bluuebunny/crossref_metadata_2025_split huggingface dataset:
(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
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.
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
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