scholarly journals Dynamic Tuning of a Thin Film Electrocatalyst by Tensile Strain

2019 ◽  
Vol 9 (1) ◽  
Author(s):  
Eric E. Benson ◽  
Mai-Anh Ha ◽  
Brian. A. Gregg ◽  
Jao van de Lagemaat ◽  
Nathan R. Neale ◽  
...  
Keyword(s):  
Active Sites ◽  
Tensile Strain ◽  
Reaction Pathway ◽  
Drastic Reduction ◽  
Onset Potential ◽  
Dynamic Tuning ◽  
Precious Metal Catalysts ◽  
Surface Active ◽  
Static Conditions ◽  
A Current

Abstract We report the ability to tune the catalytic activities for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) by applying mechanical stress on a highly n-type doped rutile TiO2 films. We demonstrate through operando electrochemical experiments that the low HER activity of TiO2 can reversibly approach those of the state-of-the-art non-precious metal catalysts when the TiO2 is under tensile strain. At 3% tensile strain, the HER overpotential required to generate a current density of 1 mA/cm2 shifts anodically by 260 mV to give an onset potential of 125 mV, representing a drastic reduction in the kinetic overpotential. A similar albeit smaller cathodic shift in the OER overpotential is observed when tensile strain is applied to TiO2. Results suggest that significant improvements in HER and OER activities with tensile strain are due to an increase in concentration of surface active sites and a decrease in kinetic and thermodynamics barriers along the reaction pathway(s). Our results highlight that strain applied to TiO2 by precisely controlled and incrementally increasing (i.e. dynamic) tensile stress is an effective tool for dynamically tuning the electrocatalytic properties of HER and OER electrocatalysts relative to their activities under static conditions.

Catalytic Resonance Theory: Parallel Reaction Pathway Control

2019 ◽  
Author(s):  
M. Alexander Ardagh ◽  
Manish Shetty ◽  
Anatoliy Kuznetsov ◽  
Qi Zhang ◽  
Phillip Christopher ◽  
...  
Keyword(s):  
Chemical Reactions ◽  
Active Site ◽  
Active Sites ◽  
Reaction Pathway ◽  
Control Strategies ◽  
Oscillation Amplitude ◽  
Catalytic Performance ◽  
Parallel Reaction ◽  
Resonance Theory ◽  
Static Conditions

Catalytic enhancement of chemical reactions via heterogeneous materials occurs through stabilization of transition states at designed active sites, but dramatically greater rate acceleration on that same active site is achieved when the surface intermediates oscillate in binding energy. The applied oscillation amplitude and frequency can accelerate reactions orders of magnitude above the catalytic rates of static systems, provided the active site dynamics are tuned to the natural frequencies of the surface chemistry. In this work, differences in the characteristics of parallel reactions are exploited via selective application of active site dynamics (0 < ΔU < 1.0 eV amplitude, 10<sup>-6</sup> < f < 10<sup>4</sup> Hz frequency) to control the extent of competing reactions occurring on the shared catalytic surface. Simulation of multiple parallel reaction systems with broad range of variation in chemical parameters revealed that parallel chemistries are highly tunable in selectivity between either pure product, even when specific products are not selectively produced under static conditions. Two mechanisms leading to dynamic selectivity control were identified: (i) surface thermodynamic control of one product species under strong binding conditions, or (ii) catalytic resonance of the kinetics of one reaction over the other. These dynamic parallel pathway control strategies applied to a host of chemical conditions indicate significant potential for improving the catalytic performance of many important industrial chemical reactions beyond their existing static performance.

scholarly journals Flexible freestanding MoS2-based composite paper for energy conversion and storage

2019 ◽  
Vol 10 ◽  
pp. 1488-1496 ◽  
Author(s):  
Florian Zoller ◽  
Jan Luxa ◽  
Thomas Bein ◽  
Dina Fattakhova-Rohlfing ◽  
Daniel Bouša ◽  
...  
Keyword(s):  
Composite Material ◽  
Energy Storage ◽  
Mechanical Strength ◽  
Current Density ◽  
Active Sites ◽  
High Energy ◽  
Onset Potential ◽  
High Flexibility ◽  
A Current ◽  
Composite Paper

The construction of flexible electrochemical devices for energy storage and generation is of utmost importance in modern society. In this article, we report on the synthesis of flexible MoS2-based composite paper by high-energy shear force milling and simple vacuum filtration. This composite material combines high flexibility, mechanical strength and good chemical stability. Chronopotentiometric charge–discharge measurements were used to determine the capacitance of our paper material. The highest capacitance achieved was 33 mF·cm−2 at a current density of 1 mA·cm−2, demonstrating potential application in supercapacitors. We further used the material as a cathode for the hydrogen evolution reaction (HER) with an onset potential of approximately −0.2 V vs RHE. The onset potential was even lower (approximately −0.1 V vs RHE) after treatment with n-butyllithium, suggesting the introduction of new active sites. Finally, a potential use in lithium ion batteries (LIB) was examined. Our material can be used directly without any binder, additive carbon or copper current collector and delivers specific capacity of 740 mA·h·g−1 at a current density of 0.1 A·g−1. After 40 cycles at this current density the material still reached a capacity retention of 91%. Our findings show that this composite material could find application in electrochemical energy storage and generation devices where high flexibility and mechanical strength are desired.

Catalytic Resonance Theory: Parallel Reaction Pathway Control

2019 ◽  
Author(s):  
M. Alexander Ardagh ◽  
Manish Shetty ◽  
Anatoliy Kuznetsov ◽  
Qi Zhang ◽  
Phillip Christopher ◽  
...  
Keyword(s):  
Chemical Reactions ◽  
Active Site ◽  
Active Sites ◽  
Reaction Pathway ◽  
Control Strategies ◽  
Oscillation Amplitude ◽  
Catalytic Performance ◽  
Parallel Reaction ◽  
Resonance Theory ◽  
Static Conditions

Catalytic enhancement of chemical reactions via heterogeneous materials occurs through stabilization of transition states at designed active sites, but dramatically greater rate acceleration on that same active site is achieved when the surface intermediates oscillate in binding energy. The applied oscillation amplitude and frequency can accelerate reactions orders of magnitude above the catalytic rates of static systems, provided the active site dynamics are tuned to the natural frequencies of the surface chemistry. In this work, differences in the characteristics of parallel reactions are exploited via selective application of active site dynamics (0 < ΔU < 1.0 eV amplitude, 10<sup>-6</sup> < f < 10<sup>4</sup> Hz frequency) to control the extent of competing reactions occurring on the shared catalytic surface. Simulation of multiple parallel reaction systems with broad range of variation in chemical parameters revealed that parallel chemistries are highly tunable in selectivity between either pure product, even when specific products are not selectively produced under static conditions. Two mechanisms leading to dynamic selectivity control were identified: (i) surface thermodynamic control of one product species under strong binding conditions, or (ii) catalytic resonance of the kinetics of one reaction over the other. These dynamic parallel pathway control strategies applied to a host of chemical conditions indicate significant potential for improving the catalytic performance of many important industrial chemical reactions beyond their existing static performance.

A Pyridinic Fe-N4 Macrocycle Effectively Models the Active Sites in Fe/N-Doped Carbon Electrocatalysts

2020 ◽  
Author(s):  
Travis Marshall-Roth ◽  
Nicole J. Libretto ◽  
Alexandra T. Wrobel ◽  
Kevin Anderton ◽  
Nathan D. Ricke ◽  
...  
Keyword(s):  
Oxygen Reduction ◽  
Active Sites ◽  
Catalytic Properties ◽  
Reduction Reaction ◽  
Iron Phthalocyanine ◽  
Electrochemical Studies ◽  
Onset Potential ◽  
Nitrogen Doped Carbon ◽  
Iron Active Sites

Iron- and nitrogen-doped carbon (Fe-N-C) materials are leading candidates to replace platinum in fuel cells, but their active site structures are poorly understood. A leading postulate is that iron active sites in this class of materials exist in an Fe-N<sub>4</sub> pyridinic ligation environment. Yet, molecular Fe-based catalysts for the oxygen reduction reaction (ORR) generally feature pyrrolic coordination and pyridinic Fe-N<sub>4</sub> catalysts are, to the best of our knowledge, non-existent. We report the synthesis and characterization of a molecular pyridinic hexaazacyclophane macrocycle, (phen<sub>2</sub>N<sub>2</sub>)Fe, and compare its spectroscopic, electrochemical, and catalytic properties for oxygen reduction to a prototypical Fe-N-C material, as well as iron phthalocyanine, (Pc)Fe, and iron octaethylporphyrin, (OEP)Fe, prototypical pyrrolic iron macrocycles. N 1s XPS signatures for coordinated N atoms in (phen<sub>2</sub>N<sub>2</sub>)Fe are positively shifted relative to (Pc)Fe and (OEP)Fe, and overlay with those of Fe-N-C. Likewise, spectroscopic XAS signatures of (phen<sub>2</sub>N<sub>2</sub>)Fe are distinct from those of both (Pc)Fe and (OEP)Fe, and are remarkably similar to those of Fe-N-C with compressed Fe–N bond lengths of 1.97 Å in (phen<sub>2</sub>N<sub>2</sub>)Fe that are close to the average 1.94 Å length in Fe-N-C. Electrochemical studies establish that both (Pc)Fe and (phen<sub>2</sub>N<sub>2</sub>)Fe have relatively high Fe(III/II) potentials at ~0.6 V, ~300 mV positive of (OEP)Fe. The ORR onset potential is found to directly correlate with the Fe(III/II) potential leading to a ~300 mV positive shift in the onset of ORR for (Pc)Fe and (phen<sub>2</sub>N<sub>2</sub>)Fe relative to (OEP)Fe. Consequently, the ORR onset for (phen<sub>2</sub>N<sub>2</sub>)Fe and (Pc)Fe is within 150 mV of Fe-N-C. Unlike (OEP)Fe and (Pc)Fe, (phen<sub>2</sub>N<sub>2</sub>)Fe displays excellent selectivity for 4-electron ORR with <4% maximum H<sub>2</sub>O<sub>2</sub> production, comparable to Fe-N-C materials. The aggregate spectroscopic and electrochemical data establish (phen<sub>2</sub>N<sub>2</sub>)Fe as a pyridinic iron macrocycle that effectively models Fe-N-C active sites, thereby providing a rich molecular platform for understanding this important class of catalytic materials.<p><b></b></p>

Dose COVID-19 Uncovered a New Feature of Metronidazole Drug?

2020 ◽  
Author(s):  
Mohammad Seyedhamzeh ◽  
Bahareh Farasati Far ◽  
Mehdi Shafiee Ardestani ◽  
Shahrzad Javanshir ◽  
Fatemeh Aliabadi ◽  
...  
Keyword(s):  
Molecular Docking ◽  
Drug Discovery ◽  
Virtual Screening ◽  
Active Sites ◽  
Initial Plasma ◽  
New Feature ◽  
Metronidazole Benzoate ◽  
Global Health Problem ◽  
A Current ◽  
Pro Inflammatory Cytokines

Studies of coronavirus disease 2019 (COVID-19) as a current global health problem shown the initial plasma levels of most pro-inflammatory cytokines increased during the infection, which leads to patient countless complications. Previous studies also demonstrated that the metronidazole (MTZ) administration reduced related cytokines and improved treatment in patients. However, the effect of this drug on cytokines has not been determined. In the present study, the interaction of MTZ with cytokines was investigated using molecular docking as one of the principal methods in drug discovery and design. According to the obtained results, the IL12-metronidazole complex is more stable than other cytokines, and an increase in the surface and volume leads to prevent to bind to receptors. Moreover, ligand-based virtual screening of several libraries showed metronidazole phosphate, metronidazole benzoate, 1-[1-(2-Hydroxyethyl)-5- nitroimidazol-2-yl]-N-methylmethanimine oxide, acyclovir, and tetrahydrobiopterin (THB or BH4) like MTZ by changing the surface and volume prevents binding IL-12 to the receptor. Finally, the inhibition of the active sites of IL-12 occurred by modifying the position of the methyl and hydroxyl functional groups in MTZ. <br>

2,2’-Dipyridylamine as Organic Molecular Electrocatalyst for Hydrogen Evolution Reaction in Acidic Electrolytes

2019 ◽  
Author(s):  
Xi Yin ◽  
Ling Lin ◽  
Hoon T. Chung ◽  
Ulises Martinez ◽  
Andrew M. Baker ◽  
...  
Keyword(s):  
Hydrogen Evolution ◽  
Hydrogen Evolution Reaction ◽  
Density Functional ◽  
Low Cost ◽  
Membrane Electrode Assembly ◽  
Carbon Surface ◽  
Membrane Electrode ◽  
Durability Test ◽  
Onset Potential ◽  
Precious Metal Catalysts

Finding a low-cost and stable electrocatalyst for hydrogen evolution reaction (HER) as a replacement for scarce and expensive precious metal catalysts has attracted significant interest from chemical and materials research communities. Here, we demonstrate an organic catalyst based on 2,2’-dipyridylamine (dpa) molecules adsorbed on carbon surface, which shows remarkable hydrogen evolution activity and performance durability in strongly acidic polymer electrolytes without involving any metal. The HER onset potential at dpa adsorbed on carbon has been found to be less than 50 mV in sulfuric acid and in a Nafion-based membrane electrode assembly (MEA). At the same time, this catalyst has shown no performance loss in a 60-hour durability test. The HER reaction mechanisms and the low onset overpotential in this system are revealed based on electrochemical study. Density functional theory (DFT) calculations suggest that the pyridyl-N functions as the active site for H adsorption with a free energy of -0.13 eV, in agreement with the unusually low onset overpotential for an organic molecular catalyst.<br>

2,2’-Dipyridylamine as Organic Molecular Electrocatalyst for Hydrogen Evolution Reaction in Acidic Electrolytes

2019 ◽  
Author(s):  
Xi Yin ◽  
Ling Lin ◽  
Hoon T. Chung ◽  
Ulises Martinez ◽  
Andrew M. Baker ◽  
...  
Keyword(s):  
Hydrogen Evolution ◽  
Hydrogen Evolution Reaction ◽  
Density Functional ◽  
Low Cost ◽  
Membrane Electrode Assembly ◽  
Carbon Surface ◽  
Membrane Electrode ◽  
Durability Test ◽  
Onset Potential ◽  
Precious Metal Catalysts

Finding a low-cost and stable electrocatalyst for hydrogen evolution reaction (HER) as a replacement for scarce and expensive precious metal catalysts has attracted significant interest from chemical and materials research communities. Here, we demonstrate an organic catalyst based on 2,2’-dipyridylamine (dpa) molecules adsorbed on carbon surface, which shows remarkable hydrogen evolution activity and performance durability in strongly acidic polymer electrolytes without involving any metal. The HER onset potential at dpa adsorbed on carbon has been found to be less than 50 mV in sulfuric acid and in a Nafion-based membrane electrode assembly (MEA). At the same time, this catalyst has shown no performance loss in a 60-hour durability test. The HER reaction mechanisms and the low onset overpotential in this system are revealed based on electrochemical study. Density functional theory (DFT) calculations suggest that the pyridyl-N functions as the active site for H adsorption with a free energy of -0.13 eV, in agreement with the unusually low onset overpotential for an organic molecular catalyst.<br>

Role of the Structure and Electronic Properties of Fe2O3-MoO3 Catalyst on the Dehydration of Isopropyl Alcohol

1993 ◽  
Vol 58 (7) ◽  
pp. 1591-1599 ◽  
Author(s):  
Abd El-Aziz A. Said
Keyword(s):  
Active Sites ◽  
Isopropyl Alcohol ◽  
Oxide Catalyst ◽  
Flow System ◽  
Charge Carriers ◽  
X Ray Diffraction ◽  
X Ray ◽  
Catalyst Composition ◽  
Surface Active

Molybdenum oxide catalyst doped or mixed with (1 - 50) mole % Fe3+ ions were prepared. The structure of the original samples and the samples calcined at 400 °C were characterized using DTA, X-ray diffraction and IR spectra. Measurements of the electrical conductivity of calcined samples with and without isopropyl alcohol revealed that the conductance increases on increasing the content of Fe3+ ions up to 50 mole %. The activation energies of charge carriers were determined in presence and absence of the alcohol. The catalytic dehydration of isopropyl alcohol was carried out at 250 °C using a flow system. The results obtained showed that the doped or mixed catalysts are active and selective towards propene formation. However, the catalyst containing 40 mole % Fe3+ ions exhibited the highest activity and selectivity. Correlations were attempted to the catalyst composition with their electronic and catalytic properties. Probable mechanism for the dehydration process is proposed in terms of surface active sites.

scholarly journals Defect-Rich Heterogeneous MoS2/rGO/NiS Nanocomposite for Efficient pH-Universal Hydrogen Evolution

Nanomaterials ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 662 ◽  
Author(s):  
Guangsheng Liu ◽  
Kunyapat Thummavichai ◽  
Xuefeng Lv ◽  
Wenting Chen ◽  
Tingjun Lin ◽  
...  
Keyword(s):  
Graphene Oxide ◽  
Hydrogen Evolution ◽  
Hydrogen Evolution Reaction ◽  
Active Sites ◽  
Reduced Graphene ◽  
Heterogeneous Interfaces ◽  
Wide Ph Range ◽  
Ph Range ◽  
A Current ◽  
Poor Stability

Molybdenum disulfide (MoS2) has been universally demonstrated to be an effective electrocatalytic catalyst for hydrogen evolution reaction (HER). However, the low conductivity, few active sites and poor stability of MoS2-based electrocatalysts hinder its hydrogen evolution performance in a wide pH range. The introduction of other metal phases and carbon materials can create rich interfaces and defects to enhance the activity and stability of the catalyst. Herein, a new defect-rich heterogeneous ternary nanocomposite consisted of MoS2, NiS and reduced graphene oxide (rGO) are synthesized using ultrathin αNi(OH)2 nanowires as the nickel source. The MoS2/rGO/NiS-5 of optimal formulation in 0.5 M H2SO4, 1.0 M KOH and 1.0 M PBS only requires 152, 169 and 209 mV of overpotential to achieve a current density of 10 mA cm−2 (denoted as η10), respectively. The excellent HER performance of the MoS2/rGO/NiS-5 electrocatalyst can be ascribed to the synergistic effect of abundant heterogeneous interfaces in MoS2/rGO/NiS, expanded interlayer spacings, and the addition of high conductivity graphene oxide. The method reported here can provide a new idea for catalyst with Ni-Mo heterojunction, pH-universal and inexpensive hydrogen evolution reaction electrocatalyst.

Cathodic Corrosion Activated Fe-based Nanoglass as Highly-Active and -Stable Oxygen Evolution Catalyst for Water Splitting

2021 ◽  
Author(s):  
Kaiyao Wu ◽  
Fei Chu ◽  
Yuying Meng ◽  
Kaveh Edalati ◽  
Qingsheng Gao ◽  
...  
Keyword(s):  
Water Splitting ◽  
Oxygen Evolution ◽  
Oxygen Evolution Reaction ◽  
Amorphous Alloys ◽  
Precious Metal ◽  
Active Sites ◽  
Metal Free ◽  
Highly Active ◽  
Stable Oxygen ◽  
Surface Active

Transition metal-based amorphous alloys have attracted increasing attention as precious-metal-free electrocatalysts for oxygen evolution reaction (OER) of water splitting due to their high macro-conductivity and abundant surface active sites. However,...

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