scholarly journals Probing the Effects of Electron Deficient Aryl Substituents and a π‐System Extended NHC Ring on the Photocatalytic CO 2 Reduction Reaction with Re‐pyNHC‐Aryl Complexes**

ChemPhotoChem ◽  
2021 ◽  
Author(s):  
Hunter Shirley ◽  
Thomas More Sexton ◽  
Nalaka P. Liyanage ◽  
Morgan A. Perkins ◽  
Shane A. Autry ◽  
...  
Keyword(s):  
Reduction Reaction ◽  
Aryl Complexes

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>

Promoting Nitrogen Electroreduction to Ammonia with Bismuth Nanocrystals and Potassium Cations in Water

2020 ◽  
Author(s):  
Jaecheol Choi ◽  
Hoang-Long Du ◽  
Manjunath Chatti ◽  
Bryan H. R. Suryanto ◽  
Alexandr Simonov ◽  
...  
Keyword(s):  
Electrocatalytic Activity ◽  
Aqueous Electrolyte ◽  
Electrolyte Solutions ◽  
Reduction Reaction ◽  
Nitrogen Reduction ◽  
Aqueous Electrolyte Solutions

We demonstrate that bismuth exhibits no measurable electrocatalytic activity for the nitrogen reduction reaction to ammonia in aqueous electrolyte solutions, contrary to several recent reports on the highly impressive rates of Bi-catalysed electrosynthesis of NH<sub>3</sub> from N<sub>2</sub>.

Graphene Supported Tungsten Carbide as Catalyst for Electrochemical Reduction of CO2

2019 ◽  
Author(s):  
Sahithi Ananthaneni ◽  
Rees Rankin
Keyword(s):  
Tungsten Carbide ◽  
Electrochemical Reduction ◽  
Low Cost ◽  
Co2 Reduction ◽  
Platinum Group Metal ◽  
Reduction Reaction ◽  
Metal Carbides ◽  
Depth Study ◽  
Reduction Of Co2 ◽  
Co2 Reduction Reaction

<div>Electrochemical reduction of CO2 to useful chemical and fuels in an energy efficient way is currently an expensive and inefficient process. Recently, low-cost transition metal-carbides (TMCs) are proven to exhibit similar electronic structure similarities to Platinum-Group-Metal (PGM) catalysts and hence can be good substitutes for some important reduction reactions. In this work, we test graphenesupported WC (Tungsten Carbide) nanocluster as an electrocatalyst for the CO2 reduction reaction. Specifically, we perform DFT studies to understand various possible reaction mechanisms and determine the lowest thermodynamic energy landscape of CO2 reduction to various products such as CO, HCOOH, CH3OH, and CH4. This in-depth study of reaction energetics could lead to improvements and develop more efficient electrocatalysts for CO2 reduction.<br></div>

Ordered Intermetallic Nanoparticles with High Catalytic Activity Prepared by an Electrochemically Induced Phase Transformation

2019 ◽  
Author(s):  
Du Sun ◽  
yunfei wang ◽  
Kenneth Livi ◽  
chuhong wang ◽  
ruichun luo ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Diffusion Mechanism ◽  
Reduction Reaction ◽  
Atomic Scale ◽  
High Catalytic Activity ◽  
Ambient Conditions ◽  
Magnetic Devices ◽  
Disordered Alloys ◽  
Ordered Intermetallic ◽  
Intermetallic Nanoparticles

<div> <p>The synthesis of alloys with long range atomic scale ordering (ordered intermetallics) is an emerging field of nanochemistry. Ordered intermetallic nanoparticles are useful for a wide variety of applications such as catalysis, superconductors, and magnetic devices. However, the preparation of nanostructured ordered intermetallics is challenging in comparison to disordered alloys, hindering progress in materials development. We report a process for converting colloidally synthesized ordered intermetallic PdBi<sub>2</sub> to ordered intermetallic Pd<sub>3</sub>Bi nanoparticles under ambient conditions by an electrochemically induced phase transition. The low melting point of PdBi<sub>2</sub> corresponds to low vacancy formation energies which enables the facile removal of the Bi from the surface, while simultaneously enabling interdiffusion of the constituent atoms via a vacancy diffusion mechanism under ambient conditions. The resulting phase-converted ordered intermetallic Pd<sub>3</sub>Bi exhibits 11x and 3.5x higher mass activty and high methanol tolerance for the oxygen reduction reaction compared to Pt/C and Pd/C, respectively,which is the highest reported for a Pd-based catalyst, to the best of our knowledge. These results establish a key development in the synthesis of noble metal rich ordered intermetallic phases with high catalytic activity, and sets forth guidelines for the design of ordered intermetallic compounds under ambient conditions.</p> </div>

High-Entropy Alloys as Catalysts for the CO2 and CO Reduction Reactions

2019 ◽  
Author(s):  
Jack Pedersen ◽  
Thomas Batchelor ◽  
Alexander Bagger ◽  
Jan Rossmeisl
Keyword(s):  
Density Functional ◽  
Rational Design ◽  
Hydrogen Adsorption ◽  
Co Adsorption ◽  
Reduction Reaction ◽  
Supervised Machine Learning ◽  
High Entropy Alloys ◽  
High Entropy ◽  
Co Reduction ◽  
Disordered Alloy

Using the high-entropy alloys (HEAs) CoCuGaNiZn and AgAuCuPdPt as starting points we provide a framework for tuning the composition of disordered multi-metallic alloys to control the selectivity and activity of the reduction of carbon dioxide (CO2) to highly reduced compounds. By combining density functional theory (DFT) with supervised machine learning we predicted the CO and hydrogen (H) adsorption energies of all surface sites on the (111) surface of the two HEAs. This allowed an optimization for the HEA compositions with increased likelihood for sites with weak hydrogen adsorption{to suppress the formation of molecular hydrogen (H2) and with strong CO adsorption to favor the reduction of CO. This led to the discovery of several disordered alloy catalyst candidates for which selectivity towards highly reduced carbon compounds is expected, as well as insights into the rational design of disordered alloy catalysts for the CO2 and CO reduction reaction.

N and S Co-doped Ordered Mesoporous Carbon: An Efficient Electrocatalyst for Oxygen Reduction Reaction in Microbial Fuel Cells

2020 ◽  
Vol 16 (4) ◽  
pp. 625-638
Author(s):  
Leila Samiee ◽  
Sedigheh Sadegh Hassani
Keyword(s):  
Oxygen Reduction Reaction ◽  
Oxygen Reduction ◽  
Microbial Fuel Cells ◽  
Carbon Materials ◽  
Reduction Reaction ◽  
Carbon Substrate ◽  
Promising Candidate ◽  
X Ray ◽  
Carbon Framework ◽  
Co Doped

Background: Porous carbon materials are promising candidate supports for various applications. In a number of these applications, doping of the carbon framework with heteroatoms provides a facile route to readily tune the carbon properties. The oxygen reduction reaction (ORR), where the reaction can be catalyzed without precious metals is one of the common applications for the heteroatom-doped carbons. Therefore, heteroatom doped catalysts might have a promising potential as a cathode in Microbial fuel cells (MFCs). MFCs have a good potential to produce electricity from biological oxidization of wastes at the anode and chemical reduction at the cathode. To the best of our knowledge, no studies have been yet reported on utilizing Sulfur trioxide pyridine (STP) and CMK-3 for the preparation of (N and S) doped ordered porous carbon materials. The presence of highly ordered mesostructured and the synergistic effect of N and S atoms with specific structures enhance the oxygen adsorption due to improving the electrocatalytic activity. So the optimal catalyst, with significant stability and excellent tolerance of methanol crossover can be a promising candidate for even other storage and conversion devices. Methods: The physico-chemical properties of the prepared samples were determined by Small Angle X-ray Diffraction (SAXRD), N2 sorption-desorption, Transmission Electron Microscopy (TEM), Field Emission Scanning Electron Microscopy (FESEM) and X-ray Photoelectron Spectroscopy (XPS). The prepared samples were further applied for oxygen reduction reaction (ORR) and the optimal cathode was tested with the Microbial Fuel Cell (MFC) system. Furthermore, according to structural analysis, The HRTEM, and SAXRD results confirmed the formation of well-ordered hexagonal (p6mm) arrays of mesopores in the direction of (100). The EDS and XPS approved that N and S were successfully doped into the CMK-3 carbon framework. Results: Among all the studied CMK-3 based catalysts, the catalyst prepared by STP precursor and pyrolysis at 900°C exhibited the highest ORR activity with the onset potential of 1.02 V vs. RHE and 4 electron transfer number per oxygen molecule in 0.1 M KOH. The high catalyst durability and fuel-crossover tolerance led to stable performance of the optimal cathode after 5000 s operation, while the Pt/C cathode-based was considerably degraded. Finally, the MFC system with the optimal cathode displayed 43.9 mW·m-2 peak power density showing even reasonable performance in comparison to a Pt/C 20 wt.%.cathode. Conclusions: The results revealed that the synergistic effect of nitrogen and sulfur co-doped on the carbon substrate structure leads to improvement in catalytic activity. Also, it was clearly observed that the porous structure and order level of the carbon substrate could considerably change the ORR performance.

Facile Synthesis of Cu2O nanoparticle-loaded Carbon Nanotubes Composite Catalysts for Reduction of 4-Nitrophenol

2020 ◽  
Vol 16 (4) ◽  
pp. 617-624 ◽  
Author(s):  
Yao Feng ◽  
Ran Wang ◽  
Juanjuan Yin ◽  
Fangke Zhan ◽  
Kaiyue Chen ◽  
...  
Keyword(s):  
Carbon Nanotubes ◽  
Mechanical Stability ◽  
Catalytic Reduction ◽  
High Surface ◽  
High Surface Area ◽  
Reduction Reaction ◽  
Cycle Performance ◽  
Simple Method ◽  
Composite Catalysts ◽  
Cu2o Nanoparticles

Background: 4-nitrophenol (4-NP) is one of the pollutants in sewage and harmful to human health and the environment. Cu is a non-noble metal with catalytic reduction effect on nitro compounds, and.has the advantages of simple preparation, abundant reserves, and low price. Carbon nanotubes (CNT) are widely used for substrate due to their excellent mechanical stability and high surface area. In this study, a simple method to prepare CNT-Cu2O by controlling different reaction time was reported. The prepared nanocomposites were used to catalyze 4-NP. Methods: CNTs and CuCl2 solution were put into a beaker, and then ascorbic acid and NaOH were added while continuously stirring. The reaction was carried out for a sufficiently long period of time at 60°C. The prepared samples were dried in a vacuum at 50°C for 48 h after washing with ethyl alcohol and deionized water. Results: Nanostructures of these composites were characterized by scanning electron microscope and transmission electron microscopy techniques, and the results at a magnification of 200 nanometers showed that Cu2O was distributed on the surface of the CNTs. In addition, X-ray diffraction was performed to further confirm the formation of Cu2O nanoparticles. The results of ultraviolet spectrophotometry showed that the catalytic effect of the compound on 4-NP was obvious. Conclusions: CNTs acted as a huge template for loading Cu2O nanoparticles, which could improve the stability and cycle performance of Cu2O. The formation of nanoparticles was greatly affected by temperature and the appropriate concentration, showing great reducibility for the 4-NP reduction reaction.

scholarly journals Nitrogen-Doped Graphene Iron-Based Particle Electrode Outperforms Activated Carbon in Three-Dimensional Electrochemical Water Treatment Systems

Water ◽  
2020 ◽  
Vol 12 (11) ◽  
pp. 3121
Author(s):  
Hosna Ghanbarlou ◽  
Nikoline Loklindt Pedersen ◽  
Morten Enggrob Simonsen ◽  
Jens Muff
Keyword(s):  
Activated Carbon ◽  
Three Dimensional ◽  
Cell Voltage ◽  
Reduction Reaction ◽  
Process Data ◽  
Nitrogen Doped ◽  
Pesticide Removal ◽  
Optimal Value ◽  
Nitrogen Doped Graphene ◽  
Doped Graphene

The synergy between electrochemical oxidation and adsorption on particle electrodes was investigated in three-dimensional (3D) systems for p-nitrosodimethylaniline (RNO) decolorization and pesticide removal. A comparison was made between granular activated carbon (GAC) and a novel synthesized nitrogen-doped graphene-based particle electrode (NCPE). Experiments on RNO decolorization show that the synergy parameter of the 3D-NCPE system was improved 3000 times compared to the studied 3D-GAC system. This was due to the specific nanostructure and composition of the NCPE material. Nitrogen-doped graphene triggered an oxygen reduction reaction, producing hydrogen peroxide that simultaneously catalyzed on iron sites of the NCPEs to hydroxyl radicals following the electro-Fenton (EF) process. Data showed that in the experimental setup used for the study, the applied cell voltage required for the optimal value of the synergy parameter could be lowered to 5V in the 3D-NCPEs process, which is significantly better than the 15–20 V needed for synergy to be found in the 3D-GAC process. Compared to previous studies with 3D-GAC, the removal of pesticides 2,6 dichlorobenzamide (BAM), 2-methyl-4-chlorophenoxyaceticacid (MCPA), and methylchlorophenoxypropionic acid (MCPP) was also enhanced in the 3D-NCPE system.

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