In perovskites, exsolution of transition metals has been proposed as a smart catalyst design for energy applications. Although there exist transition metals with superior catalytic activity, they are limited by their ability to exsolve under a reducing environment. When a doping element is present in the perovskite, it is often observed that the surface segregation of the doping element is changed by oxygen vacancies. However, the mechanism of co-segregation of doping element with oxygen vacancies is still an open question. Here we report trends in the exsolution of transition metal (Mn, Co, Ni and Fe) on the PrBaMn2O5+δ layered perovskite oxide related to the co-segregation energy. Transmission electron microscopic observations show that easily reducible cations (Mn, Co and Ni) are exsolved from the perovskite depending on the transition metal-perovskite reducibility. In addition, using density functional calculations we reveal that co-segregation of B-site dopant and oxygen vacancies plays a central role in the exsolution.
This study evaluated the emissions characteristics of hazardous material during fused deposition modeling type 3D printing. Particulate and gaseous materials were measured before, during, and after 3D printing in an exposure chamber. One ABS and two PLA (PLA1 and PLA2) cartridges were tested three times. For online monitoring, a scanning mobility particle sizer, light scattering instrument, and total volatile organic compound (TVOC) monitor were employed and a polycarbonate filter and various adsorbent tubes were used for offline sampling. The particle concentration of 3D printing using ABS material was 33-38 times higher than when PLA materials were used. Most particles were nanosize (<100 nm) during ABS (96%) and PLA1 (98%) use, but only 12% were nanosize for PLA2. The emissions rates were 1.61 × 10(10) ea/min and 1.67 × 10(11) ea/g cartridge with the ABS cartridge and 4.27-4.89 × 10(8) ea/min and 3.77-3.91 × 10(9) ea/g cartridge with the PLA cartridge. TVOCs were also emitted when the ABS was used (GM; 155 ppb, GSD; 3.4), but not when the PLA cartridges were used. Our results suggest that more research and sophisticated control methods, including the use of less harmful materials, blocking emitted containments, and using filters or adsorbents, should be implemented.
This study aimed to evaluate particle emission characteristics and to evaluate several control methods used to reduce particle emissions during three-dimensional (3D) printing. Experiments for particle characterization were conducted to measure particle number concentrations, emission rates, morphology, and chemical compositions under manufacturer-recommended and consistent-temperature conditions with seven different thermoplastic materials in an exposure chamber. Eight different combinations of the different control methods were tested, including an enclosure, an extruder suction fan, an enclosure ventilation fan, and several types of filter media. We classified the thermoplastic materials as high emitter (>10 #/min), medium emitters (10 #/min -10 #/min), and low emitters (<10 #/min) based on nanoparticle emissions. The nanoparticle emission rate was at least 1 order of magnitude higher for all seven filaments at the higher consistent extruder temperature than at the lower manufacturer-recommended temperature. Among the eight control methods tested, the enclosure with a high-efficiency particulate air (HEPA) filter had the highest removal effectiveness (99.95%) of nanoparticles. Our recommendations for reducing particle emissions include applying a low temperature, using low-emitting materials, and instituting control measures like using an enclosure around the printer in conjunction with an appropriate filter (e.g., HEPA filter) during 3D printing.
Exsolution has been intensively studied in the fields of energy conversion and storage as a method for the preparation of catalytically active and durable metal nanoparticles. Under typical conditions, however, only a limited number of nanoparticles can be exsolved from the host oxides. Herein, we report the preparation of catalytic nanoparticles by selective exsolution through topotactic ion exchange, where deposited Fe guest cations can be exchanged with Co host cations in PrBaMn1.7Co0.3O5+δ. Interestingly, this phenomenon spontaneously yields the host PrBaMn1.7Fe0.3O5+δ, liberating all the Co cations from the host owing to the favorable incorporation energy of Fe into the lattice of the parent host (ΔEincorporation = −0.41 eV) and the cation exchange energy (ΔEexchange = −0.34 eV). Remarkably, the increase in the number of exsolved nanoparticles leads to their improved catalytic activity as a solid oxide fuel cell electrode and in the dry reforming of methane.
Postischemic injury in recipients of 3-7-d-old renal allografts was classified into sustained ( n ϭ 19) or recovering ( n ϭ 20) acute renal failure (ARF) according to the prevailing inulin clearance. Recipients of optimally functioning, long-standing allografts and living donors undergoing nephrectomy served as functional ( n ϭ 14) and structural controls ( n ϭ 10), respectively. Marked elevation above control of fractional clearance of dextrans of graded size was consistent with transtubular backleak of 57% of filtrate (inulin) in sustained ARF. No backleak was detected in recovering ARF. To explore a structural basis for backleak, allograft biopsies were taken intraoperatively, 1 h after reperfusion in all recipients, and again on day 7 after transplant in a subset ( n ϭ 10). Electron microscopy revealed disruption of both apical and basolateral membranes of proximal tubule cells in both sustained and recovering ARF, but cell exfoliation and tubule basement membrane denudation were negligible.
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