Physical Chemistry Commons^™

Single-Atom Catalysts For Electrochemical Energy Conversion: Copper Single-Atom Catalyst For Oxygen Reduction Reaction And Quantification Of Site Density By Co Stripping Voltammetry, Dawatage Perera

Theses and Dissertations--Chemistry

Fuel cells are considered a promising technology for achieving cleaner and more sustainable energy production and utilization. However, one of the current major challenges is the economic viability associated with the extensive use of Pt group metal (PGM) catalysts, particularly on the cathode side. Therefore, non-PGM single-atom catalysts (SACs) have received considerable attention as alternatives for PGM catalysts in the oxygen reduction reaction (ORR), which occurs at the cathode of the fuel cell. Among various SAC structures, the non-PGM/nitrogen-doped carbon-based structure (M-N-C) stands out for its excellent ORR performance.

Chapter 2 illustrates the use of copper metal in place of …

Research Progress In Cucurbit[N]Uril-Based Metal Nanomaterials For Electrocatalytic Applications, Zong-Nan Wei, Min-Na Cao, Rong Cao

Journal of Electrochemistry

Metal nanomaterials have exhibited excellent performance in electrocatalytic applications, but they still face the problems of poor stability and limited regulation strategies. It is an efficient strategy for greatly enhanced catalytic activity and stability by introducing a second component. In this review, we provide the sketch for the combination of metal nanomaterials and cucurbit[n]urils (CB[n]s) in electrocatalytic applications. CB[n]s are a series of macrocycles with rigid structure, high stability, and function groups for coordinating with metal sites, which make them promising to stabilize and modulate the metal nanomaterials for ideal performance. The discussion classifies the roles of CB[n]s, involving CB[n]s …

Application Of Atomically Precise Metal Nanoclusters In Electrocatalysis, Zhi-Hua Zhuang, Wei Chen

Journal of Electrochemistry

Metal nanoclusters (M NCs) consist of only several to a few hundred of metal atoms and possess core sizes less than 2 nm. Owing to the quantum size effect, the electronic states of M NCs evolve to discrete levels similar to the molecule energy gaps, other than a continuous density of states to produce plasmon characteristic of bulk metal nanoparticles (M NPs). In comparison with the conventional M NPs, M NCs exhibit dramatically unique electronic and optical properties, such as molecule-like energy gaps, strong photoluminescence and high catalytic properties, which make them promising for potential application in numerous fields, such …

Pd-Based Electrocatalysts For Oxygen Reduction And Ethanol Oxidation Reactions: Some Recent Insights Into Structures And Mechanisms, Zhi-Peng Wu, Chuan-Jian Zhong

Journal of Electrochemistry

The development of efficient electrocatalysts for applications in fuel cells, including proton-exchange membrane fuel cell (PEMFC) and direct ethanol fuel cell (DEFC), has attracted extensive research attention in recent years. Oxygen reduction reaction and ethanol oxidation reaction are two of the key reactions where the design of active, stable and low-cost electrocatalysts is critical for the mass commercializations of PEMFCs and DEFCs. This challenge stems largely from the limited understanding of the catalyst structures and reaction mechanisms. Progress has been made in investigations of electrocatalysts derived from Pd-based alloy nanomaterials both experimentally and computationally. We highlight herein some of the …

Effect Of The Electrodeposition Potential Of Platinum On The Catalytic Activity Of A Pt/Gc Catalyst Toward Formic Acid Electro−Oxidation, Islam M. Al-Akraa, Bilquis A. Al-Qodami Ms., Ahmad M. Mohammad Prof

Chemical Engineering

The electrocatalytic activity of platinum (Pt)–modified glassy carbon (GC) (referred as Pt/GC) electrodes toward the formic acid electro−oxidation (FAO) was investigated. The Pt deposition on the GC substrate was carried out by a potentiostatic technique at different potentials (from 0.2 V to −0.2 V vs. Hg/Hg2Cl2/KCl (sat.) reference electrode) and the corresponding influence on the catalytic activity toward FAO was monitored. The electrocatalytic inspection revealed a potential role for the Pt deposition potential in boosting the catalytic efficiency of the catalyst toward FAO and further in mitigating the CO poisoning that eventually deactivate the catalyst. Interestingly, the highest activity toward …

A Promising Modification Of Pt Surfaces With Cnts For Decreasing Poisoning Impact In Direct Methanol Fuel Cells, Islam M. Al-Akraa Dr., Yaser M. Asal Mr, Aya A. Khalifa Ms.

Chemical Engineering

Direct methanol fuel cells (DMFCs) are clean energy sources that have many applications due to the high energy density of methanol as a fuel. However, this type of fuel cells (FCs) has limitations that are preventing it from being commercialized. One such limitation is the adsorption of intermediates such as CO into the surface of the Platinum (Pt) catalyst during methanol oxidation (MO) which deactivates its active sites, where the reaction is taking place, and leads to poisoning of the electrode over the long term. In this study, multi-walled carbon nanotubes (MWCNTs) have been introduced to the Pt-modified glassy carbon …

Enhanced Electro-Oxidation Of Methanol At Pt-Au Nanocatalyst For Direct Methanol Fuel Cells, Islam M. Al-Akraa Dr., Yaser M. Asal Mr, Ahmad M. Mohammad Prof

Chemical Engineering

In this investigation, a Pt-Au nanocatalyst prepared by the coelectrodeposition of Pt (PtNPs) and Au (AuNPs) nanoparticles is assembled onto a glassy carbon (GC) electrode for efficient methanol oxidation (MO). Several molar ratios between PtNPs and AuNPs have been used and the corresponding catalytic activity towards MO is tracked. The Pt1:Au1 catalyst showed the highest catalytic activity (5 times higher oxidation peak current (Ip) and a 126 mV negative shift in the onset potential (Eonset) toward MO). The catalyst’s morphology, composition and activity are investigated and the ehancement mechanism is recognized.

Recent Progress In Pt-Based Catalysts For Oxygen Reduction Reaction, Jing Li, Xin Feng, Zi-Dong Wei

Journal of Electrochemistry

One major challenge for a large-scale commercialization of the proton-exchange membrane fuel cells (PEMFCs) technologies that enable a shift to ‘zero-emission’ personal transportation, is the expensive and unstable Pt catalysts, which are mainly used to catalyze the sluggish kinetics of the oxygen reduction reaction (ORR) occurred on the air electrode of PEMFCs. Many research works have targets to improve the stability of Pt-based catalysts and to construct Pt/transitional metal alloys with low Pt loading amount. Herein, we provide a minireview for the Pt-based ORR catalysts based on our recent work, which covers a brief background introduction, the stability improvement of …

Palladium Adatoms On Gold Nanoparticles As Electrocatalysts For Ethanol Electro-Oxidation In Alkaline Solutions, Hui-Mei Chen, Shang-Qian Zhu, Jia-Le Huang, Min-Hua Shao

Journal of Electrochemistry

Palladium (Pd) is a good catalyst for ethanol electro-oxidation in alkaline solutions. The activity of Pd is further improved in this study by modifying the gold (Au) nanoparticles with Pd adatoms using a simple spontaneous deposition process. The Pd overlayer on the Au core (Au@Pd) is un-uniform with some Au atoms exposed to the electrolyte. The activity of Au@Pd/C toward ethanol oxidation reaction (EOR) is much higher than that of Pd/C in an alkaline solution. The peak current density of Au@Pd/C is 4.6 times higher than that of Pd/C with a 100 mV lower onset potential. The enhanced activity may …

Morphological Control Of Ptcu2 Octahedron And Oxygen Reduction Electrocatalytic Performance Of Ptcu For Fuel Cell, Long-Sheng Cao, Lei Wan, Zhi-Gang Shao, Hong-Mei Yu, Ming Hou, Bao-Lian Yi

Journal of Electrochemistry

Platinum acetylacetonate (Pt(acac)₂) and copper acetylacetonate (Cu(acac)₂) were co-reduced to prepare PtCu₂ octahedron alloy catalyst in N,N-dimethylformamiade by solvothermal method. The PtCu₂ showed lattice compression, and high ratio of non-oxidized Pt with high electronic binding energy. All those structural features contributed to weak adsorption strength of oxygen species on Pt and lower d-band centre position. The influence of structure-directing agent on morphology of PtCu alloy was systematically studied. In the half cell test, as a result of the uniform morphology and regular octahedron of PtCu₂ formed, the mass activity and area specific activity …

Preparation Of Nanoprobes And Their Possible Applications In Nanoscale Scanning Electrochemical Microscopy For Studying Electrocatalytic Oxygen And Hydrogen Reactions, Xing-Xing Chen

Journal of Electrochemistry

Scanning electrochemical microscopy (SECM) is a type of scanning probe microscopy, which can not only provide the topographical information, but also offer the electrochemical properties of different samples. The interrelationship of physical and electrochemical properties of a sample can be searched at a high-resolution scale due to the introduction of ultramicroelectrode (UME). With the continuous development of modern nanotechnology, the SECM probe has been improved with drastically decreasing its size down to nanometer. Meanwhile, to evaluate and understand the electrochemical performance of various electrocatalysts for both oxygen and hydrogen reactions with high-efficiency is highly demanded in the research area of …

Recent Progress For Fe-N-C Electrocatalysts In Alkaline Fuel Cells, Xin Deng, Heng-Quan Chen, Ye Hu, Qing-Gang He

Journal of Electrochemistry

Fuel cells are highly recommended nowadays due to their intrinsic advantages such as high energy conversion efficiency, nearly no pollution, and convenient operation. With the development of anion exchange membrane, alkaline fuel cells have gone through a renaissance thanks to their superiorities such as faster reaction kinetics, wider choices for both fuels and electrocatalysts. It is essential to find an appropriate electrocatalyst for oxygen reduction reaction (ORR) to improve the performance of alkaline fuel cells. Further commercialization of the widely used Pt-based materials has suffered from disadvantages such as scarcity and high cost. As alternatives to largely investigated Pt-based materials, …

Fabrication Of Cuox-Pd Nanocatalyst Supported On A Glassy Carbon Electrode For Enhanced Formic Acid Electro-Oxidation, Islam M. Al-Akraa Dr., Ahmad M. Mohammad Prof, Mohamed S. El-Deab Prof, Bahgat E. El-Anadouli Prof

Chemical Engineering

Formic acid (FA) electro-oxidation (FAO) was investigated at a binary catalyst composed of palladium nanoparticles (PdNPs) and copper oxide nanowires (CuOxNWs) and assembled onto a glassy carbon (GC) electrode. /e deposition sequence of PdNPs and CuOxNWs was properly adjusted in such a way that could improve the electrocatalytic activity and stability of the electrode toward FAO. Several techniques including cyclic voltammetry, chronoamperometry, field-emission scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction were all combined to report the catalyst’s activity and to evaluate its morphology, composition, and structure. /e highest catalytic activity and stability were obtained at the CuOx/Pd/GC …

The Study Of Dynamical Electrochemical Impedance Spectroscopy For Oxygen Reduction Reaction On Pt/C Catalyst, Kun-Ming Shi, Jian-Wei Guo, Jia Wang

Journal of Electrochemistry

With joint techniques of rotating disc electrode(RDE) and electrochemical impedance spectroscopy(EIS), and further establishment on equivalent circuit model, this paper studied oxygen reduction reaction(ORR) on commercial Pt/C catalyst in acid medium. Our results found that the dynamical interface on Pt/C consists of two independent processes: 1) the PtO reduction from Pt surface, 2) the new PtO formation from ORR, thus providing key clues for catalyst stability and activity. This also implied that the dynamical interface facilitates reconstruction for porous electrode, and matches with mass transfer. One important issue is discovered that at high overpotential, the high reaction rate for ORR …

Developments Of Photo-Assisted Fuel Cells, Ling-Ling Zhang, Shao-Jun Dong

Journal of Electrochemistry

The exploitation and utilization of fossil fuels have led to serious energy crisis and environmental pollution. In this case, the development of renewable energy is an alternative to traditional energy consumption. Fuel cells (FCs) can convert chemical energy into electricity via the electrochemical reaction, which is green and environment-friendly. Photo-assisted FCs integrate photo-responsive components into FCs, leading to the dual routes of energy conversion including light energy to electricity and chemical energy to electricity, and thus, improving the energy utilization efficiency. The development of photo-assisted FCs is significant for practical application and promising to solve the coming energy crisis. In …

Mini-Review: Possible Applications Of Scanning Electrochemical Microscopy (Secm) In Characterizations Of Oxygen Reduction Reaction And Oxygen Evolution Reaction, Xing-Xing Chen

Journal of Electrochemistry

Scanning electrochemical microscopy (SECM) has been proved to be a unique technique for combinatorial screening of localized phenomena for different electrocatalysts potentially used in new energy conversion and storage systems. This mini-review provides a brief summary of different SECM working modes, such as direct mode, feedback mode, generation-collection mode, redox competition mode and noise mode, which are especially applied for characterizing the oxygen reactions. Particularly, a series of important development in SECM screening of electrocatalysts for oxygen reduction reaction and oxygen evolution reaction from the author and W. Schuhmann’s group in Germany has been highlighted and overviewed. Finally, some prospects …

On The Catalytic Activity Of Palladium Nanoparticles-Based Anodes Towards Formic Acid Electro-Oxidation: Effect Of Electrodeposition Potential, Islam M. Al-Akraa Dr., Ahmad M. Mohammad Prof, Mohamed S. El-Deab Prof, Bahgat E. El-Anadouli Prof

Chemical Engineering

In this investigation, the catalytic activity of palladium nanoparticles (PdNPs)-modified glassy carbon (GC) (simply noted as PdNPs/GC) electrodes towards the formic acid electro-oxidation (FAO) was investigated. The deposition of PdNPs on the GC substrate was carried out by a potentiostatic technique at different potentials and the corresponding influence on the particles size and crystal structure of PdNPs as well as the catalytic activity towards FAO was studied. Scanning electron microscopy (SEM) demonstrated the deposition of PdNPs in spherical shapes and the average particle size of PdNPs deposited at a potential of 0 V vs. Ag/AgCl/KCl(sat.) was the smallest (ca. 8 …

Novel Electrochemical Interfaces Based On Functional Nanomaterials And Their Related Applications, Cheng-Zhou Zhu, Lei Han, Shao-Jun Dong

Journal of Electrochemistry

Due to the unique optical, electronic, magnetic and catalytic properties, functional nanomaterials provide new opportunities for the rapid development in a variety of disciplines and show considerable promise in different fields. Specifically, constructions of the novel electrochemical interface using various nanomaterials and exploring their advanced electrochemical properties have received great attention to develop electrochemical devices with potential applications. In this account, we focus on our up-to-date progress in the construction of novel electrochemical interfaces based on nanomaterials, mainly highlighting our research advances on electrochemical sensors, fuel cells and fluorescence spectroelectrochemistry. These novel advanced nanomaterials endow them excellent performances and open …

Preparation And Methanol Electrooxidation Of Pt/Pmo12/Pedot/Gc Electrodes, Jing-Hua Ma, Rui-Xiang Wang, Yi-Liang Tan, Shan-Shan Wang, Yan-Qin Zhang, You-Jun Fan

Journal of Electrochemistry

Modification of phosphomolybdic acid (PMo₁₂) on poly(3,4-ethylenedioxythiophene) (PEDOT) film (PEDOT/GC) obtained through the electrochemical polymerization was performed using adsorption method (PMo₁₂/PEDOT/GC), followed by electrodepositing Pt on PMo₁₂/PEDOT/GC to prepare Pt/PMo₁₂/PEDOT/GC electrode. Effects of PMo₁₂ and PEDOT on the methanol oxidation performance of electrode were investigated. Results showed that PMo₁₂ obviously changed the morphology and structure of Pt loaded on the electrode, leading to the formation of sharp thorns at the edge of Pt nanostructures. Cyclic voltammetry and chronoamperometry data demonstrated that the catalytic activities of methanol electrooxidation on the Pt/PMo …

Porous Electrodes With High Pt Utilization Obtained By Ion-Exchange/Electrodeposition, Si-Guo Chen, Wei Ding, Xue-Qiang Qi, Li Li, Zi-Hua Deng, Zi-Dong Wei

Journal of Electrochemistry

We report a novel method based on ion-exchange/electrodeposition (IEE) for constructing high Pt utilization porous electrodes. The electrode prepared using IEE was assessed by linear sweep voltammetry (LSV), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and single cell test. The preliminary results show that the undesired ion-exchange between Pt anion and surface functional group in carbon black can be eliminated through the electrode preparation process, and every Pt particle prepared by IEE is expected to be deposited on the three-phase reaction zone and thus can be fully utilized in fuel cell reactions. The Pt particle size, shape and distribution …

Ternary Alloy Electrocatalysts For Oxygen Reduction Reaction, Jin Luo, Lefu Yang, Binghui Chen, Chuanjian Zhong

Journal of Electrochemistry

Proton exchange membrane fuel cell represents an important electrochemical energy conversion device with many attractive features in terms of efficiency of energy conversion and minimization of environmental pollution. However, the large overpotential for oxygen reduction reaction at the cathode and the low activity, poor durability and high cost of platinum-based catalysts in the fuel cells constitute a focal point of major barriers to the commercialization of fuel cells. The development of nanostructured catalysts shows promises to addresses some of the challenging problems. The ability to engineer the composition and nanostructure of nanoalloy catalysts is important for developing active, robust and …

Progress And Perspective Of Fuel Cell Technology, Ming Hou, Bao-Lian Yi

Journal of Electrochemistry

Fuel cell, a clean and high-efficiency electrochemical power source, has being paid much attention worldwide recent years. In this paper, the progress and perspective of fuel cell technology are elucidated in detail. Fuel cells have been applied in some special fields such as spacecraft, shuttle and submarines. However, in the areas of transportation, stationary station and portable power source, fuel cells are still under demonstration due to the durability and cost problems. The reliability and surrounding survivability of fuel cells should be enhanced in the special application. Meanwhile, the durability and cost of fuel cells are the main issues to …

Development Of Tailor-Designed Gold-Platinum Nanoparticles Binary Catalysts For Efficient Formic Acid Electrooxidation, Islam M. Al-Akraa Dr, Ahmad M. Mohammad Prof, Mohamed S. El-Deab Prof, Bahgat E. El-Anadouli Prof

Chemical Engineering

The modification of a glassy carbon (GC) electrode with platinum (PtNPs) and gold (AuNPs) nanoparticles is targeted to fabricate efficient anodes for the electrooxidation of formic acid (FA). A proper adjustment of the deposition sequence of PtNPs and AuNPs could eventually enhance the electrocatalytic activity of the electrode in such a way that suppresses the CO poisoning effect during FA oxidation. The highest catalytic activity is obtained at the Au/Pt/GC electrode (with PtNPs firstly deposited on the GC electrode followed by AuNPs). This superb enhancement is quantified by comparing the relative ratio of the direct vs. the indirect oxidation peaks …

A Theoretical Study Of Methanol Oxidation Mechanisms By Methanol Dehydrogenase Enzymes For Fuel Cell Applications, Nagesh B. Idupulapati

Doctoral Dissertations

Enzymes are considered for electrochemical generation of power in fuel cells. Methanol dehydrogenase (MDH) is one such enzyme, which has been used as an anodic catalyst for a methanol-fed biofuel cell producing enough power for small electronic device applications. In practice, however, there are power output limitations associated with this MDH fuel cell, which may potentially be eliminated or reduced if the reactivity of this enzyme during the oxidation of methanol at the molecular level is clearly understood.

Two mechanisms for the methanol oxidation process by MDH have been proposed in the literature, Addition-Elimination (A-E) and Hydride Transfer (H-T), but …

Hydrolysis Of Sodium Borohydride By Ru-Ni Foam Catalyst, Jie Cheng, Feng Ye, Tong-Tao Wang, Jing-Jing Li, Yong-Liang Wang, Xin-Dong Wang

Journal of Electrochemistry

This paper presented a method of hydrogen generation from sodium borohydride solution for fuel cells.The Ru-Ni foam catalyst which was prepared by chemical plating showed strong activity and stability.The pretreatment of Ni foam before chemical plating was very important for the catalyst's strong activity and stability.This easy-to-prepared catalyst exhibited a good activity after being used several times.The effects of NaBH₄ concentration,temperature and used times on the hydrogen generation rate were investigated.The results showed that the rate was remarkablely increased with the temperature rising and the rate increased more than ten times when the temperature of reaction rised from 15 …

Electrocatalytic Oxidation Of Glucose On Nano Pt/C Electrode, Cui-Lian Chen, Xiao-Lan Wei, Pei Kang Shen

Journal of Electrochemistry

Nano Pt/C electrocatalysts were prepared by intermittent microwave heating method.The electrooxidation of glucose on smooth Pt and～Pt/C electrodes has been studied and compared.The results showed that the electrochemical properties on nano Pt/C were improved due to the reduction of the overpotential and the increase in the kinetic rate.The surface area would be significantly increased when the particle size of the catalyst was reduced to nano-scale,resulting in the increase in the activity.The enhancement in the resistance to poisoning could be explained that the oxygen-containing species are easier to react with poisoning species on nano Pt/C and re-active the electrode.

The Study On Carbon Nanotube-Loaded Pt Catalysts For Proton Exchange Membrane Fuel Cells, Hong Zhu, Feng-Juan Ge, Xiao-Hong Kang, Yu-Guo Yang, Yun-Hua Xu

Journal of Electrochemistry

Carbon nanotube-supported-platinum (Pt/CNTs) and carbon-supported-platinum (Pt/C) catalysts were synthesized by in-situ chemical reduction. They were analyzed using TEM and XRD, then made into electrodes to be part of assemable PEMFC for the performence tests. The resulted show that Pt clusters in both catalysts are of small particle size (about 4nm), and Pt/CNTs exhibits a higher catalytic activity than Pt/C.

Study Of Proton Exchange Membrane Fuel Cells(Pemfc), Shan-Hai Ge, Bao-Lian Yi, Hong-Fen Xu, Ming Han, Zhi-Gang Shao

Journal of Electrochemistry

The electrode kinetic parameters for proton exchange membrane fuel cells(PEMFC) were investigated by measuring the relations of cell potential and current density. An experimental stack of PEMFC which can be operated at E cell =0.7V, I =0.55A/cm² steadily is presented, and the effects of electrode structure and operation conditions such as temperature, pressure, humidification, flow rate on the performance of PEMFC are discussed.

Anchor Effect Of Iron And Cobalt To Platinum On Carbon Substrates, Zidong Wei, Hetong Guo, Zhiyuan Tan

Journal of Electrochemistry

The cathodic reduction of oxygen is studied on porous carbonbased electrodes carrying platinumiron and/or cobalt alloy catalysts. Electrodes using such electrocatalysts, particularly when used as cathodes in acidic electrolytes, remain stable for longer periods. The cathodic polarization of oxygen reduction on such electrodes is 20 mV to 40 mV lower than that on the conventional electrode on which only platinum alone is used as an electrocatalysts. An accelerated aging test (AAT) is used to evaluate the corrosion resistance and sintering resistance of each catalyst. The dissolution of the catalyst in the AAT filtrate is analysed and provides a measure of …