Experimental methods in chemical engineering: Electron paramagnetic resonance spectroscopy-EPR/ESR

Electron paramagnetic resonance (EPR) spectroscopy, also known as electron spin resonance spectroscopy (ESR), utilizes absorption of microwave radiation by unpaired electrons in a magnetic field. The interaction between the unpaired electron(s) and nearby magnetic nuclei helps identify paramagnetic species and can provide information about the motion of the molecule and the local polarity, pH, viscosity, concentration, and accessibility to other paramagnetic species. This mini-review discusses the fundamental underpinnings of EPR needed to correctly interpret EPR spectra. We describe various types of EPR spectra encountered by chemical engineers, and use application examples drawn from the chemical engineering literature to illustrate the information available from the technique. Few chemical engineering departments or even chemistry departments have EPR instruments, which contributes to the significant barrier that prevents this being adopted as a routine measurement technique. However, in 2016 and 2017, Web of Science indexed 7000 articles that applied EPR spectroscopy. A bibliometric map categorized the keywords in four categories based on co-occurrences: magnetic properties, films, and luminescence; crystal structure, complexes, and ligands; nanoparticles, oxidation, and degradation; and, systems, radicals, and H₂ O₂ .     

基于动态模态分解的缸内流场演变及动能分析

采用高速粒子图像测速技术(particle image velocimetry,PIV)测量了一台直喷式光学发动机的缸内流场,利用动态模态分解(dynamic mode decomposition,DMD)算法,提取了发动机从进气冲程早期到压缩冲程后期中出现的多尺度涡团结构,量化了涡团的比动能在整个冲程阶段的衰减程度。结果表明:从进气冲程早期开始,缸内流场主要由低阶DMD模态表现的大尺度流场结构和高阶DMD模态表现的小尺度涡团结构组成;DMD模态的比动能变化可清楚地反映从大尺度流场结构到小尺度涡团的能量级联和耗散过程。同时还发现,与压缩冲程相比,进气冲程期间的流场可形成更多小尺度的涡团结构,并表现出更快的能量衰减特征,且该阶段流场能量衰减现象对发动机转速更加敏感。     

Production of hydrogen by catalytic methane decomposition using biochar and activated char produced from biosolids pyrolysis

Catalytic methane decomposition (CMD) was studied by employing biochar and activated char of biosolids’ origin under different reaction temperatures and methane concentrations. Higher reaction temperatures and lower inlet methane concentrations were found to be favourable for achieving higher methane conversion. A maximum initial methane conversion of 71.0 ± 2.5 and 65.2 ± 2.3% was observed for activated char and biochar, respectively at 900 °C and for 10% CH₄ in N₂ within the first 0.5 h of experiment. Active sites from oxygen containing carboxylic acid functional groups and smaller pore volume and pore diameter were attributed to assist in higher initial methane conversion for biochar and activated char respectively. However, rapid blockages of active sites and surfaces of biochar and activated char due to carbon formation have caused a rapid decline in methane conversion values in the first 0.5 h. Later on, crystalline nature of the newly formed carbon deposits due to their higher catalytic activity have stabilised methane conversion values for an extended experimental period of 6 h for both biochar and activated char. The final conversion values at the end of 6 h experiment with biochar and activated char at 900 °C and for 10% CH₄ in N₂, were found to be 40 ± 1.9 and 35 ± 1.6% respectively. Analysing carbon deposits in detail revealed that carbon nanofiber type structures were observed at 700 °C while nanospheres of carbon were found at 900 °C.     

Methane thermocatalytic decomposition to COx-free hydrogen and carbon nanomaterials over Ni–Mn–Ru/Al2O3 catalysts

Thermocatalytic decomposition of methane is proposed to be an economical and green method to produce CO_x-free hydrogen and carbon nanomaterials. In this work, the catalytic performance of Ni–Mn–Ru/Al₂O₃ catalyst under different reaction parameters (such as, pre-reduction temperature, reaction temperature, space velocity, etc.) were investigated to obtain optimum reaction conditions. The catalysts were characterized by N₂ adsorption/desorption, X-ray diffraction, inductively coupled plasma optical emission spectrometer and hydrogen temperature programmed reduction. For the 60 wt% Ni-5 wt% Mn-10 wt% Ru/Al₂O₃ catalyst using Ru(NO)(NO₃)_x(OH)_y(x + y = 3) as Ru precursor, the methane conversion rate obtained is high as 93.76% under optimum reaction conditions (reduction at 700 °C for 1 h, reaction at 750 °C, GSHV = 36,000 mL/g_cat h). Carbon nanomaterials formed during the process of methane thermocatalytic decomposition were characterized by scanning electron microscopy, thermal gravimetric analyzer and Raman spectroscopy. Carbon nanofibers were formed over all the Ni–Mn–Ru/Al₂O₃ catalysts.     

High-temperature degradation of butadiene-based model elastomers by reactive molecular dynamics simulation

Thermal degradation of butadiene-based model elastomers was analyzed via a novel reactive molecular dynamics simulation (ReaxFF) method. The molecular simulation was carried out on 40 monomer units connected together. Degradation pathways of both homopolymer and copolymer of butadiene-based model elastomers such as polybutadiene (BR) and poly (styrene-co-butadiene) (SBR) were studied. The evolution of different fragmented products was examined as a function of time and heating rate. The formation mechanisms of different degraded fragments were visualized via the simulation method. The major decomposition products obtained from these model compounds were the monomers and comonomers. Pyrolysis gas chromatography–mass spectrometry (py-GC–MS) analysis was performed on the commercial samples of BR and SBR to verify the simulation results. The results obtained from the reactive simulation were very consistent with the experimental results. The activation energy required for the thermal decomposition of butadiene-based model elastomers were calculated both from the ReaxFF simulation and thermogravimetric analysis (TGA). The results were also in good agreement. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48592.     

Concept design of a novel reformer producing hydrogen for internal combustion engines using fuel decomposition method: Performance evaluation of coated monolith suitable for on-board applications

Hydrogen addition effectively reduces the fuel consumption of spark ignition engines. We propose a new on-board reformer that produces hydrogen at high concentrations and enables multi-mode operations. For the proposed reformer, we employ a catalytic fuel decomposition reaction via a commercial NiO–CaAl₂O₄ catalyst. We explore the physical and chemical aspects of the reforming process using a fixed bed micro-reactor operating at temperatures of 550–700 °C. During reduction, methane is decomposed to form hydrogen and carbon. Carbon formation is critical to hydrogen production, and free space for carbon growth is essential at low temperatures (≤600 °C). We define a new accumulated conversion ratio that quantitatively measures highly transient catalytic decomposition. The free space of the coated monolith clearly aided low-temperature decomposition with negligible pressure drop. The coated substrate is therefore suitable for on-board applications considering that our reformer concept also utilizes the catalytic fuel decomposition reaction.     

Correlation of hydrogen generation and optical emission properties of plasma in water photolysis on perovskite photocatalysts

Photocatalytic decomposition of organic materials-contained aqueous solution is assessed using a plasma discharged into the liquid directly. The correlation of H₂ generation and optical emission spectroscopy is discussed in terms of photocatalytic H₂ production using plasma and photocatalysts. Variations of the active species are evaluated according to the conditions of the plasma in the liquid phase. The optical emission spectra vary according to the plasma discharging conditions in the liquid phase. The intensities of the OH· peaks at 309 nm increase with the addition of ethanol or acetaldehyde in water. The highest intensities and rate of H₂ evolution are observed at a 10% acetaldehyde concentration in the aqueous solution. The rates of H₂ evolution in the ethanol or acetaldehyde solution correspond to the concentration of OH· in the solution. The photocatalytic reaction using liquid plasma generates hydrogen at the same time as the decomposition of the organic chemicals. The rate of hydrogen evolution in aqueous solutions containing the organic chemicals is higher than that in pure water. This is because hydrogen is further generated due to hydrogen generation by photolysis of the organic chemicals. CaTiO₃ perovskite photocatalyst shows better photocatalytic activity than TiO₂. Ni loading on the photocatalyst lead to an increase in H₂ production.     

Plasmonic Bi nanoparticle decorated BiVO4/rGO as an efficient photoanode for photoelectrochemical water splitting

We report the application of plasmonic Bi nanoparticles supported rGO/BiVO₄ anode for photoelectrochemical (PEC) water splitting. Nearly, 2.5 times higher activity was observed for Bi-rGO/BiVO₄ composite than pristine BiVO₄. Typical results indicated that Bi-rGO/BiVO₄ exhibits the highest current density of 6.05 mA/cm² at 1.23 V, whereas Bi–BiVO₄ showed the current density of only 3.56 mA/cm². This enhancement in PEC activity on introduction of Bi-rGO is due to the surface plasmonic behavior of BiNPs, which improves the absorption of radiation thereby reduces the charge recombination. Further, the composite electrode showed good solar to hydrogen conversion efficiency, appreciable incident photon-to-current efficiency and low charge transfer resistance. Hence, Bi-rGO/BiVO₄ provides an opportunity to realize PEC water splitting.     

铝空气电池废电解液生产超细氢氧化铝工艺条件研究

以铝空气电池的废电解液为原料, 采用种分法生产氢氧化铝。结果表明, 当种分时间为24 h、晶种系数为2%~4%时, 可生产出超细氢氧化铝, 且粒径分布宽度窄, 阻燃性能优良, 达到HG/T4530-2013氢氧化铝阻燃剂ATH-1一等品的要求。     

Preparation and enhanced photoelectrocatalytic properties of a three-dimensional TiO2-Au porous structure fabricated using superaligned carbon nanotube films

Three dimensional TiO₂–Au cross-nanoporous structure (3D TiO₂–Au CNS) as an efficient photoelectrocatalytic system was fabricated using superaligned carbon nanotube films as etching masks and electron-beam evaporation. The 3D TiO₂–Au CNS exhibited a broad absorption band in the visible region, and the incident photon-to-current conversion efficiency of 3D TiO₂–Au CNS/Ti electrode was 3–4 times higher than that of pure TiO₂ electrode. The photocurrent density of the 3D TiO₂–Au CNS device was 0.079 mA cm⁻² at 0 V vs. Ag/AgCl with a solar irradiance of 100 mW cm⁻². This developed preparation method was simple, of high flexibility and can be adopted for mass production due to its low cost and good compatibility with other processing technologies. The 3D TiO₂–Au CNS and its preparation method have important value in design of photoelectrocatalytic system for research and practical applications, which may have a potential utility in photocatalytic and other photoelectrocatalytic reactions.