Chemical Engineering Commons^™

Recent Developments In Surface/Interface Modulation And Structure-Performance Relationship Of Cathode Catalysts For Li-Air Batteries, Rui Gao, Jun-Kai Wang, Zhong-Bo Hu, Xiang-Feng Liu

Journal of Electrochemistry

Lithium-air battery has been considered to be one of the most promising secondary battery systems because of its high energy density. However, the sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) on the cathode, and the high overpotential, poor cycle stability and low rate capacity have severely blocked the development and application of Li-air battery. One of the effective strategies to alleviate these issues is to develop cathode catalysts for Li-air batteries. The design and development of bifunctional cathode catalysts with high activity and efficiency on both ORR and OER is highly desired for Li-air …

Synthesis Of Flower-Like Vanadium Disulfide For Lithium Storage Application, Pan Li, Jian Liu, Wei-Yi Sun, Hai-Xia Li, Zhan-Liang Tao

Journal of Electrochemistry

In order to improve the electrochemical properties of vanadium disulfide (VS₂) as an electrode material in Li-ion battery, the flower-like VS₂ was prepared by a one-step hydrothermal method with the addition of polyethylene glycol 400. The phase and morphology of the product were characterized by using X-ray diffraction and field emission scanning electron microscopy. During the growth process, it was observed that the flower-like VS₂ was interspersed with several hexagonal vanadium disulfide nanosheets, which had a high specific surface area and excellent structural stability. The flower-like VS₂ was used for the cathode material test in …

Effect Of Pt Promotion On The Ni-Catalyzed Deoxygenation Of Tristearin To Fuel-Like Hydrocarbons, Ryan Loe, Kelsey Huff, Morgan Walli, Tonya Morgan, Dali Qian, Robert Pace, Yang Song, Mark Isaacs, Eduardo Santillan-Jimenez, Mark Crocker

Center for Applied Energy Research Faculty and Staff Publications

Pt represents an effective promoter of supported Ni catalysts in the transformation of tristearin to green diesel via decarbonylation/decarboxylation (deCO_x), conversion increasing from 2% over 20% Ni/Al₂O₃ to 100% over 20% Ni-0.5% Pt/Al₂O₃ at 260 °C. Catalyst characterization reveals that the superior activity of Ni-Pt relative to Ni-only catalysts is not a result of Ni particle size effects or surface area differences, but rather stems from several other phenomena, including the improved reducibility of NiO when Pt is present. Indeed, the addition of a small amount of Pt to the supported Ni …

Carboxylic Acids Accelerate Acidic Environment-Mediated Nanoceria Dissolution, Robert A. Yokel, Matthew L. Hancock, Eric A. Grulke, Jason M. Unrine, Alan K. Dozier, Uschi M. Graham

Pharmaceutical Sciences Faculty Publications

Ligands that accelerate nanoceria dissolution may greatly affect its fate and effects. This project assessed the carboxylic acid contribution to nanoceria dissolution in aqueous, acidic environments. Nanoceria has commercial and potential therapeutic and energy storage applications. It biotransforms in vivo. Citric acid stabilizes nanoceria during synthesis and in aqueous dispersions. In this study, citrate-stabilized nanoceria dispersions (∼4 nm average primary particle size) were loaded into dialysis cassettes whose membranes passed cerium salts but not nanoceria particles. The cassettes were immersed in iso-osmotic baths containing carboxylic acids at pH 4.5 and 37 °C, or other select agents. Cerium atom material …

Continuous Catalytic Deoxygenation Of Waste Free Fatty Acid-Based Feeds To Fuel-Like Hydrocarbons Over A Supported Ni-Cu Catalyst, Ryan Loe, Yasmeen Lavoignat, Miranda Maier, Mohanad Abdallah, Tonya Morgan, Dali Qian, Robert Pace, Eduardo Santillan-Jimenez, Mark Crocker

Center for Applied Energy Research Faculty and Staff Publications

While commercial hydrodeoxygenation (HDO) processes convert fats, oils, and grease (FOG) to fuel-like hydrocarbons, alternative processes based on decarboxylation/decarbonylation (deCO_x) continue to attract interest. In this contribution, the activity of 20% Ni-5% Cu/Al₂O₃ in the deCO_x of waste free fatty acid (FFA)-based feeds—including brown grease (BG) and an FFA feed obtained by steam stripping a biodiesel feedstock—was investigated, along with the structure-activity relationships responsible for Ni promotion by Cu and the structural evolution of catalysts during use and regeneration. In eight-hour experiments, near quantitative conversion of the aforementioned feeds to diesel-like hydrocarbons was achieved. …

An Experimental And Numerical Investigation Of Flow Accelerated Flibe Corrosion, David B. Weitzel

Nuclear Engineering ETDs

Renewed interest in molten salt reactor technology has brought to light the need for a better understanding of FLiBe corrosion. To this end a flowing FLiBe corrosion test loop was designed to test the flow effects of FLiBe corrosion. The loop consists of a pump, melt tank, and stainless-steel tubing assembly that heats the molten salt to high temperatures and circulates it over test specimens. The experiment has been constructed and has completed initial shakedown testing.

To support the flowing FLiBe experiment, a numerical corrosion model that couples FLiBe electrochemistry, solid metal diffusion, and mass transport was implemented. The model …

Facile Synthesis Of A Tailored-Designed Au/Pt Nanoanode For Enhanced Formic Acid, Methanol, And Ethylene Glycol Electrooxidation, Yaser M. Asal Mr., Islam M. Al-Akraa Dr, Ahmad M. Mohammad Prof

Chemical Engineering

The recent revolution in nanoscience and global energy demand have motivated research in liquid fuel cells (LFCs) due to their enhanced efficiency, moving flexibility, and reduced contamination. In line with this advancement, a glassy carbon (GC) electrode was modified with platinum (PtNPs) and gold (AuNPs) nanoparticles to fabricate a nanosized anode for formic acid, methanol, and ethylene glycol electrooxidation (abbreviated, respectively, to FAO, MO, and EGO), of the key anodic reactions of LFCs. The deposition sequence of the catalyst’s layers was important where the Au/Pt/GC electrode (in which PtNPs were directly deposited onto the GC surface followed by AuNPs—surface coverage …

Anchoring Cu 1 Species Over Nanodiamond-Graphene For Semi-Hydrogenation Of Acetylene, Fei Huang, Yuchen Deng, Yunlei Chen, Xiangbin Cai, Mi Peng, Zhimin Jia, Jinglin Xie, Dequan Xiao, Xiaodong Wen, Ning Wang, Zheng Jiang, Hongyang Liu, Ding Ma

Chemistry and Chemical Engineering Faculty Publications

The design of cheap, non-toxic, and earth-abundant transition metal catalysts for selective hydrogenation of alkynes remains a challenge in both industry and academia. Here, we report a new atomically dispersed copper (Cu) catalyst supported on a defective nanodiamondgraphene (ND@G), which exhibits excellent catalytic performance for the selective conversion of acetylene to ethylene, i.e., with high conversion (95%), high selectivity (98%), and good stability (for more than 60 h). The unique structural feature of the Cu atoms anchored over graphene through Cu-C bonds ensures the effective activation of acetylene and easy desorption of ethylene, which is the key for the outstanding …

A Versatile Route To Fabricate Single Atom Catalysts With High Chemoselectivity, Xiaohui He, Qian He, Yuchen Deng, Mi Peng, Hongyu Chen, Ying Zhang, Siyu Yao, Mengtao Zhang, Dequan Xiao, Ding Ma, Binghui Ge, Hongbing Ji

Chemistry and Chemical Engineering Faculty Publications

Preparation of single atom catalysts (SACs) is of broad interest to materials scientists and chemists but remains a formidable challenge. Herein, we develop an efficient approach to synthesize SACs via a precursor-dilution strategy, in which metalloporphyrin (MTPP) with target metals are co-polymerized with diluents (tetraphenylporphyrin, TPP), followed by pyrolysis to N-doped porous carbon supported SACs (M₁/N-C). Twenty-four different SACs, including noble metals and non-noble metals, are successfully prepared. In addition, the synthesis of a series of catalysts with different surface atom densities, bi-metallic sites, and metal aggregation states are achieved. This approach shows remarkable adjustability and generality, providing …

Development Of Functional Ionic Liquids For Separation And Recovery Of Rare Earth Elements, Mostafa Khodakarami

Doctoral Dissertations

“This research focused on the design and synthesis of task-specific ionic liquids for enhanced extraction and separation of rare earth elements (REEs). Two novel ammonium-based functional ionic liquids (FILs) with oxygen donating groups: trioctyl(2-ethoxy-2-oxoethyl)ammonium dihexyl diglycolamate, [OcGBOEt][DHDGA], and tricaprylmethylammonium dihexyl diglycolamate, [A336][DHDGA] were synthesized and tested for the recovery and separation of selected REEs from aqueous solutions. Functionalities with different denticities were incorporated into both anionic and cationic parts of ionic liquids, which are solely composed of incinerable atoms including C, H, O, and N. The structural, physical, and chemical properties of the synthesized FILs were studied using nuclear magnetic …

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 …

Novel Adsorbent For Industrial Wastewater Treatment Applications, Islam M. Al-Akraa, Ahmed Y. Zakaria Eng, Dalia A. Ali Eng, Hany A. Elazab Dr, Hoda A. Elsawy Dr

Chemical Engineering

In this study, the hydroxyapatite powder is investigated for both of methylene blue and thymol blue in aqueous solution. The physical and chemical properties of the adsorbent were evaluated systematically using the different techniques including Microsoft Excel programming, linear regression model and also the coefficient of determination. Batch adsorption experiments were conducted to determine the effect of contact time, solution pH, initial dye concentrations, and also the adsorbent dosage on adsorption. The adsorption kinetic parameters confirmed the better fitting of pseudo-second order kinetic model for both of methylene blue and thymol blue. The isotherm data of methylene blue and thymol …

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.

A Simple And Effective Way To Overcome Carbon Monoxide Poisoning Of Platinum Surfaces In Direct Formic Acid Fuel Cells, Islam M. Al-Akraa Dr., Yaser M. Asal Mr, Sohair A. Darwish Ms

Chemical Engineering

A glassy carbon (GC) electrode modified with multi-walled carbon nanotubes (MWCNTs) and platinum nanoparticles (PtNPs), Pt/MWCNTs-GC, has been introduced for formic acid electro-oxidation (FAO). A similar loading of PtNPs has been conserved for a proper comparison between the Pt/MWCNTs-GC and the unmodified Pt/GC electrodes. The modification with MWCNTs could enhance the loading of PtNPs onto the GC electrode in a way that minimizes its agglomeration and increases its dispersion in the CNTs network. This not only increases the surface area exposed to the reaction but also interrupts the contiguity of the Pt active sites minimizing the adsorption of the poisoning …

The Effect Of Curing And Zirconium Content On The Wettability And Structure Of A Silicate Hybrid Sol-Gel Material, Emma Machugh, Maikki Cullen, Alicja Kaworek, Brendan Duffy, Mohamed Oubaha

Articles

Functional hybrid sol-gel coatings have been developed for numerous applications with a wide range of wettabilities. This study proposes to investigate the relationship between the structure and the wetting properties of a zirconium modified silicate hybrid sol-gel coating. The structures of the coatings were altered by varying the content of zirconium, and the curing process, while keeping the sol-gel preparation conditions identical. The structure of the materials was characterized by FTIR, 29Si NMR and SEM. The thermal properties and the wettability are identified by DSC and contact angle measurements, respectively. By corroborating the structural and wettability analyses, it is shown …

Molecular Exchange Monte Carlo. A Generalized Method For Identity Exchanges In Grand Canonical Monte Carlo Simulations, Mohammad Soroush Barhaghi

Wayne State University Theses

A generalized identity exchange algorithm is presented for Monte Carlo simulations in the grand canonical ensemble. The algorithm, referred to as Molecular Exchange Monte Carlo (MEMC), may be applied to multicomponent systems of arbitrary molecular topology, and provides significant enhancements in the sampling of phase space over a wide range of compositions and temperatures. Three different approaches are presented for the insertion of large molecules, and the pros and cons of each method are discussed. The performance of the algorithms is highlighted through grand canonical Monte Carlo histogram-reweighting simulations performed on several systems, including 2,2,4-trimethylpentane+neopentane, butane+perfluorobutane, methane+n-alkanes, and water+impurity. Relative …

Charged Nanoparticles Quench The Propulsion Of Active Janus Colloids, Marola W. Issa, Nicky R. Baumgartner, Mohammed A. Kalil, Shawn D. Ryan, Christopher L. Wirth

Mathematics and Statistics Faculty Publications

Active colloidal particles regularly interact with surfaces in applications ranging from microfluidics to sensing. Recent work has revealed the complex nature of these surface interactions for active particles. Herein, we summarize experiments and simulations that show the impact of charged nanoparticles on the propulsion of an active colloid near a boundary. Adding charged nanoparticles not only decreased the average separation distance of a passive colloid because of depletion attraction as expected but also decreased the apparent propulsion of a Janus colloid to near zero. Complementary agentbased simulations considering the impact of hydrodynamics for active Janus colloids were conducted in the …

A Critical Review Of Using High Viscosity Friction Reducers As Fracturing Fluids For Hydraulic Fracturing Applications, Mohammed Ba Geri, Abdulmohsin Imqam, Ralph E. Flori

Geosciences and Geological and Petroleum Engineering Faculty Research & Creative Works

The primary purpose of using traditional friction reducers in stimulation treatments is to overcome the tubular drag while pumping at high flow rates. Hydraulic fracturing is the main technology used to produce hydrocarbon from extremely low permeability rock. Even though slickwater (water fracturing with few chemical additives) used to be one of the most common fracturing fluids, several concerns are still associated with its use, including usage of freshwater, high-cost operation, and environmental issues. Therefore, current practice in hydraulic fracturing is to use alternative fluid systems that are cost effective and have less environmental impact, such as fluids which utilize …

Multidimensional Mass Spectrometry Of Chemonic™ Ccg-6 Nonionic Surfactant With Separation By Polarity And Shape, Charles Johnson

Williams Honors College, Honors Research Projects

Chemonic™ CCG-6 surfactant is a water-soluble poly(ethylene glycol) (PEG) conjugated alkyl glyceride emollient. This surfactant exists as a complex mixture of a glycerol cores conjugated with poly(ethylene glycol) branches (PEGylation) that were partially esterified with caprylic (C8) and capric (C10) acids. These may be esterified on one, two, or all three arms of the glyceride. The architecture of the structures in this mixture was studied using multidimensional mass spectrometry (MS). Mass spectrometry was interfaced with ultra-performance liquid chromatography (UPLC) and ion mobility (IM) separation. The mixture was separated by reversed-phase LC, oligomers of the star-branched polymer were separated according to …

Microfluidic Study Of Gravity-Driven Drainage And Coalescence Of Aqueous Two Dimensional Foams, Justin D. Heftel

Dissertations and Theses

Foams, a two-phase dispersion, are staples of the cosmetic, personal care, petroleum, pharmaceutical, and other industries. Central to these applications is the stability of the dispersion against separation. Foams break down by two mechanisms: the first is bubble coalescence, which is driven by the gravity drainage of the continuous phase. The drainage acts to push the bubbles against each other, and leads to the formation of thin lamellae, which break and cause the coalescence. The second is the mass transfer of the dispersed phase through the continuous phase, which is caused by the difference in pressures between the bubbles and …

Thermal Analysis And Design Of Conduction Links For A Superconducting Radio Frequency Resonator, Aaron Mckeown

Graduate Research Theses & Dissertations

The SRF conduction link project at Fermi National Accelerator Laboratory aims to develop an SRF particle accelerator design that is more applicable for industrial use. Collaboration between NIU college of engineering and NIU department of physics provided the bulk of design and analysis for this project. Currently, cooling systems, used in SRF particle accelerators, pump liquid helium across the SRF cavity to provide convection based cooling. The goal of this project is to incorporate a conduction based cooling system. In a conduction based cooling system, heat will flow from the SRF cavity into a cryocooler through a conduction link. In …

Characterization Of A Green Electric Solid Propellant For Electric Propulsion, Matthew Scott Glascock

Doctoral Dissertations

"Electric solid propellants are advanced solid chemical rocket propellants that can be controlled (ignited, throttled and extinguished) through the application and removal of an electric current. These propellants are also being considered for use in ablative pulsed plasma thruster and multimode systems. In this work, the behavior and performance of a novel green electric solid propellant operating in an electrothermal ablation-fed pulsed plasma thruster was investigated. Using an inverted pendulum micro-Newton thrust stand, the impulse bit and specific impulse of the device using the electric solid propellant were measured for short-duration and long-duration runs to end-of-life, at energy levels of …

Towards Sustainable Production Of Chemicals And Fuels From The Fast Pyrolysis Of Waste Polyolefin Plastics, Ulises Gracida Alvarez

Dissertations, Master's Theses and Master's Reports

The increasing amount of plastic waste (PW) generation has become an important concern due to the leveled-off recycling rates. Therefore, governmental agencies around the world, including state governments in the United States, have proposed initiatives to minimize the amount of PW that is landfilled and encourage recycling or energy recovery. Circular economy is a strategy that attempts on reusing PW to produce new polymers while avoiding its disposal and the use of virgin material. Chemical recycling raises an interesting technology prospect due to the potential reduction of pollutant emissions and the establishment of a circular economy through the production of …

Stabilization Strategies Of Pt Catalysts Forproton Exchange Membrane Fuel Cells, Da-Ping He, Shi-Chun Mu

Journal of Electrochemistry

The low service lifetime of proton exchange membrane fuel cells (PEMFCs) is the main bottleneck for their commercial applications. One of the main factors is that the expensive metal Pt catalyst is easy to degradation under the harsh working environment of PEMFC (such as variable voltage, strong acidity, gas-liquid two-phase flow), which leads to the inevitable decay of the catalytic performance, thus, seriously restricting the lifetime of PEMFC. Therefore, the electrochemical stability of Pt-based electrocatalysts has become an important and hot topic to improve the PEMFC lifetime. In this paper, we review the recent development in enhancing the stability of …

The Pilot Application Of Electrochemical Impedance Spectroscopy On Dynamic Proton Exchange Membrane Fuel Cell, Jian-Wei Guo, Jian-Long Wang

Journal of Electrochemistry

By analyzing Electrochemical Impedance Spectroscopy (EIS) in applications of dynamic proton exchange membrane fuel cell (PEMFC), bottlenecks which restrict EIS tool development have been pointed out in this paper. Though the high-frequency resistance in EIS is largely accepted as cell inner-resistance, this can only be applied for cell with low current. The low-frequency resistance is difficult to be realized due to its relation with mass transfer. Furthermore, the improved Randles equivalent circuits are built up preliminarily, thus, penetrating into studies for mass transfer reaction, cell operation/degeneration, and high temperature fuel cell. Inspiringly, EIS is becoming an analyzing tool for stack …

Research Progress In Hydrogen Evolution Low Noble/Non-Precious Metal Catalysts Of Water Electrolysis, Yang Li, Zhao-Yan Luo, Jun-Jie Ge, Chang-Peng Liu, Wei Xing

Journal of Electrochemistry

Hydrogen energy technology with hydrogen as an energy carrier is gaining more and more attention due to its cleanliness and high energy density. Hydrogen fuel cell vehicles have been listed as one of the ultimate energy technologies in the 21st century. Among them, sustainable hydrogen production technology is a necessary prerequisite for the future development of hydrogen energy economy. Electrolyzed water technology driven by renewable resources represents an important way to support the sustainable development of hydrogen energy economy. The development and utilization of high activity, low cost hydrogen evolution catalysts is a key factor in improving the efficiency and …

Fuel Cell Performance Curve After Mea Optimization Structural Optimization Of Low Pt Membrane Electrode Assembly, Yan Rao, Shang Li, Fen Zhou, Tian Tian, Qing Zhong, Zhao-Hui Wan, Jin-Ting Tan, Mu Pan

Journal of Electrochemistry

Membrane electrode assemblies (MEAs) are the key component of proton exchange membrane fuel cell. For a long time, much attention has been paid to develop MEA technology. At present, the research, development and industrialization of fuel cell has entered a new era. More strict requirements for MEA, especially for the reduction of Pt loading with a challenging target of 0.125 mg·W^-1 have to be met. In this paper, the performance losses under low Pt loading are analyzed in terms of activation polarization, ohm polarization and mass-transfer polarization. It is proposed that research should be focused on the activity of …

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 …

Effects Of So2 In Air On Performance Of Direct Methanol Fuel Cell, Bin Qin, Fen-Ning Jing, Xue-Jing Sun, Gong-Quan Sun, Hai Sun

Journal of Electrochemistry

Direct methanol fuel cells (DMFC) generally use oxygen as an oxidant. Contaminants such as sulfides and nitrides in the air can affect the performance of the DMFC. In this work, the effects of SO₂ on the performance of DMFC were investigated and the mechanism of poisoning was analyzed, by means of constant current discharge curve, polarization performance curve, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). In the CV scan, the permeated methanol was oxidized at a low potential to eliminate its effect on the SO₂ poisoning behavior test. The results showed that the SO₂ poisoning resulted …

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 …