Experimental methods in chemical engineering: X-ray absorption spectroscopy—XAS,XANES, EXAFS

Although X-ray absorption spectroscopy (XAS) was conceived in the early 20th century, it took 60 years after the advent of synchrotrons for researchers to exploit its tremendous potential. Counterintuitively, researchers are now developing bench type polychromatic X-ray sources that are less brilliant to measure catalyst stability and work with toxic substances. XAS measures the absorption spectra of electrons that X-rays eject from the tightly bound core electrons to the continuum. The spectrum from 10 to 150 eV (kinetic energy of the photoelectrons) above the chemical potential—binding energy of core electrons—identifies oxidation state and band occupancy (X-ray absorption near edge structure, XANES), while higher energies in the spectrum relate to local atomic structure like coordination number and distance, Debye-Waller factor, and inner potential correction (extended X-ray absorption fine structure, EXAFS). Combining XAS with complementary spectroscopic techniques like Raman, Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR) elucidates the nature of the chemical bonds at the catalyst surface to better understand reaction mechanisms and intermediates. Because synchrotrons continue to be the light source of choice for most researchers, the number of articles Web of Science indexes per year has grown from 1000 in 1991 to 1700 in 2020. Material scientists and physical chemists publish an order of magnitude articles more than chemical engineers. Based on a bibliometric analysis, the research comprises five clusters centred around: electronic and optical properties, oxidation and hydrogenation catalysis, complementary analytical techniques like FTIR, nanoparticles and electrocatalysis, and iron, metals, and complexes.     

A large-scale investigation of lateralization in cortical anatomy and word reading: Are there sex differences?

The authors report findings of a large-scale, multitask investigation of sex differences in both structural asymmetries and lateralization of word reading. Two hundred participants were tested in eight divided visual field lexical tasks, and each received a structural magnetic resonance imaging scan. The authors examined whether there was evidence for sex differences in overall measures of neuroanatomical and behavioral lateralization, in specific language tasks and brain regions, and in variation in asymmetry within and across tasks and brain regions. There was very little evidence for sex differences on any behavioral measure. The few indications of sex differences in the current report accounted for 2% or less of the individual variation in asymmetry and could not be replicated in independent subsamples. No sex differences were observed in the asymmetry of structures in Broca's and Wernicke's areas such as pars triangularis, pars opercularis, the planum temporale, planum parietale, or Heschl's gyrus. There were also no sex differences in the variability of neuroanatomical asymmetries within or between brain regions. However, a significant relationship between planum temporale and behavioral asymmetry was restricted to men. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

在线实时浓度监测减少环境压力，降低总体拥有成本

随着半导体制造业的不断发展，对现场浓度测量的需求也不断增加。化学品浓度细微变化都会对晶圆缺陷等级造成不良影响，最为重要的是会对产量产生影响。另外，减少液态化学品废弃物流，使其对环境的影响最小化面临着不断增长的压力。     

A spectro-microscopic investigation of Fe-Co bimetallic catalysts supported on MgO for the production of thin carbon nanotubes

Fe-Co bimetallic catalysts supported on MgO were studied for the catalytic chemical vapor deposition growth of carbon nanotubes (CNTs). Different wt.% metal loadings were investigated at various deposition temperatures and times. Characterization of the products involved thermal analysis (DTA-TGA), X-ray diffraction, spectroscopy (Raman, UPS, EELS and STS) and microscopy (SEM, TEM and STM) techniques. It was found that the metal content is critical, not only to the yield and the structural quality of the synthesized carbon nanotubes, but it can be also used to tune the desired type of synthesized nanotubes. Lower (2 wt.%) loadings of Fe-Co catalysts favor the formation of single- and/or double-wall CNTs for deposition time and temperature 30 min and 800 °C, respectively. Thermal analysis and Raman measurements showed that these thin CNTs were synthesized at high amounts (CNT-per-catalyst wt.% of more than 100%), exhibiting high graphitization degree with only traces of by-products (mainly amorphous carbon) among them. Microscopy results revealed the formation of CNTs bundles, consisting of individual nanotubes with less than 2 nm outer diameter, while additional energy loss measurements pointed out that the deposited CNTs are mainly single wall. Higher (10 wt.%) Fe-Co loadings resulted to the formation of multi-wall CNTs.     

Preparation by flame spray pyrolysis of ABO3±δ catalysts for the flameless combustion of methane

Perovskitic mixed oxides prepared through flame-spray pyrolysis possess a good stability in high-temperature application, viz. the catalytic flameless combustion of methane. Some preparation operating parameters are here analysed, such as O₂ pressure drop along the spraying nozzle, O₂ discharge velocity and flow rate. These parameters have been correlated with specific surface area, activity and durability of the prepared samples, as well as with flame temperature, varied by using different fuel mixtures. It was found that specific surface area increases with increasing O₂ velocity and flow rate and with decreasing the combustion enthalpy of the solvent mixture. This reflects on both activity and durability of the catalyst.     

Cerebral Asymmetries for Language: Evidence for Structural-Behavioral Correlations.

The current investigation tested 20 male right-handers in 5 divided visual field lexical tasks. Asymmetries in Heschl's gyrus, planum temporale, and planum parietale were measured using structural magnetic resonance imaging. Composite task asymmetries were positively correlated with asymmetry of the planum temporale only. There was also an association between the consistency of anatomical and behavioral asymmetries: Individuals who departed the most from the modal pattern of cortical asymmetry across regions also tended to show the greatest variability in asymmetry across tasks. Hence, individual differences in language laterality tasks may be affected by variation in asymmetry of posterior language structures. Additionally, when typical anatomical asymmetries fail to co-occur, there may be a less strictly regulated distribution of function across hemispheres. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Bihemispheric processing of redundant bilateral lexical information

Cerebral asymmetries in lexical ambiguity resolution were studied. In 2 experiments, targets related to the dominant and subordinate meanings of ambiguous word primes were presented for lexical decision after a 750-ms stimulus onset asynchrony. Experiment 1 compared presentation of target words to the left visual field/right-hemisphere (LVF/RH), to the right visual field/left-hemisphere (RVF/LH), or after redundant bilateral visual field (BVF) presentation. Experiment 2 examined unilateral priming in the absence of a BVF condition. On unilateral trials, priming was observed for dominant meanings in both the LVF/RH and RVF/LH, whereas subordinate priming was obtained only in the RVF/LH. These results suggest a possible role of hemispheric interaction in the availability of ambiguous word meanings. BVF performance evidenced a bilateral redundancy gain and priming that resembled that obtained on RVF/LH trials. Additional BVF analyses were not consistent with a strict race model interpretation and appear to implicate hemispheric cooperation in the bihemisperic processing of lexical information.     

Flame-synthesized LaCoO3-supported Pd: 2. Catalytic behavior in the reduction of NO by H2 under lean conditions

A 0.5 wt% Pd/LaCoO₃, prepared by flame-spray pyrolysis (FP), was tested as catalyst for the low-temperature selective reduction of NO by H₂ in the presence of excess O₂. In particular, the effect of the precalcination and prereduction temperature on catalytic activity was compared with that of a similar Pd/LaCoO₃ sample prepared by impregnation with a Pd solution of FP-prepared LaCoO₃. The FP-made catalyst allowed full NO conversion at 150 °C, with 78% selectivity to N₂, thus outperforming the catalytic behavior of the corresponding sample prepared by impregnation. The higher activity of the FP-made catalyst has been attributed to the formation of segregated Co metal particles, not present in the impregnated sample, formed during the precalcination at 800 °C, followed by reduction at 300 °C. Two reaction mechanisms can be deduced from the temperature-programmed experiments. The first of these, occurring at lower temperatures, indicates cooperation between the Pd and Co metal particles, with formation of active nitrates on cobalt, successively reduced by hydrogen spillover from Pd. The second, occurring at higher temperature, allows 50% conversion of NO, with >90% selectivity to N₂, and involves N adatoms formed by dissociative NO adsorption over Pd. Prereduction at 600 °C led to a slight increase in catalytic activity, due to the formation of a PdCo alloy, which is more stable on reoxidization compared with Pd alone. Moreover, the cooperative reaction mechanism seems to be favored by the proximity of Co and Pd in metal particles.