TiI4-doping induced bulk defects passivation in halide perovskites for high efficient photovoltaic devices

Power conversion efficiency (PCE) and stability are two important properties of perovskite solar cells (PSCs). Particularly, defects in the perovskite films could cause the generation of trap states, thereby increasing the nonradiative recombination. To address this issue, suitable dopants can be incorporated to react with non-bonded atoms or surface dangling bonds to passivate the defects. Herein, we introduced TiI₄ into CH₃NH₃PbI₃ (MAPbI₃) film and obtained a dense and uniform morphology with large crystal grains and low defect density. The champion cell based on 0.5% TiI₄-doped MAPbI₃ achieved a PCE as high as 20.55%, which is superior to those based on pristine MAPbI₃ (17.64%). Moreover, the optimal solar cell showed remarkable stability without encapsulation. It retained 88.03% of its initial PCE after 300 h of storage in ambient. This work demonstrates TiI₄ as a new and effective passivator for MAPbI₃ film.     

Enhanced methanol oxidation on PtNi nanoparticles supported on silane-modified reduced graphene oxide

Developing low cost, highly efficient, and long-term stability electrocatalysts are critical for direct oxidation methanol fuel cell. Despite huge efforts, designing low-cost electrocatalysts with high activity and long-term durability remains a significant technical challenge. Here, we prepared a new kind of platinum-nickel catalyst supported on silane-modified graphene oxide (NH₂-rGO) by a two-step method at room temperature. Powder X-ray diffraction, UV–vis spectroscopy, Raman, FTIR spectroscopy and X-ray photoelectron spectroscopy results confirm that GO was successfully modified with 3-aminopropyltriethoxysilane (APTES), which helps to uniformly disperse PtNi nanoparticles. Cyclic voltammetry, chronoamperometry, CO-stripping and rotating disk electrode (RDE) results imply that PtNi/NH₂-rGO catalyst has significantly higher catalytic activity, enhance the CO toxicity resistance, higher stability and much faster kinetics of methanol oxidation than commercial Pt/C under alkaline conditions.     

Stability,reactivity and decomposition kinetics of surface passivated α-AlH3 crystals

As a novel high energy fuel, aluminum hydride (AlH₃) has great potential in the field of solid propellants because of its high hydrogen capacity, which can significantly improve the specific impulse of solid propellants. In order to improve the stability of α-AlH₃, hydrochloric acid has been used to stabilize AlH₃ and the stabilization mechanism has been investigated. Various characterization techniques including scanning electron microscopy, X-ray electron spectrometer, X-ray diffraction, thermal analysis, and vacuum stability test have been employed to investigate the morphology, crystal structure, thermal stability, and decomposition kinetics of raw and passivated α-AlH₃. The results showed that the honeycomb-like structures could be formed on the surface of α-AlH₃ after passivation. First of all, the initial decomposition temperatures of the passivated samples were slightly increased. In particular, for the optimized sample with 105 min passivation time (AlH₃-105min), the initial decomposition temperature (173.4 °C) is increased by 5.6 °C. Moreover, the total decomposition time (1652 min) is improved by about 50% than that of the raw sample (1098 min). Besides, the decomposition activation energies (E_a) of passivated samples are much higher than that of the raw sample (84.8 kJ mol^?1), in which the optimized sample (AlH₃-105min) reaches 107.1 kJ. mol^?1. The decomposition kinetics model may change from 3-D nucleation and nucleus growth model to 2-D nucleation and nucleus growth model. It demonstrates the passivated samples have a lower decomposition rate and higher thermal stability. The stabilization mechanism is as follows: removing the impurities on the surface and accelerating the hydrolysis reaction of AlH₃ to generate complete and dense oxide layers.     

C-O-Co bond-stabilized CoP on carbon cloth toward hydrogen evolution reaction

Highly active, low-cost, and durable electrocatalysts toward hydrogen evolution reaction (HER) are crucial for electrochemical water splitting. Herein, a green, facial, and effective strategy was proposed to develop CoP on carbon cloth (CoP/o-CC) as efficient self-supported hydrogen evolution electrodes. The designed CoP/o-CC exhibits superior catalytic activity with overpotentials of 118 mV and 95.45 mV to deliver a current density of 10 mA cm^?2 in acidic and alkaline solution, respectively, which is superior to most reported studies. In addition, the designed CoP/o-CC electrode also possesses excellent stability even under a large current density of 100 mA cm^?2. The origin of significantly enhanced stability thereby was further systematically investigated. Experimental study reveals that the oxygenated functional groups on carbon cloth play the role to bind the CoP electrocatalysts, forming C-O-Co bonds. Thus, the enhanced electrochemical and structural stability of CoP/o-CC is predominantly caused by the interfacial interaction of the C-O-Co bonds between the CoP active materials and surface oxygenated functional groups of carbon fiber. Therefore, we believe that this work provides an in-depth insight into the role of interfacial interaction between the substrate and the catalysts and offers a new methodology to design durable and efficient electrocatalysts.     

Cooperative role of cobalt and gallium under the ethanol steam reforming on Co/CeGaOx

The performance of gallium promoted cobalt-ceria catalysts for ethanol steam reforming (ESR) was studied using H₂O/C₂H₅OH = 6/1 mol/mol at 500 °C. The catalysts were synthetized via cerium-gallium co-precipitation and wetness impregnation of cobalt. A detailed characterization by N₂-physisorption, XRD, H₂-TPR and TEM allowed the normalization of contact time and rationalization of the role of each catalysts component for ESR. The gallium promoted catalyst, Co/Ce₉₀Ga₁₀O_x, was more efficient for the ethanol conversion to H₂ and CO₂, and the production of oxygenated by-products (such as, acetaldehyde and acetone) than Co/CeO₂. The catalytic performance is explained assuming that: (i) bare ceria is able to dehydrogenate ethanol to ethylene; (ii) Ce–O–Ga interface catalyzes ethanol reforming; (iii) both Ce–O–Co and Ce–O–Ga interfaces takes part in acetone production; and (iv) cobalt sites further allow C–C scission. It is suggested that a cooperative role between Co and Ce–O–Ga sites enhance the H₂ and CO₂ yields under ESR conditions.     

A boron-11 NMR study of the stability of the alkaline aqueous solution of sodium borohydride that is both an indirect fuel and a direct fuel for low-temperature fuel cells

Alkaline aqueous solution of sodium borohydride NaBH₄ (denoted SB-fuel) is an indirect fuel when it is used to generate H₂ by hydrolysis, with the as-generated H₂ feeding a fuel cell, and it is a direct fuel when it is an anodic fuel of a direct fuel cell. However, SB-fuel suffers from a major drawback: NaBH₄ spontaneously hydrolyzes. Our study falls within this context. We studied the instability, at the NMR scale and over 12 weeks, of a series of SB-fuels (initial NaBH₄ concentration from 3.65 to 31.22 wt%, NaOH concentration from 1 to 16 M, and temperature between ?15 and 60 °C) to find the conditions at which SB-fuel can be stored for weeks in relative safety. We found that SB-fuel with a NaOH concentration of ≥8 M is relatively stable under cold conditions (?15 and 4 °C). In these conditions, NaBH₄ is not prevented from hydrolyzing, but the reaction is significantly mitigated. Otherwise, our study highlights the gaps in our understanding of the SB-fuel, emphasizes SB-fuel is a new concept of fuel (it should not be seen as any current fuel), and points out the challenges for attaining higher technology readiness levels.     

深孔爆破成井技术在三道庄钼矿的试验与应用研究

洛钼集团矿山公司三道庄矿区由于历史原因,露天开采境界地下内存在的采空区已危及矿山公司的正常安全生产,阻碍了洛钼集团可持续发展。为解决这一重大问题,经过充分调研和多方论证,认为深孔一次爆破成井技术是解决此类采空区难题唯一的经济上合理、技术可行、安全可靠的手段与途径。深孔爆破成井实现与采空区顶板的贯通,使采空区边岩稳定,顶岩暴露面积缩小,确保了采空区的稳定;保证了台阶正常推进。     

Ni-based catalysts with coke resistance enhance by radio frequency discharge plasma for CH4/CO2 reforming

Coke deposition has been considered to be one of the most important reasons hindering the stability of the catalyst during CH₄/CO₂ reforming. In this study, after the addition of P123 (PEG-PPG-PEG triblock copolymer), Ni²⁺ can be well-dispersed on the mesoporous molecular sieve MCM-41. And then, the catalysts were prepared by using N₂ radio frequency (RF) discharge plasma for different treatment times to reduce the size of Ni particles, improve the anti-coking performance, and thereby improve the stability of the catalyst. The results showed that the catalyst NM-P123-PN2h exhibits superior catalytic properties in the CH₄/CO₂ reforming. The initial conversions of CH₄ and CO₂ were 90.80% and 89.60% at 750 °C, respectively. The catalyst NM-P123-PN2h showed highly coke resistance with less carbon deposition (1.12%) at 750 °C after 10 h of continuous reaction, while the carbon deposition of the catalyst NM-C was 37.32%. Compared with the traditional calcination method, the catalyst prepared by plasma treatment has a smaller particle size and better dispersibility of nickel. In particular, the nickel particle size of the catalyst NM-C was 8.37 nm, however, that of the catalyst NM-P123-PN2h was only 1.70 nm, and the nickel particle size was reduced by 5 times. Therefore, it can be concluded that the catalyst prepared under the combined action of P123 and RF plasma-treated can effectively improve the coke resistance of the catalyst and the stability of the CH₄/CO₂ reforming.     

Adding new floors to old timber-framed buildings: An assessment of demolished and preserved courtyard houses in the historic centre of Madrid

The constructive analysis of Madrid's old timber-framed collective courtyard buildings, whether demolished, preserved intact, or enlarged, has achieved the dating of relevant case studies. New parameters established in this study set a chronology based on front sector original projects: old (1737–1788), pre-modern (1788–1847) and modern (1847–1892). The on-site inspection and archival research point to ongoing misleading construction in the historic Southern area. Some modern corralas erected on top of pre-existing buildings confirm the initial hypothesis. First dimensioning rules for new façades and the stability required in old ones before adding new storeys, maintaining the original masonry or double-layered system, are discovered. Undated buildings suggest their possible origin a la malicia and a later transformation into transitional corralas. Finally, an analysis of the demolished courtyards narrows down the dating and points to new conjectures in some preserved by showing their uneven layout, old features, and structural discordances in each sector.