bluuebunny/crossref_metadata_2025_split huggingface dataset:
Perovskite-Based Oxide Catalysts to Improve the Oxygen Evolution and Reduction Activity
Authors: Kim Nam-In , So Inseop , Park Jun-Young 
Published: February 2020

Unitized regenerative fuel cells (URFCs), which include water electrolysis and fuel cells, have received many attentions due to the production of hydrogen gas and electricity in one electrochemical device. Water electrolysis is one of the most pollution-free and renewable ways to produce hydrogen. However, the slow kinetics of oxygen evolution reactions (OERs) in the URFC anode are limited by high polarization resistance for oxidation of water. Likewise, oxygen reduction reactions (ORRs) for the fuel cell cathode also show slow rates due to the multi-step electrochemical reactions demands of 4-electrons in reactions, limiting the overall reaction rate of the fuel cells.
Up to date, the noble metal-based catalysts, such as carbon-supported iridium, ruthenium, platinum and alloys, have still used as OER and ORR catalysts. The use of precious metal-based materials is not suitable for the commercialization of the electrochemical cells. In order to replace these noble metal catalysts, studies of perovskite-based oxide catalysts for URFCs have carried out intensively these days. In particular, various dopants in the perovskite materials may help to improve the electrochemical properties significantly.
Herein, the perovskite-based catalysts are synthesized by the glycine-nitrate combustion method with various A site material (Nd, Sm and Gd) in ABO3 structure. Then, the ashes are calcined at 900 oC for 4h in electric furnace at a heating rate of 5 oC min-1. The physicochemical properties of the final products are characterized by several analytic tools such as X-ray diffraction, scanning electron microscope, transmission electron microscope and BET.
For electrochemical analysis, a rotating disk electrode system is used with an Hg/HgO and a Pt wire and a 0.1 M KOH solution for reference, counter and electrolyte, respectively. The pre-conditioning of catalysts is carried out by cyclic voltammetry (CV) at a scan rate of 100 mV s-1 for 50 cycles with nitrogen-purged electrolyte. The OER (1.2 V ~ 1.7 V) and ORR (0.05 V ~ 1.2 V) activities are measured by linear sweep voltammetry (LSV) at a scan rate of 5 mV s-1 and for the performance and long-term stability.

A. Grimaud, K.J. May, C.E. Carlton, Y.-L. Lee, M. Risch, W.T. Hong, J. Zhou and Y. Shao-Horn, Nat. Comm., 4, 2439 (2013).

Y. Liang, Y. Li, H. Wang, J. Zhou, J. Wang, T. Regier, H. Dai, Nature Materials, 10, 780 (2011).

J. Kim, X. Yin, K.-C. Tsao, S. Fang and H. Yang, J. Am. Chem. Soc., 136, 14646 (2014).

J.-I. Jung, H.Y. Jeong, M.G. Kim, G. Nam, J. Park and J. Cho, Adv. Mater., 27, 266 (2015).

J. Suntivich, K.J. May, H.A. Gasteiger, J.B. Goodenough, Y. Shao-Horn, Science, 334, 1383 (2011).

J. Suntivich, H. A. Gasteiger, N. Yabuuchi, Y. Shao-Horn, Nature Chemistry , 3, 546 (2011).

T. Reier, M. Oezaslan, P.Strasser, ACS Catal., 2, 1765 (2012).

I. C. Man, H. Y. Su, F. C. Vallejo, H. A. Hansen, J. I. Martínez, N. G. Inoglu, J. Kitchin, T. F. Jaramillo, J. K. Nørskov, J. Rossmeisl, ChemCatChem, 3, 1159 (2011)
Self-Supported Three-Dimensional Macroporous Nickel Phosphide Electrodes for Overall Electrochemical Water Splitting
Authors: Liu Lifeng , Wang Xiaoguang , Li Wei , Xiong Dehua 
Published: February 2020

Water electrolysis is considered as the “cleanest” way to produce hydrogen, when the required electricity is derived from renewable energy sources such as solar or wind. To overcome the prohibitive cost barrier to market penetration and to enable widespread deployment of water electrolyzers, it is of paramount importance to develop efficient, cheap, and durable electrocatalysts to expedite hydrogen and oxygen evolution reactions (HER and OER). Notwithstanding remarkable progress in bi-functional electrocatalysts, there are few materials that can simultaneously catalyze HER and OER in the same medium. In this presentation, we report a self-supported three-dimensional macroporous electrode composed of micro/nano-hybrid structures of nickel phosphide – an emerging non-precious electrocatalysts. The electrode is fabricated by a simple, cost-effective, and readily-scalable method, and can be directly used as either cathode or anode in an alkaline electrolyzer. Overall electrochemical water splitting has been realized using an electrolyzer constructed by two identical the as-fabricated electrodes, and a high energy efficiency of 91% is achieved at 10 mA cm-2. Our finding would significantly simplify the fabrication procedure of water electrolyzers and substantially lower the production costs, given the unique bi-functionality, easy and cost-effective synthetic process of our self-supported nickel phosphide macroporous electrodes.
Figure: SEM image showing the morphology of the self-supported three-dimensional nickel phosphide electrodes.

Figure 1
Prostate Cancer Biomarker Detection Using a 16-Sensor Electrochemical Microfluidic Immunoarray
Authors: Jones Abby L , Otieno Brunah A , Sharafeldin Mohamed , Joshi Amit A , Krause Colleen E , Rusling James F 
Published: February 2020

A semi-automated multiple biomarker-based diagnostic microfluidic device for on-line capture and detection of prostate cancer biomarkers is described herein. In the United States, the lifetime risk of men developing prostate cancer is 1 in 7. Strategies in detection and staging of prostate cancer include prostate specific antigen (PSA) test, digital rectal exam (DRE) and biopsy. These practices often fall short in terms of sensitivity, specificity and inability to distinguish between aggressive and indolent forms of prostate cancer. Inaccurate sensitivity and specificity can lead to unnecessary treatments that adversely affect the patients’ quality of life. Measurement of small panels of molecular biomarkers in serum holds tremendous potential for cancer diagnostics and personalized therapy. The protein panel includes PSA, CD-14, ERG, GOLM-1, PEDF-1, IGF-1, VEGF-D and IGFBP-3, many of which are thought to be specific for aggressive prostate cancer. The protein analytes are captured from serum samples in a two channel on-line microfluidic chamber by magnetic beads labeled with antibodies and signal transducing elements. Captured analytes are then magnetically separated, washed, and introduced into a two channel detection chamber housing an array of 8 or 16 nanostructured, antibody-labeled electrodes. Ultra-low detection limits in the sub fg ml-1 range was achieved for the protein panel. Using this strategy, 8-16 proteins can be detected simultaneously in 30 minutes. Measurements of the selected biomarker panel will be tested with prostate cancer patient samples in future to assess its diagnostic capability.
Preparation and Characterization of Bucky Paper Electrodes for Enzyme Electrocatalysis
Authors: Akinwale Mayowa Akiwande , Montealegre Roberto , Walgama Charuksha , Krishnan Sadagopan 
Published: February 2020

Nanomaterials are emerging as attractive platforms for enzyme immobilization for various electrocatalytic applications1-3. The superior electronic properties and large surface area of such nanomaterials gained significant attention in developing enzyme electrocatalytic systems4-5. In this study, we have prepared and characterized multiwalled carbon nanotube based “flexible” bucky papers for enzyme electrocatalysis. We have prepared bucky papers with different thicknesses ranging from 80 to 400 μM using the vacuum filtration method6. They are characterized by microscopy and electrochemistry for surface morphology and for electrochemical properties including conductivity and capacitance. These bucky papers are further immobilized with bilirubin oxidase enzyme to perform direct oxygen reduction without any redox mediators. Additionally, applicability of these bucky papers for membrane bound heme-enzyme catalysis is under examination. Our findings on this project will be presented.
1. S. Krishnan and J. F. Rusling, Thin Iron Heme Enzyme Films on Electrodes and
Nanoparticles for Biocatalysis, Chapter 5, p.125, in New and Future Developments

in Catalysis, S. Suib (Ed.), Elsevier Publishers (2013)
2. M. F. De Volder, S. H. Tawfick, R. H. Baughman, A. J. Hart, Science 339, 535-539 (2013).
3. R. D. Milton, F. Giroud, A. E. Thumser, S. D. Minteer, R. C. T. Slade, Chem. Commun. 50, 94-96 (2014).
4. S. Cosnier, R. Haddad, D. Moatsou, R. K. O’Reilly, Carbon 93, 713-718 (2015).
5. R. J. Lopez, S. Babanova, Y. Ulyanova, S. Singhal, P. Atanassov, ChemElectroChem 1, 241-248 (2014).
6. L. Hussein, G. Urban, M. Kruger, PCCP 13, 5831-5839 (2011).
Ultra-Low Amount of Pt Decorated Pd-Based Nanoparticles for the Oxygen Reduction Reaction
Authors: Xiao Weiping , Liu Sufen , Xin Huolin L. , Wang Deli 
Published: February 2020

Ultra-low amount of
Pt decorated
Pd-based nanoparticles
for the oxygen reduction reaction

Weiping Xiaoa,Sufen Liua, Huolin L. Xinb, and Deili Wanga,*
a, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, 430074, P.R. China
b, Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY, USA
* Email: wangdl81125@hust.edu.cn
Carbon-supported Pt-based catalysts have been considered as an ideal catalyst for the oxygen reduction reaction (ORR)1. In this regard, it is of great essential to enhance the utilization efficiency of Pt to reduce the overall fuel cell system cost. Recently, Pd-based nanomaterials as catalysts for ORR have attracted much attention because of their unique properties, such as the similar properties to Pt, and the relatively low cost compared with Pt2
,
3. Based on this, it is of great significance to design a highly active and stable PdM@Pt core-shell structure nanoparticle with PdM core and ultrathin Pt shell.
Here, carbon supported Pd3V@Pt/C core-shell structure nanoparticle has been systematically synthesized via a simple impregnation-reduction method, followed by a spontaneous displacement of Pt. Electrochemical tests reveal that the half-wave potential of Pd3V@Pt/C shifts positively of 80 mV compared with that of Pd/C and the Pt mass activity of Pd3V@Pt/C improves by factors of 10.9 at 0.80 V relative to that of Pt/C. This can be attributed to the strain arising from the mismatch in lattice constant between the Pd3V core and ultrathin Pt shell. Furthermore, the morphology and elemental composition of the Pd3V@Pt/C nanoparticles before and after potential cycling tests are determined using an aberration-corrected Nion scanning transmission electron microscopy (STEM) equipped with an Enfina electron energy loss spectrometer (EELS). After 10 K potential cycling tests, there is no obvious morphology change, because the Pt-rich shell plays an important role in preventing degradation.
Acknowledgements
This work was supported by the National Natural Science Foundation (21306060, 21573083), the Program for New Century Excellent Talents in Universities of China (NCET-13-0237), the Doctoral Fund of Ministry of Education of China (20130142120039), the Fundamental Research Funds for the Central University (2013TS136, 2014YQ009).
References
(1) Wang, Y. J.; Zhao, N.; Fang, B.; Li, H.; Bi, X. T.; Wang, H., Chem
. rev
., 2015, 115, 3433-3467.
(2) Zhao, X.; Chen, S.; Fang, Z.; Ding, J.; Sang, W.; Wang, Y.; Zhao, J.; Peng, Z.; Zeng, J. , J
. Am
. Chem
. Soc
., 2015, 137, 2804-2807.
(3) Park, J.; Zhang, L.; Choi, S.-I.; Roling, L. T.; Lu, N.; Herron, J. A.; Xie, S.; Wang, J.; Kim, M. J.; Mavrikakis, M., ACS nano, 2015, 9, 2635-2647.
Synthesis and Conductivity of Directly Cross-Linked Chitosan / Bis(2-chloroethyl) Ether-1,3-Bis[3-(dimethylamino)Propyl]Urea Copolymer As Alkaline Anion-Exchange Membranes
Authors: Qiao Jinli 
Published: February 2020

Anion-exchange membrane fuel cells (AEMFCs) researches have recently made a noticeable comeback from proton-exchange membrane fuel cells (PEMFCs) dominant era. The alkaline membrane fuel cells can get faster electrokinetics, lower fuel crossover, reduced CO poisoning, and use of non-precious metal catalysts. 1-3However, the conductivity and stability of AAEMs are still far less than commercial membrane Nafion.4

Chitosan (CS) is a low-cost biopolymer, which has very good mechanical and chemical stability along with good film formation property. 5However, since CS is just a weak alkaline conductivity, it cannot be directly used to fuel cell membrane. In this work, we report a novel series of alkaline anion-exchange membranes: Chitosan /Bis(2-chloroethyl)ether-1,3-bis[3-(dimethylamino)propyl]urea copolymer (PUB) membranes. By incorporation of PUB, the OH- conductivity of the CS/PUB membrane was found to be greatly improved and reached high up to 4.25×10-3S cm-1.
The membranes were prepared by a solution-casting method, where 2g chitosan (degree of deacetylation=80.0-95.0，supplied by Sinopharm Chemical Reagent Co.Ltd.China) was dissolved in deionized water with 2 wt.% acetic acid to form 2 wt.% chitosan solution. Then, PUB was mixed with the above chitosan solution at room temperature. At last, 0.5mg GA was mixed with Chitosan/ PUB composite solution to get a homogeneous appearance. Membranes were obtained with a thickness about 50-100µm. The membrane characteristics were measured using OH-conductivity and water uptake.
Fig. 1 shows the picture of as-prepared Chitosan/ PUB. It is obvious that the membrane is standing and flexible.
Fig. 2 displays the OH- conductivity and WU of Chitosan:PUB=1:0.25;1:0.5,1:0.75 membranes. The OH- value is different with increasing PUB contents and reached 4.25×10-3 S cm-1 when polymer composition is 1:0.25:0.1 by mass. The more details, including the effect of cross-linking method on its conductivity, will be reported in the meeting.
References
1. J. Zhou, M. Ünlü, I. Anestis-Richard, P.A. Kohl,J. Membr. , 350,286(2010)
2. Merle, Géraldine, Matthias Wessling, Kitty Nijmeijer, J. Membr. 377, 1 (2011)
3. J. Ma, Nurul A. Choudhury, Yogeshwar Sahai*, Rudolph G. Buchheit, J. Power Sources, 196, 8257 (2011)
4. Y. Liu, X.H. Cao, R. Hua, Y.Q. Wang , Y.T. Liu , C. Pang , Y. Wang, Hydrometallurgy, 104
,150 (2010)
5. G. Wang, Y. Weng, D. Chu, D. Xie, R. Chen, J. Membr. 326(2009) 4e8
Fig. 1 Membrane pictures of Chitosan/PUB membrane. Polymer composition:Chitosan/ PUB/GA = 1: 0.5:0.1 by mass.
Fig.2 OH- conductivity and water uptake of PVA/PUB/GA membranes in different PUB contents in polymer.

Figure 1
(Invited) Overcoming Biocathode Limitations in Bfcs: Enhancing O2 Concentration with Micelles
Authors: Hickey David P , Albertson Kelan , Milton Ross D , Minteer Shelley D. 
Published: February 2020

Enzymatic fuel cells (EFCs) are capable of utilizing a wide range of sugars and short-chain alcohols as fuel sources. Using an enzymatic catalyst at either the anode or cathode, EFCs are able to operate under physiological pH and temperature. Recent advancements in bioanodic materials have allowed for generation of current densities in excess of 2 mA cm-2; however, the majority of EFCs are limited by current density generated at the biocathode. Typical enzymatic biocathodes utilize a copper oxidase, such as laccase or bilirubin oxidase, to bioelectrocatalytically reduce molecular oxygen to H2O. However, biocathodes are often limited by slow diffusion of O2 to the electrode interface, which is ultimately the result of relatively low solubility of O2 in aqueous solutions (mole fraction solubility, xO2
= 2.3×10-5). By contrast, the solubility of O2 in organic solvents such as nonane or perfluorooctane (xO2
= 2.1×10-3 and 5.3×10-3, respectively) are much higher than in aqueous conditions.
We have developed a strategy to combine the high O2 solubility of organic solvents with the biocompatibility afforded by aqueous solutions, in which phospholipid micelles are used to trap O2 and transport it to the cathode surface. By modifying the phospholipid composition, various properties of the corresponding micelle can be tuned to cause dispersion upon contact with the electrode surface thereby increasing the localized O2 concentration. The net result is a dramatic increase in current density generated at the biocathode.
Characterization and Optimization of Gas Diffusion Cathode for Single-Chamber Microbial Fuel Cells Application
Authors: Chan Shirley , Phan Tony , Babanova Sofia , Santoro Carlo , Atanassov Plamen , Bretschger Orianna 
Published: February 2020

Microbial fuel cells (MFCs) are bioelectrochemical systems that utilize different species of microorganisms to break down organic substrates and generate electricity. Those microorganisms are able to transfer the electrons from the oxidation process to electron acceptors, such as carbon anode electrodes. The electrons are transferred through an electrical circuit from the anode to the cathode, where the oxygen reduction reaction (ORR) occurs. The rate of organic substrate removal and magnitude of electricity generation from MFCs depend on the operational efficiency of both electrodes - biotic anode and abiotic cathode.
Our study focuses on the development, characterization, and optimization of gas diffusion ORR cathodes for single-chamber MFC applications. Gas diffusion cathodes rely on the passive diffusion of oxygen from air to complete the ORR. The gas diffusion cathode developed for this study (GDC) had a novel PTFE and polyethylene (PE) diffusion layer. The gas diffusion layer was heat pressed onto a carbon cloth substrate. The carbon cloth substrate was used as a current collector and support for the catalytic layer. Different combinations and concentrations of catalyst and binder were evaluated in this study. Activated carbon, nickel, plain carbon and non-platinum based catalysts were tested. After the best catalyst had been selected, different binder materials were evaluated. These include PTFE, PE, and a PTFE/Polyethylene glycol mixture.

The initial electrochemical characterization of the cathodes was performed in a three-electrode setup with a titanium mesh counter electrode and Ag/AgCl reference electrode. 0.1M phosphate buffer solution was used as the electrolyte. Durability studies of the cathode were conducted in a single chamber MFC, with swine waste as the organic substrate and carbon brush as the anode.
Potentiostatic polarization curves were carried out to evaluate the influence of the catalyst and the binder on the cathode performance (Fig. 1). As can be seen, the non-platinum based catalyst demonstrated the highest performance, with a current density of 0.34 mA/cm2 at -0.2 V vs. Ag/AgCl, followed by the activated carbon/carbon black catalytic layer with current output of 0.14 mA/cm2 at the same potential. The cathode with PE as the binder (Fig. 1b) showed the highest performance and reproducibility, but had low durability. It has also been established that MFC operation under continuous flow results in a loss of cathode performance, attributed to the presence of pollutants in the wastewater.

Figure 1
Paper-Based Biofuel Array for Self-Powered Wearable Biosensors
Authors: Shitanda Isao , Momiyama Misaki , Nohara Saki , Iwashita Risa , Tsujimura Seiya , Hoshi Yoshinao , Itagaki Masayuki 
Published: February 2020

We name the Printable Electrochemistry for the development field of printable electrochemical devices [1,2]. Recently, we focus on several paper-based fully-printable electrochemical devices such as biofuel cell [3], biosensor [4] and reference electrode [5].
Paper-based biofuel cell have been attracted as a potential application as energy harvesting power sources in Internet of things (IoT) field [6,7]. In the present study, we newly developed paper-based wearable biofuel cell array fabricated by screen-printing.
Figure 1 shows a schematic illustration of one of our wearable biofuel cell array. The paper-based biofuel cell array exhibited a maximum power density of 1 mW. The present flexible paper-based biofuel cell is highly applicable to the development of low cost, flexible, ubiquitous energy devices. In the present study, we discuss the characteristics of the wearable biofuel cells in detail.
[1] I. Shitanda et al., Electrochim. Acta 54 (2009) 4933.
[2] I. Shitanda et al., Sens. Actu. B: Chem. 160 (2011) 1606.
[3] I. Shitanda et al., Chem. Commun. 49 (2013) 11110.
[4] I. Shitanda et al., Chem. Lett. 42 (2013) 1369.
[5] I.Shitanda et al., Analyst, 140 (2015) 6481.
[6] Claudia W. Narváez Villarrubia et al., Electrochem. Commun, 45 (2014) 44.
[7] Carolin Lau et al., Int. J. Hydrogen. Energy, 42 (2015) 14661.

Figure 1
Electrocatalytic CO2 Reduction on Nanosized Ag Dendrites Electrodeposited on Indium Doped SnO2 Electrodes Immersed in Aprotic Medium
Authors: Banda-Alemán Jorge Alberto , Sepúlveda Selene , Manríquez Juan 
Published: February 2020

Electrochemical reduction of CO2 by means of metallic nanostructures (i.e. Ag, Au, Cu), sp2 carbon derivatives (i.e. graphite oxide, graphene) and their combinations is considered as a promising pathway for aiding to decrease the effects of the global warming. However, the electrochemical reduction of CO2 contained in aqueous medium requires large overpotentials with a significant competition with the H2 evolution reaction, thus resulting in low faradaic efficiencies. On the other hand, reactivity of metallic nanostructures is strongly dependent from the size and the aspect ratio in nanoparticles and nanorods, respectively, as well as from the crystalline faces exposed to the electrolytic medium. In order to overcome this trouble, we studied the electrocatalytic CO2 electroreduction in aprotic medium by employing nanosized Ag dendrites, which were previously electrodeposited on In-doped SnO2 (ITO) electrodes by means of a double-pulse potential (DPP) technique (deposition conditions were defined by means of cyclic voltammetry (CV) technique). These experiments were carried out in a three-electrode cell containing aqueous 0.1M KNO3+1mM AgNO3. In this sense, the presence of dendritic nanostructures on the silver-modified ITO electrodes (ITO/Ag) was confirmed by scanning electron microscopy. CV results showed that the electrical charge associated to the Ag dissolution is clearly dependent from the growth time (duration ~ms) and independent from the nucleation time (duration ~sec). This result demonstrated that the Ag deposition is kinetically-controlled by one-electron transfer. Furthermore, CV results demonstrated that the thermodynamic potential for the Ag reduction E°Ag+|Ag was observed at -0.32 vs. Ag|AgCl (3M NaCl) during the first scan but, it becomes less cathodic at E°Ag+|Ag= -0.08 vs. Ag|AgCl (3M NaCl) during the successive scans; thus confirming that the dendritic shape of the Ag deposits is promoted immediately after some seeds of metallic atoms are confined on the ITO surface. Complementarily, electrochemical CO2 reduction in a three-electrode cell containing propylene carbonate + 0.1M Bu4NPF6 was confirmed on the as-prepared ITO/Ag electrodes by means of linear voltammetry (LV). In this way, two reduction peaks were localized at -0.3 and -0.5V vs. Ag|AgCl (0.01M AgNO3 + 0.1M Bu4NCl in MeCN), which can be associated to the semireactions 1 and 3, respectively. Electrochemical contribution from the ITO substrate was absent during the CO2 reduction reaction.
(1) CO2 + e- → CO2
·
-
(slow)
(2) CO2 + CO2
·
-
→ (CO2)2
·
-

(3) (CO2)2
·
-
+ e- → -OOC-COO·
-