scholarly journals Enzymatic Hydrogen Electrosynthesis at Enhanced Current Density Using a Redox Polymer

Catalysts ◽  
2021 ◽  
Vol 11 (10) ◽  
pp. 1197
Author(s):  
John C. Ruth ◽  
Fabian M. Schwarz ◽  
Volker Müller ◽  
Alfred M. Spormann

High-temperature tolerant enzymes offer multiple advantages over enzymes from mesophilic organisms for the industrial production of sustainable chemicals due to high specific activities and stabilities towards fluctuations in pH, heat, and organic solvents. The production of molecular hydrogen (H2) is of particular interest because of the multiple uses of hydrogen in energy and chemicals applications, and the ability of hydrogenase enzymes to reduce protons to H2 at a cathode. We examined the activity of Hydrogen-Dependent CO2 Reductase (HDCR) from the thermophilic bacterium Thermoanaerobacter kivui when immobilized in a redox polymer, cobaltocene-functionalized polyallylamine (Cc-PAA), on a cathode for enzyme-mediated H2 formation from electricity. The presence of Cc-PAA increased reductive current density 340-fold when used on an electrode with HDCR at 40 °C, reaching unprecedented current densities of up to 3 mA·cm−2 with minimal overpotential and high faradaic efficiency. In contrast to other hydrogenases, T. kivui HDCR showed substantial reversibility of CO-dependent inactivation, revealing an opportunity for usage in gas mixtures containing CO, such as syngas. This study highlights the important potential of combining redox polymers with novel enzymes from thermophiles for enhanced electrosynthesis.

Author(s):  
Xiulin Yang ◽  
Defei Liu ◽  
Shenghong Zhong ◽  
Xiaofeng Zhou ◽  
Kuo-Wei Huang ◽  
...  

Selective conversion of CO2 to formate with high current densities is highly desirable but still challenging. Copper hollow fibers with interconnected pore structures were fabricated via a facile method and used as a stand-alone cathode for highly efficient electrochemical reduction of CO2 to formate. Our studies revealed that delivering the reactant CO2 gas to the inner space of the hollow fiber could build up a higher CO2 partial pressure in the pores and presumably reduce the concentration of H[Formula: see text] from the electrolyte to effectively suppress the major competing reaction, hydrogen evolution reaction (HER), from 46.9% faradaic efficiency (FE) to 15.0%. A high selectivity for CO2 reduction to formate with a maximum FE of 77.1% was achieved with a high current density of 34.7[Formula: see text]mA cm[Formula: see text], which is one of the highest FEs on Cu-based materials. Mechanistic studies suggest that the abundant active sites along with the unique crystal facets induced by the high pressure of CO2 at the pore surface in the “gas in” mode are attributed to the superior electroactivity and selectivity for the CO2 reduction to formate. The Cu hollow fiber electrodes exhibit an outstanding long-term stability at high current density, showing great potential for large-scale practical applications.


Author(s):  
I-Fei Tsu ◽  
D.L. Kaiser ◽  
S.E. Babcock

A current theme in the study of the critical current density behavior of YBa2Cu3O7-δ (YBCO) grain boundaries is that their electromagnetic properties are heterogeneous on various length scales ranging from 10s of microns to ˜ 1 Å. Recently, combined electromagnetic and TEM studies on four flux-grown bicrystals have demonstrated a direct correlation between the length scale of the boundaries’ saw-tooth facet configurations and the apparent length scale of the electrical heterogeneity. In that work, enhanced critical current densities are observed at applied fields where the facet period is commensurate with the spacing of the Abrikosov flux vortices which must be pinned if higher critical current density values are recorded. To understand the microstructural origin of the flux pinning, the grain boundary topography and grain boundary dislocation (GBD) network structure of [001] tilt YBCO bicrystals were studied by TEM and HRTEM.


Author(s):  
M. R. McCartney ◽  
J. K. Weiss ◽  
David J. Smith

It is well-known that electron-beam irradiation within the electron microscope can induce a variety of surface reactions. In the particular case of maximally-valent transition-metal oxides (TMO), which are susceptible to electron-stimulated desorption (ESD) of oxygen, it is apparent that the final reduced product depends, amongst other things, upon the ionicity of the original oxide, the energy and current density of the incident electrons, and the residual microscope vacuum. For example, when TMO are irradiated in a high-resolution electron microscope (HREM) at current densities of 5-50 A/cm2, epitaxial layers of the monoxide phase are found. In contrast, when these oxides are exposed to the extreme current density probe of an EM equipped with a field emission gun (FEG), the irradiated area has been reported to develop either holes or regions almost completely depleted of oxygen. ’ In this paper, we describe the responses of three TMO (WO3, V2O5 and TiO2) when irradiated by the focussed probe of a Philips 400ST FEG TEM, also equipped with a Gatan 666 Parallel Electron Energy Loss Spectrometer (P-EELS). The multi-channel analyzer of the spectrometer was modified to take advantage of the extremely rapid acquisition capabilities of the P-EELS to obtain time-resolved spectra of the oxides during the irradiation period. After irradiation, the specimens were immediately removed to a JEM-4000EX HREM for imaging of the damaged regions.


Coatings ◽  
2021 ◽  
Vol 11 (1) ◽  
pp. 56
Author(s):  
Ashutosh Sharma ◽  
Byungmin Ahn

Metallic and alloyed coatings are used widely in several decorative and technology-based applications. In this work, we selected Sn coatings plated on Cu substrates for joining applications. We employed two different plating baths for the fabrication of Sn and Ni coatings: acidic stannous sulfate for Sn and Watts bath for Ni layer. The plating current densities were varied from 100–500 mA/cm2. Further, the wear and friction behavior of the coatings were studied using a ball-on-disc apparatus under dry sliding conditions. The impact of current density was studied on the morphology, wear, and coefficient of friction (COF) of the resultant coatings. The wear experiments were done at various loads from 2–10 N. The sliding distance was fixed to 7 m. The wear loss was quantified in terms of the volume of the track geometry (width and depth of the tracks). The results indicate that current density has an important role in tailoring the composition and morphology of coatings, which affects the wear properties. At higher loads (8–10 N), Sn coatings on Ni/Cu had higher volume loss with a stable COF due to a mixed adhesive and oxidative type of wear mechanism.


1987 ◽  
Vol 120 ◽  
pp. 167-169
Author(s):  
Valerio Pirronello

The problem of the formation of molecular hydrogen in interstellar clouds is revisited. the role played by cosmic ray bombardment under certain circumstances is considered mainly in the light of the low formation rate of H2 on grains due to the reduced mobility of adsorbed H atoms on their amorphous surfaces at interstellar temperatures.


2012 ◽  
Vol 302 (8) ◽  
pp. H1645-H1654 ◽  
Author(s):  
Toshihide Kashihara ◽  
Tsutomu Nakada ◽  
Hisashi Shimojo ◽  
Miwa Horiuchi-Hirose ◽  
Simmon Gomi ◽  
...  

L-type Ca2+ channels (LTCCs) play an essential role in the excitation-contraction coupling of ventricular myocytes. We previously found that t-tubular (TT) LTCC current density was halved by the activation of protein phosphatase (PP)1 and/or PP2A, whereas surface sarcolemmal (SS) LTCC current density was increased by the inhibition of PP1 and/or PP2A activity in failing ventricular myocytes of mice chronically treated with isoproterenol (ISO mice). In the present study, we examined the possible involvement of inhibitory heterotrimeric G proteins (Gi/o) in these abnormalities by chronically administrating pertussis toxin (PTX) to ISO mice (ISO + PTX mice). Compared with ISO mice, ISO + PTX mice exhibited significantly higher fractional shortening of the left ventricle. The expression level of Gαi2 proteins was not altered by the treatment of mice with ISO and/or PTX. ISO + PTX myocytes had normal TT and SS LTCC current densities because they had higher and lower availability and/or open probability of TT and SS LTCCs than ISO myocytes, respectively. A selective PKA inhibitor, H-89, did not affect LTCC current densities in ISO + PTX myocytes. A selective PP2A inhibitor, fostriecin, did not affect SS or TT current density in control or ISO + PTX myocytes but significantly increased TT but not SS LTCC current density in ISO myocytes. These results indicate that chronic receptor-mediated activation of Gi/o in vivo decreases basal TT LTCC activity by activating PP2A and increases basal SS LTCC activity by inhibiting PP1 without modulating PKA in heart failure.


2015 ◽  
Vol 112 (52) ◽  
pp. 15809-15814 ◽  
Author(s):  
Sheng Zhang ◽  
Peng Kang ◽  
Mohammed Bakir ◽  
Alexander M. Lapides ◽  
Christopher J. Dares ◽  
...  

Developing sustainable energy strategies based on CO2 reduction is an increasingly important issue given the world’s continued reliance on hydrocarbon fuels and the rise in CO2 concentrations in the atmosphere. An important option is electrochemical or photoelectrochemical CO2 reduction to carbon fuels. We describe here an electrodeposition strategy for preparing highly dispersed, ultrafine metal nanoparticle catalysts on an electroactive polymeric film including nanoalloys of Cu and Pd. Compared with nanoCu catalysts, which are state-of-the-art catalysts for CO2 reduction to hydrocarbons, the bimetallic CuPd nanoalloy catalyst exhibits a greater than twofold enhancement in Faradaic efficiency for CO2 reduction to methane. The origin of the enhancement is suggested to arise from a synergistic reactivity interplay between Pd–H sites and Cu–CO sites during electrochemical CO2 reduction. The polymer substrate also appears to provide a basis for the local concentration of CO2 resulting in the enhancement of catalytic current densities by threefold. The procedure for preparation of the nanoalloy catalyst is straightforward and appears to be generally applicable to the preparation of catalytic electrodes for incorporation into electrolysis devices.


Author(s):  
Cindy X. Su ◽  
Luyao Xu ◽  
Frank Y. Cheng

In this work, a real-time AC/DC signal data acquisition (DAQ) technique was developed, which is capable of separating the DC and AC potential components from the recorded total potential, providing mechanistic information about the steel corrosion in the presence of AC interference. It was found that the corrosion of the steel is enhanced by the applied AC current density from 0 to 400 A/m2. With the further increase to 600 A/m2 and 800 A/m2, the corrosion rate of the steel decreases, which is attributed to passivation of the steel at sufficiently high AC current densities, and a compact film is formed on the steel surface. Moreover, the derived mathematic relationships between AC potential and AC current density provides a potential alternative to determine AC current density on pipelines based on measurements of AC potential in the field.


1994 ◽  
Vol 369 ◽  
Author(s):  
Steen Skaarup ◽  
L.M.W.K. Gunaratne ◽  
Keld West ◽  
Birgit Zachau-Christiansen

AbstractPolyaniline has been synthesized in propylene carbonate by galvanostatic electrochemical polymerization at current densities between 16 and 1000 μA/cm2. Earlier results for polypyrrole have shown that low and high current density films have different properties: The films synthesized at low current density have a higher conjugation length and a more regular structure. The corresponding effect in PANI has been investigated by cyclic voltammetry and UV/visible spectroscopy. Simultaneous measurement of cyclic voltammograms and the absorbtion of selected spectral lines is used because of the complex nature of the PANI system which involves several redox systems as well as forms differing in the degree of protonation and morphology.The main result is that the method of galvanostatic synthesis at low current densities (-16 μA/cm2) produces polyaniline polymers of different, more conjugated and more regular structure than those prepared at higher current densities. The standard method of in situ layer-by-layer polymerization of conducting polymers during cyclic voltammetry often results in uncontrolled and unmeasured current densities of 0.5-2 mA/cm2 which produces a film that probably has a less regular structure containing more deviations from ideality.


2014 ◽  
Vol 635 ◽  
pp. 204-207 ◽  
Author(s):  
Ondrej Milkovič ◽  
Mária Hagarová ◽  
Jana Michaliková ◽  
Matúš Horváth

In this article we focused to influence of current density on the structure parameters evaluated by microdiffraction experiment in transmission mode using synchrotron radiation. For this purpose the coatings of Ni-Co alloy were deposited on the Cu substrate using different current densities during the electrodeposition process. The results of the microdiffraction experiment showed the structure uniformity of the coatings along their thickness, as well as changes in the structure parameters depending on the used current density during the deposition process.


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