Synthesis-Structure-Activity Relationships in Co3O4 Catalyzed CO Oxidation

In this work, a statistical design and analysis platform was used to develop cobalt oxide based oxidation catalysts prepared via one pot metal salt reduction. An emphasis was placed upon understanding the effects of synthesis conditions, such as heating regimen and Co2+ concentration on the metal salt reduction mechanism, the resultant nanomaterial properties (i.e., size, crystal structure, and crystal faceting), and the catalytic activity in CO oxidation. This was accomplished by carrying out XRD, TEM, and FTIR studies on synthesis intermediates and products. Additionally, high-throughput experimentation was employed to study the performance of Co3O4 oxidation catalysts over a wide range of reaction conditions using a 16-channel fixed bed reactor equipped with a parallel infrared imaging system. Specifically, Co3O4 nanomaterials of varying properties were evaluated for their performance as CO oxidation catalysts. Figure-of-merits including light-off temperatures and activation energies were measured and mapped back to the catalyst properties and synthesis conditions. Statistical analysis methods were used to elucidate significant property-activity relationships as well as the design rules relevant in the synthesis of active catalysts. It was found that the degree of grain boundary consolidation and anisotropic growth in fcc and hcp CoO intermediates significantly influenced the catalytic activity. By utilizing the discovered synthesis-structure-activity relationships, CO oxidation light off temperatures were decreased to \u3c90°C

Fingering Instabilities on Reaction Fronts in the CO Oxidation Reaction on Pt(100)

Fingering instabilities arising from local perturbations to planar reaction fronts in the CO oxidation reaction on Pt(100) are presented. CO oxidation represents a heterogeneous nonlinear system with the necessary kinetic and diffusive transport properties to support the development of fingered wave fronts. External forcing was utilized to create CO wave fronts on an otherwise monostable, O-covered surface, which, upon destabilization, gave rise to fingers of adsorbed CO extending into the O adlayer ahead of the reaction front. Finger spreading and tip-splitting were observed as the finger pattern evolved towards an intrinsic wavelength, independent of the length of the reaction front, calculated to be approximately 40 μm. Our data also show the presence of a shielding process, where at wavelengths less than twice the observed intrinsic value, additional fingers were created on the reaction front through a tip-splitting bifurcation of an existing finger. At wavelengths greater than twice the intrinsic value, additional fingers formed in the troughs between adjacent fingers, apparently unaffected by the presence of the larger surrounding fingers

Statistically Guided Synthesis of MoV- Based Mixed Oxide Catalysts for Ethane Partial Oxidation

The catalytic performance of Mo8V2Nb1-based mixed-oxide catalysts for ethane partial oxidation is highly sensitive to the doping of elements with redox and acid functionality. Specifically, control over product distributions to ethylene and acetic acid can be afforded via the specific pairing of redox elements (Pd, Ni, Ti) and acid elements (K, Cs, Te) and the levels at which these elements are doped. The redox element, acid element, redox/acid ratio, and dopant/host ratio were investigated using a three-level, four-factor factorial screening design to establish relationships between catalyst composition, structure, and product distribution for ethane partial oxidation. Results show that the balance between redox and acid functionality and overall dopant level is important for maximizing the formation of each product while maintaining the structural integrity of the host metal oxide. Overall, ethylene yield was maximized for a Mo8V2Nb1Ni0.0025Te0.5 composition, while acetic acid yield was maximized for a Mo8V2Nb1Ti0.005Te1 catalyst

One-Step Production of Long-Chain Hydrocarbons from Waste-Biomass-Derived Chemicals using Bi-Functional Heterogeneous Catalysts

n this study, we demonstrate the production of long-chain hydrocarbons (C8+) from 2-methylfuran (2MF) and butanal in a single step reactive process by utilizing a bi-functional catalyst with both acid and metallic sites. Our approach utilizes a solid acid for the hydroalkylation function and as a support as well as a transition metal as hydrodeoxygenation catalyst. A series of solid acids was screened, among which MCM-41 demonstrated the best combination of activity and stability. Platinum nanoparticles were then incorporated into the MCM-41. The Pt/MCM-41 catalyst showed 96% yield for C8+ hydrocarbons and the catalytic performance was stable over four reaction cycles of 20 hour each. The reaction pathways for the production of long-chain hydrocarbons is probed with a combination of infrared spectroscopy and steady-state reaction experiments. It is proposed that 2MF and butanal go through hydroalkylation first on the acid site followed by hydrodeoxygenation to produce the hydrocarbon fuels

Statistically Guided Synthesis of MoV-Based Mixed-Oxide Catalysts for Ethane Partial Oxidation

The catalytic performance of Mo8V2Nb1-based mixed-oxide catalysts for ethane partial oxidation is highly sensitive to the doping of elements with redox and acid functionality. Specifically, control over product distributions to ethylene and acetic acid can be afforded via the specific pairing of redox elements (Pd, Ni, Ti) and acid elements (K, Cs, Te) and the levels at which these elements are doped. The redox element, acid element, redox/acid ratio, and dopant/host ratio were investigated using a three-level, four-factor factorial screening design to establish relationships between catalyst composition, structure, and product distribution for ethane partial oxidation. Results show that the balance between redox and acid functionality and overall dopant level is important for maximizing the formation of each product while maintaining the structural integrity of the host metal oxide. Overall, ethylene yield was maximized for a Mo8V2Nb1Ni0.0025Te0.5 composition, while acetic acid yield was maximized for a Mo8V2Nb1Ti0.005Te1 catalyst

A Novel Laboratory Course on Advanced Chemical Engineering Experiments

The chemical engineering curriculum in the United States has trained generations of technical experts who have successfully optimized chemical processes and products once they entered the chemical industry. The U.S. chemical industry, however, has entered a critical stage in which it must be able to create new and differentiated value through technical innovations that arc essential for long-term survival. This innovation process will require new skills that go far beyond the traditional expertise for the optimization of tasks possessed by young chemical engineers. The innovators must be able to identify new opportunities, explore the boundaries of technology, evaluate critical issues, develop and implement technologies, and communicate effectively with scientists and engineers from other disciplines. Therefore, one of the most important educational tasks of a modern university, in combination with a strong theoretical foundation, is to challenge students in laboratory courses to think, explore, hypothesize, plan, solve, and evaluate. The typical sequence of laboratory skills development stops short of introducing young engineers to the most critical aspects of experimental work. Chemical engineers usually begin developing their laboratory skills in chemistry courses, where experiments are closely managed. At this early stage in their development, students follow detailed instructions and learn basic principles by observing the results. In the undergraduate engineering laboratory course (the unit operations lab ), students have more freedom in experimental design but still have well-defined objectives and manipulate equipment someone else has set up. It is rare, however, for undergraduate students to be taught how to create new experiments. It is also rare for undergraduate students, and hence beginning graduate students, to have an appreciation for the care, planning, design, and testing required to produce equipment that will give reliable and useful results. Even such simple issues as leak testing or adapting analytical devices to new tasks are outside most students* experience. Even more important is an absence of opportunities to learn how the lessons learned from the failure of an approach can be fed back into the empirical process to seed the finally successful idea. All these skills require more creative freedom than is usually allowed in a well-structured laboratory course. In the novel laboratory teaching approach described here, we try to provide students with a learning environment that allows them to develop advanced experimental skills that are necessary for success in research and development environments

Bio-Oils From Vacuum Ablative Pyrolysis of Torrefied Tobacco Residues

Fast pyrolysis, in combination with torrefaction pretreatment, was used to convert tobacco residues to value-added bio-fuels and chemicals. Tobacco plant residues were torrefied at 220, 260, and 300 °C, before being pyrolyzed at 450, 500, 550, and 600 °C in a rotating blade ablative reactor under vacuum conditions to test the effects on product yields. With torrefaction, tobacco residues thermally decomposed 20-25% w/w at low temperatures. Torrefaction and pyrolysis temperatures were found to markedly affect pyrolytic product yields of bio-chars and bio-oils, while having no effect on gas-phase products. Bio-oil yields exhibited a direct relation with pyrolysis temperature and an inverse relation with torrefaction temperature. Bio-oils produced were separated into light and heavy oils and analyzed by GC-MS, and1H and13C NMR. Nicotine was found to be the main compound in the light and heavy oils along with several phenols and cresols in the heavy oil

Bio-Oils From Vacuum Ablative Pyrolysis of Torrefied Tobacco Residues

Fast pyrolysis, in combination with torrefaction pretreatment, was used to convert tobacco residues to value-added bio-fuels and chemicals. Tobacco plant residues were torrefied at 220, 260, and 300 °C, before being pyrolyzed at 450, 500, 550, and 600 °C in a rotating blade ablative reactor under vacuum conditions to test the effects on product yields. With torrefaction, tobacco residues thermally decomposed 20-25% w/w at low temperatures. Torrefaction and pyrolysis temperatures were found to markedly affect pyrolytic product yields of bio-chars and bio-oils, while having no effect on gas-phase products. Bio-oil yields exhibited a direct relation with pyrolysis temperature and an inverse relation with torrefaction temperature. Bio-oils produced were separated into light and heavy oils and analyzed by GC-MS, and1H and13C NMR. Nicotine was found to be the main compound in the light and heavy oils along with several phenols and cresols in the heavy oil

Self-Healing Catalysts: CO\u3csub\u3e3\u3c/sub\u3eO\u3csub\u3e4\u3c/sub\u3e Nanorods for Fischer-Tropsch Synthesis

We combine kinetic and spectroscopic data to demonstrate the concept of a self-healing catalyst, which effectively eliminates the need for catalyst regeneration. The observed self-healing is triggered by controlling the crystallographic orientation at the catalyst surface

Kinetics Study of the Hydrodeoxygenation of Xylitol over a ReO\u3csub\u3ex\u3c/sub\u3e-Pd/CeO\u3csub\u3e2\u3c/sub\u3e Catalyst

In this study, we elucidate the reaction kinetics for the simultaneous hydrodeoxygenation of xylitol to 1,2-dideoxypentitol and 1,2,5-pentanetriol over a ReOx-Pd/CeO2 (2.0 weight% Re, 0.30 weight% Pd) catalyst. The reaction was determined to be a zero-order reaction with respect to xylitol. The activation energy was elucidated through an Arrhenius relationship as well as non-Arrhenius kinetics. The Arrhenius relationship was investigated at 150–170◦ C and a constant H2 pressure of 10 bar resulting in an activation energy of 48.7 ± 10.5 kJ/mol. The investigation of non-Arrhenius kinetics was conducted at 120–170◦ C and a sub-Arrhenius relation was elucidated with activation energy being dependent on temperature, and ranging from 10.2–51.8 kJ/mol in the temperature range investigated. Internal and external mass transfer were investigated through evaluating the Weisz–Prater criterion and the effect of varying stirring rate on the reaction rate, respectively. There were no internal or external mass transfer limitations present in the reaction