine; Cc-PAA) to wire Mo-FDH at carbon electrode surfaces and simultaneously mediate electrons to facilitate the CO2 reduction. The polymer film shows good stability and formate was the exclusive product. This electroenzymatic interface is able to reduce CO2 to formate at a mild applied potential (-0.66 V. vs SHE) with a high Faradaic efficiency (99 ± 5%).
(Keynote) Understanding Selective C-C Coupling Reaction on Cu Based Nanoparticle from Electrochemical CO2 Reduction Reaction
Authors: Hwang Yun Jeong , Won Da Hye , Oh Hyung-Suk , Lee Ung
Published: December 2020

Cu is one of the interesting CO2 reduction reaction catalysts due to its unique capability to produce many of the hydrocarbon chemicals in addition to H2, and the nanostructures of the Cu-based electrocatalyst significantly affect the product selectivity for C2+ over C1 chemicals. Although material engineering strategies have aimed at the design of a selective C2+-producing catalyst, the role of the fundamental descriptor allowing control of the desired pathway is not yet well-understood. In this context, reliable guidelines for highly selective reactions require understanding the catalyst material and the reaction pathways. Both of a H-cell and gas-diffusion-electrode (GDE) based gas-fed cells have shown the enhanced ethylene selectivity with Cu nanoparticles prepared by oxide forms. The fragmented Cu surfaces having high defects or grain boundaries are proposed as active sites for C-C coupling based on the material characterization. In addition, in-situ spectroscopy such as X-ray absorption spectroscopy, Raman spectroscopy, and infrared absorption spectroscopy can provide additional information of the catalyst and intermediate operando condition. We demonstrated that the sites showing high vibrational frequency of *CO on the fragmented Cu surface are the potential active sites for the fast dimerization of CO, and C-C coupling occurs exclusively by CO dimerization toward *OCCO, without the participation of *CHO which is an intermediate for CH4 production. We propose that the reactions leading to formation of *CHO and *OCCO are non-competitive and kinetically independent, implying the selective C-C coupling is potentially controllable.
(Invited) Highly Selective and Efficient Conversion of CO2 to Fomate and Oxalate
Authors: Shin Woonsup , Jang Suji , Park Mijung
Published: December 2020

We succeeded in fabricating a dental amalgam composition on a copper foam electrode and could convert CO2 selectively to formate. The formate could be produced at a current efficiency of 80~100% in a wide range of the potential of 0.6 V. The remaining electricity was used only for producing H2. The concentration of the produced formate is over 1.2 M in the batch electrolysis of 30-hours operation. The CO2-to-formate conversion system, built based on the electrode in the dimension of 9 cm x 9, is shown to be stable in continuous operation at 100 mA/cm2 for more than a month. In the case of the conversion to oxalate, the electrolysis of CO2 in an organic solvent with a sacrificial anode, the current efficiency of 95%, and the production of 80 g of the oxalate salt could be obtained for 18-hour electrolysis using the three- stack-cell electrolysis unit.

Figure 1
Enhanced Ethylene Selectivity during CO2 Reduction Using Polymers with Intrinsic Microporosity at Copper Gas Diffusion Electrodes
Authors: Perry Samuel Charles , Gateman Samantha Michelle , Malpass-Evans Richard , McKeown Neil , Wegener Moritz , Nazarovs Pāvels , Mauzeroll Janine , Wang Ling , Ponce-de-Leon-Albarran Carlos
Published: December 2020

CO2 reduction is a rapidly expanding area, and a key part of the global mission to reduce carbon emissions and reduce our impact on our environment. The CO2 reduction reaction (CO2RR) presents a synthetic route to a number of industrially relevant materials, such as methane, ethylene, formate and CO.1 This provides a two-fold environmental benefit; CO2 can be captured from industrial processes before being released into the environment and produce a material usually sourced from fossil fuels.

Much work has been dedicated to CO2RR at copper electrodes thanks to its ability to produce C2 species such ethylene with reasonable selectivity. However, the currently attainable selectivity is not sufficient for practical applications. The outflow contains mixtures of CO2RR products, along with a substantial amount of H2 from water reduction at the same potentials.

This work improves the selectivity of copper gas diffusion electrodes (GDEs) towards ethylene using Polymers with Intrinsic Microporosity (PIMs). PIMs are easily drop-cast onto the GDE, forming a microporous layer at the catalyst – electrolyte interface. The microporous structure stores gases in a triphasic interface at the electrode surface,2 which has previously been shown to improve catalyst activity towards oxygen reduction.3

We show that the introduction of a PIMs triphasic interface to copper GDEs improves the CO2RR towards ethylene, evidenced by an increased Faradaic efficiency, improved GDE stability and shift in the reduction wave to lower overpotentials.4 The impact of the PIMs is significantly dependent on the loading, with thin layers enhancing performance, but thicker layers having a surprisingly detrimental effect. This work is a proof of concept, showing the potential of triphasic interfaces for enhancing the activity of GDEs for CO2RR towards ethylene production.

References:

[1] S. C. Perry, et al., Curr. Opin. Electrochem., 2020, Accepted

[2] F. Marken, et al., ChemElectroChem, 2019, 6, 1

[3] E. Madrid, et al., ChemElectroChem, 2019, 6, 252

[4] S. C. Perry, et al., Chemosphere, 2020, 248, 125993

Figure 1. Schematic role of PIMs at a copper GDE surface. PIMs increase both the selectivity and activity towards ethylene during CO2 reduction. Bottom right inset shows the structure of the PIM used (PIM EA-TB).

Figure 1
(Invited) Lignin for Power- and Solar-to-Chemical Energy Conversion: An Alternative Electron Source and Its Valorization
Authors: Ryu Jungki , Choi Yuri , Oh Hyeonmyeong
Published: December 2020

Electrochemical and photoelectrochemical synthesis is a promising technology for the efficient use of clean but intermittent renewable energy resources. In principle, various chemicals can be produced in a sustainable manner through (photo)electrochemical reduction using water as a cheap and clean source of electrons. However, oxidation of water is a challenging task and acts as a bottleneck for the practical application of solar- and power-to-chemical energy conversion due to slow kinetics originating from its complex four-electron transfer process. In addition, it requires the use of expensive catalysts and causes reliability issues. In this presentation, we report that various types of biomass wastes can be used as cheap and efficient electron sources. In particular, electrons can be readily extracted from biomass using phosphomolybdic acid (PMA), which can act as a catalyst for oxidative depolymerization of biomass and an electron mediator. PMAs can be reduced upon oxidation of biomass and then oxidized on an anode at a potential much lower than that for water oxidation. Furthermore, value-added chemicals such as CO and vanillin are produced as byproducts upon oxidative depolymerization of lignin. As a result, this approach allows efficient (photo)electrochemical production of hydrogen at acidic pHs and brings additional economic benefits from byproducts.
(Invited) Integrated Green Engineering Process for Simultaneous Hydrogen Production and Fertigation
Authors: Han Dong Suk , Zavahir Fathima , Gulied Mona , ElMakki Tasneem , Shon Ho Kyong , Park Hyunwoong
Published: December 2020

The constant utilization of hydrocarbon-based fuels such as petroleum, coal, and natural Gas has resulted in the detection of high concentration levels of sulfur containing gases in the atmosphere of many countries, including Qatar. Among those potential air pollutants, the rising concentrations of H2S and SO2 are of serious concern. In this work, sulfur-based seed solutions (SBSSs) such as sulfite or sulfide solutions are made by purging sulfur-containing gases released from industry into alkaline solutions. These SBSS solutions are simultaneously utilized towards the production of renewable hydrogen energy via a photoelectrochemical (PEC) process, and are used as draw solutions (DS) to produce diluted fertilizer water by a forward osmosis (FO) desalination process for agricultural irrigation purposes. The continuous bench scale of the integrated PEC-FDFO system was successfully demonstrated for simultaneous hydrogen production and dilution of SBSS DS. The experimental results showed that the reduction potential of SBSS DS in the PEC cell changes with variation of SBSS DS concentration and pH. This resulted in the continuous oxidation of sulfite into sulfate and led to more hydrogen production. Moreover, FDFO process exhibited high percentage of water recovery and DS dilution up to 80% and 68% at high SBSS DS concentration, respectively. In binary mixture of SBSS DS, increasing the concentration of ammonium sulfate (NH4)2SO4 led to high water flux to about 42%. The outcomes of this experimental study showed a successful practical continuous integrated system toward hydrogen production and fertigation.
IoT-Based Sensor Systems for Intelligence in Transportation, Healthcare and Natural Gas Detection
Authors: Agi Kamil , Ian Robert , Tsui Lok-kun , Garzon Fernando H , Jordan Ramiro
Published: December 2020

In the last decade, significant advances have been made to enhance the deployment of sensors. Everything from novel manufacturing technologies (including additive manufacturing techniques) to topologies to material systems.

Here we are defining the utility of a sensor as the ability to provide intelligence. Intelligence comes from collecting
data
, extracting
information
, which comes from data analytics, and interpreting the information is what we are calling
intelligence
. Many tools are available, even off-the-shelf capabilities, which include machine learning, artificial intelligence, and even sets of toolboxes in MatLab that have changed the way we obtaining intelligence.

In order to obtain viable data, integrity on the collection of the data becomes important. Collection can be done by assigning IP addresses to sensors, on-board data storage and/or Internet of things-type (IoT-type) platforms that have really enabled the utilization of sensors to explode. The challenge is always about obtaining intelligence.

This paper introduces the concept of SensorComm’s emission monitoring solution, Wi-NOx™. Wi-NOx™ is an IoT-based real-time NOx emission monitoring system. Installed at the tailpipe, it provides key stakeholders with real-time business intelligence by capturing the pollution footprint of vehicles. Operational efficiencies of up to 15% include fuel savings, predictive maintenance, and performance optimization, all obtained through analytics. This system was developed to monitor emissions from vehicles, more recently modified to monitor patients remotely for healthcare applications, and now to monitor natural gas for oil & gas applications.

This talk will discuss the systems strategy for data surety, data analytics, and examples of the intelligence extracted specifically from an application.

This material is based upon work supported by the U.S. Department of Energy, National Energy Technology Office program under Award Number DE-FOA-0031864, and by the National Science Foundation under Grant No. 1632498.

Figure 1
Electroplated Tin Absorbers in Microcalorimeter Detectors for Ionizing Radiation
Authors: Arrington Christian L. , Pillars Jamin R. , St. John Christopher R. , Lewis Rupert , Carr Stephen , Bland Jesse J , Hamel Michael , Schmidt Daniel R. , Ullom Joel N , Croce Mark P.
Published: December 2020

State-of-the-art microcalorimeter gamma-ray detectors
1, 2
show promise for nuclear material characterization because their spectral resolution is substantially better than high purity germanium sensors. Microcalorimeter detectors have been fabricated and tested by National Institute of Standards and Technology (NIST) and Los Alamos National Laboratory (LANL) by combining microfabricated transition edge sensors (TESs) with bulk tin gamma-ray absorbers. The ability to integrate the tin electroplating into the microfabrication process has potential benefits for performance, scalability, reliability, and ease of manufacturing.

This work investigates a commercially available tin/silver chemistry traditionally used for 3-D semiconductor packaging. Samples were electroplated on a sacrificial substrate changing chemistry makeup, current density, and time to realize pure tin deposition at thicknesses of 380-400 micron. Characterization was performed using SEM, EDS, XRF, and XPS and compared to bulk tin properties used in past microcalorimeter devices. The electroplated tin samples were diced into individual 1.3x1.3 mm sizes and integrated with TES detectors at NIST and LANL. The assembled devices were tested with gamma radiation sources to evaluate performance. This work will provide an overview of the project, current progress, and future ideas for realizing a fully integrated microcalorimeter fabrication process.

D. A. Bennett, R. D. Horansky, D. R. Schmidt, A. S. Hoover, R. Winkler, B. K. Alpert, J. A. Beall, W. B. Doriese, J. W. Fowler, C. P. Fitzgerald, G. C. Hilton, K. D. Irwin, V. Kotsubo, J. A. B. Mates, G. C. O'Neil, M. W. Rabin, C. D. Reintsema, F. J. Schima, D. S. Swetz, L. R. Vale, and J. N. Ullom, Rev Sci Instrum,
83 (9), (2012).

D. T. Becker, B. K. Alpert, D. A. Bennett, M. P. Croce, J. W. Fowler, J. D. Gard, A. S. Hoover, Y. I. Joe, K. E. Koehler, J. A. B. Mates, G. C. O'Neil, M. W. Rabin, C. D. Reintsema, D. R. Schmidt, D. S. Swetz, P. Szypryt, L. R. Vale, A. L. Wessels, and J. N. Ullom, Ieee T Nucl Sci,
66 (12), 2355-2363 (2019).

Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA-0003525, SAND2020-5481 A . The views expressed in the article do not necessarily represent the views of the U.S. Department of Energy or the United States Government.
Effect of Boron Doping Level on BDD Electrode for Heavy Metal Ion Sensor
Authors: Kim Shin , Jeong Yesul , Song Pung-Keun , Yoon Jang-Hee
Published: December 2020

Recently, industrial wastewater is being discharged in large quantities due to the development of industry and this wastewater contains a various heavy metal ion. Exposure to high levels of trace metal ions [Cd (II), Pb (II), Cu (II)] causes a variety of health and environmental problems. These toxic species accumulated in the human body through the water source have a low rate of clearance. [1,2]

To minimize the exposure of humans to these contaminants through effective water quality monitoring, anode stripping voltammetry (ASV) method was used. ASV method has wide linear dynamic range, low detection limit (ppb), multi-element analysis capability and the simplicity of the instrumentation, which is relatively inexpensive and small in size, requires low levels of electrical power and is sufficiently portable to permit its use in the field. So, ASV has been used successfully for the determination of heavy metals in water. The sensitivity of differential pulse anode stripping voltammetry (DPASV) is higher than other classical voltammetry, because of its enhanced faradaic current and decreased non-faradaic charging current. [2]

In generally, Ir, Au, Ag and Hg electrodes have been used for stripping analysis of trace metals, but the Ir, Au, Ag electrodes have low sensitivity, Hg electrode have toxicity and volatility. [2] To solve this drawbacks, we fabricate a Boron-doped diamond (BDD) electrodes. BDD electrodes are candidate for use in the detection of a trace heavy metal ions, because these show good electrical conductivity, low background current, and non-toxicity.

In this study, BDD electrodes on Si substrate deposited by hot filament chemical vapour deposition (HFCVD) and applied to DPASV measurement. Through the optimization of the deposition condition of BDD electrodes and measurement condition of DPASV, we increased the detection sensitivity of heavy metal ions. The BDD electrode with the optimum boron doping concentration by controlling the boron doping concentration from 100 to 10000 ppm in the deposition process optimization step has excellent durability and selectivity of heavy metal ions. As a result of electrochemical measurement, BDD electrode with 8000 ppm B was displayed high sensitive response and wide potential window range of -1.7 V to 1.6 V with the detection limit of 0.001 mg/L to 0.01 mg/L ±5 % about heavy metal ions [Cd (II), Pb (II), Cu (II)].

[1] M.O. Park et al, Electroanalysis. 2017, 29, pp. 514 – 520

[2] J. –H. Yoon et al, Bull.
Korean Chem. Soc.
2010, Vol. 31, No. 1

This study was supported by the Korea Environmental Industry & Technology Institute[grant number 20190027400012] and R&D Center for Green Patrol Technologies through R&D for Global Top Environmental Technologies [grant number 20180018400013] funded by the Ministry of Environment, Republic of Korea (MOE),

Figure 1
Electrochemical Sensors for Biological and Environmental Application
Authors: Park Suji , Koley Dipankar
Published: December 2020

Electrochemical sensors have been developed for last few decades in many different types and ways. They can be applied in various fields of study such as biomedical or biomaterials, environment, and energy, etc. Few projects will be introduced in the conference to show how these sensors can solve such problems. One of the sensors we’ve developed is used to quantify pH and H2O2 simultaneously in real-time to study oral bacterial metabolism in micro-environment. One species of oral bacteria takes glucose and produces H2O2 which plays a key role in maintaining healthy oral condition. We assume that the H2O2 production will increase at higher pH. Since bacterial metabolism and interspecies interaction occurs in few-micron surrounding from bacterial community, it is very challenging to approach there without destroying samples. Thus, we are using few techniques here; Scanning electrochemical microscopy enables us to control and fix the distance between a substrate and an extremely small microelectrode. Another sensor we are working on has unique composition of ion-selective electrode (ISE) membrane. ISE membrane is primarily made of insulating PVC that limits its use as an amperometric electrode. However, our sensor has a carbon-based dual function ISE membrane. It is capable of switching between amperometric and potentiometric measurements without affecting the selectivity coefficients of ISEs. It showed an impressive nM and pM detection limit of Cu2+ and thus opening new avenues of exploiting the excellent selectivity of ISEs and low detection limit of ASWSV techniques. This sensor can be applied to trace heavy metal ions concentration in unknown liquid sample and to determine their solubility depending on pH. The design of sensor and experimental setup will be presented.
Preparation of Low Invasive Type Glucose Sensor for Continuous Glucose Monitoring
Authors: Yasuzawa Mikito , Osugi Kazumasa , Terauchi Takeru , Li Jiang , Kurashina Masashi
Published: December 2020

Implantable glucose sensors for a continuous glucose monitoring (CGM) system are getting more attractive, since it not only provide an instant glucose value but also its continuous value trend, which help to provide an effective medical treatment. However, the current commercialized or presented conventional CGM sensor devise are required to have about an length of 1.0 cm to be inserted inside the skin. Therefore, it is desirable to develop a lower invasive type glucose sensor to improve the quality of life of diabetic patients.

We have previously proposed an unique glucose sensor, which has a sensing region at the tip of a fine tapered needle. Therefore, it only require a short tip of the sensor devise to be implanted to perform as an CGMS sensor. We attempted to implant this sensor device for a length of 1.0 mm in the skin, and the glucose monitoring was performed. As a result, we could obtain sensor response, which had a good correlation with blood glucose value trend. This result indicate that the glucose measurement in a lighter region than subcutaneous tissue, which might be in dermis, may also provide valuable information for diabetes patients’ blood glucose management. Nevertheless, low-invasive sensor, which is essential with miniaturization of sensing region, leads to a decrease of glucose response current. Therefore, the improvement of sensor sensitivity is also indispensable. In this study, we prepared glucose sensors in various procedures to develop a sensor with high sensor sensitivity.
Rapid Coronavirus Detection Sensor
Authors: Ramanujam Ashwin , Almodovar Sharilyn , Botte Gerardine G.
Published: December 2020

With an everyday surge in the number of COVID-19 confirmed cases, it is still being debated in different parts of the world on how the tests per day have to be increased and available to everyone. This would help identifying the affected people at the earliest stages and treat the symptoms when they are benign. The standard laboratory diagnostic tests, such quantitative reverse transcriptase polymerase chain reaction (qRT-PCR), although effective in the detection of virus, lack the ability to return test results quickly. Also, there is a mismatch between the number of samples collected per day to the number of samples that can be tested timely by the approved laboratories. This calls for alternate test kits that are rapid and can be used at the frontlines and elsewhere for point-of-care applications. In this talk, we will describe an electrochemical approach for detecting the pandemic 2019 Coronavirus (SARS-CoV-2), the Rapid 2019-novel Coronavirus Detection Sensor (RAnCODS-19). We have demonstrated the performance of our sensor with SARS-CoV-2 spike protein in samples. Our results indicate a positive/negative response for the presence/absence of the protein within 100 milliseconds. In this talk, we will describe the sensor and present further results. Implementation of multiple of these sensors at the frontlines would make a difference in early detection of COVID-19 in patients. Our multidisciplinary team includes experts in electrochemistry, molecular virology and biomedical sciences.

Keywords:

COVID-19 detection; Electrochemical biosensor; Point-of-care diagnostic devices
Synthesis and Applications of Dendrimer-Encapsulated Pt Nanoparticles in Chemical Sensors
Authors: Kim Joohoon
Published: December 2020

Synthesis of nanoparticles having well-defined small sizes especially less than ~3 nm has been in the forefront of research attention in diverse fields including biological and chemical sensors because of unique features of such very small particles. Synthesis and characterization of such tiny particles still remains challenging due to the extremely small dimension of the particles, too. Here, I present the synthesis of ultra-small Pt nanoparticles having different but uniform sizes using dendrimers as a molecular template, which is usually denominated as dendrimer-encapsulated nanoparticles (DENs). Specifically, I present a new synthesis strategy of Pt DENs to expand the applicable number of Pt atoms in Pt DENs by utilizing repetitively coupled chemical reduction and galvanic exchange reactions. The applications of Pt DENs is also discussed in chemical sensors. For example, I present the modification of indium tin oxide (ITO) with Pt DENs to provide enhanced stable electrochemiluminescence (ECL) of Ru(bpy)3
2+/tripropylamine while preserving optical transparency of ITO for sensitive ECL-based analyses.
Non-Invasive Cytokine Detection Via Organic Color Center Patch
Authors: Kim Mijin , McCaan Jim , Chen Chen , Manzari Mandana Taghizadeh , Yaari Zvi A , Koder Ronald , Heller Daniel A.
Published: December 2020

Organic color centers (OCCs) are synthetic color-centers that are incorporated into semiconducting single-walled carbon nanotubes by chemical reaction. The color centers create new photoluminescence peaks, which act as optical antennae, making OCCs the molecular focal points for chemical sensing. We will present a new diagnostic technology that uses OCCs augmented by biodesigned supercharged molecular recognition proteins. We will discuss the physical and optical properties of the OCC based nanosensors that ensure stability and sensor response for robust, transient detection of cytokines in biofluids. Development of in vivo sensing devices for long-term, minimally-invasive monitoring of disease biomarkers will also be discussed.