Electronic regulation and core-shell hybrids engineering of palm-leaf-like NiFe/Co(PO3)2 bifunctional electrocatalyst for efficient overall water splitting

Constructing efficient and stable bifunctional electrocatalysts for overall water splitting remains a challenge because of the sluggish reaction kinetics. Herein, the core-shell hybrids composed of Co(PO₃)₂ nanorod core and NiFe alloy shell in situ grown on nickel foam (NiFe/Co(PO₃)₂@NF) are synthesized. Owing to the hierarchical palm-leaf-like structures and strong adhesion between NiFe alloys, Co(PO₃)₂ and substrates, the catalyst provides a large surface area and rapid charge transfer, which facilitates active sites exposure and conductivity enhancement. The interfacial effect in the NiFe/Co(PO₃)₂ core-shell structure modulates the electronic structure of the active sites around the boundary, thereby boosting the intrinsic activity. Benefiting from the stable structure, the durability of the catalyst is not impaired by the inevitable surface reconfiguration. The NiFe/Co(PO₃)₂@NF electrode presents a low cell voltage of 1.63 V to achieve 10 mA cm^?2 and manifests durability for up to 36 h at different current densities.     

Co?N graphene encapsulated cobalt catalyst for H2O2 decomposition under acidic conditions

Hydrogen peroxide (H₂O₂) has been listed as one of the 100 most important chemicals in the world. However, huge amount of residual H₂O₂ is hard to timely decomposed into O₂ and H₂O under acidic condition, easily resulting in explosion hazard. Here, we reported a core–shell structure catalyst, that is graphene with Co N structure encapsulated Co nanoparticles. Co N graphene shell serves as the active site for the H₂O₂ decomposition, and Co core further enhance this decomposition. Benefiting from it, the H₂O₂ decomposition were close to 100% after 6 cycles without pH adjustment, which increased 6 orders of magnitude compared with no catalyst. At the same time, the O₂ generation reached 99.67% in 2 h with little metal leaching, and ·OH has been greatly inhibited to only 0.08%. This work can cleanly remove H₂O₂ with little deep oxidation and protect the process of H₂O₂ utilization to achieve a safer world.     

Double pyrovanadates CaMgV2O7: Formation mechanism,phase structure,and thermodynamic properties

A double pyrovanadate CaMgV₂O₇ sample was synthesized via a facile solid-state route under an air atmosphere. The nonequilibrium formation pathways of the CaMgV₂O₇ were investigated via powder X-ray diffraction. A multistep reactions path (metavanadates–pyrovanadates–double pyrovanadate CaMgV₂O₇) was proposed to describe the formation of the CaMgV₂O₇ considering the thermodynamic and kinetic factors. The cell unit parameters of the CaMgV₂O₇ sample indicated the crystallization according to a monoclinic system with space group P12/c1(14), and the lattice parameters of a = 6.756 Å, b = 14.495 Å, c = 11.253 Å, β = 99.12, and V = 108.806 Å³. X-ray photoelectron spectroscopy also confirmed the +5 oxidation state vanadium in CaMgV₂O₇. The endothermic effects at 1033 and 1143 K were related to the incongruent melting and liquidus temperatures of CaMgV₂O₇, respectively. The comprehensive thermodynamic properties of CaMgV₂O₇ were established in both low- and high-temperature regions, utilizing a physical property measurement system and multi-high-temperature calorimetry (96 lines). The heat capacity (200 J mol K⁻¹) and entropy (198 J mol K⁻¹) at 298.15 K were computed based on the low-temperature heat capacity values, and the enthalpy of formation at 298.15 K was also estimated. The fitted high-temperature capacity can be used to obtain the changes in the enthalpy, entropy, and Gibbs free energy. This study is part of building a reliable thermodynamic database of the CaO–MgO–V₂O₅ system.     

Physical properties of microwave and solid state synthesized La0.7Na0.3MnO3

We report the structural, magnetic, electrical and broadband microwave absorption in La_0.7Na_0.3MnO₃ sample synthesized by microwave (MW) irradiation (Na_0.3LMO_MW) and compare them to the sample synthesized by solid-state (SS) reaction method (Na_0.3LMO_SS). Single phase Na_0.3LMO_MW was synthesized at 800 °C in 30 min, whereas, Na_0.3LMO_SS sample was obtained by sintering at 1200 °C for 48 h. Although both these samples show ferromagnetic transition at T_C ～324.8 K, the MW-synthesized sample shows distinct physical properties: broad ferromagnetic transition, smaller saturation magnetization, a large difference between the magnetic ordering and metal-insulator transition temperatures, a large high-field magnetoresistance, a table top-like magnetocaloric effect, and a large low-field microwave absorption compared to the solid state synthesized sample. These differences are suggested to arise from magnetic heterogeneity induced by smaller grain size and surface spin disorder in the MW synthesized La_0.7Na_0.3MnO₃.     

Molecular dynamics study of interfacial load transfer capability in amorphous SiOx films deposited on alumina surfaces

Effective adhesion between AlO_x and SiO_x is important for protective coatings and high-k films under extreme operating conditions. Here, we study the chemo-mechanical behavior of the AlO_x/SiO_x interface and its delamination mechanism using all-atom reactive molecular dynamics simulations. The structure of the interface is examined by the formation of bridge oxygen and the distribution of nanopores. The cleavage of ionic bonds during delamination and the resulting adhesion strength of the system are quantified using pull-out simulations. The results reveal the dependence of the nanopores and ionic bond formation on the oxide structure. The ionic bond density at the interface increases as the oxidation of the aluminum surface proceeds, which directly increases the adhesion strength with SiO_x. In particular, the global coordination distribution in the homogeneously grown oxide inhibits the formation of nanopores inside the aluminum substrate and contributes to extremely high adhesion strength. This reveals a fundamental relationship between physicochemical parameters and engineering mechanics for hetero-oxide structure design.     

一种“KooN”结构的马尔可夫简并建模和简化计算的方法

IEC61508等标准提出了几种计算安全仪表系统需求时平均失效概率的方法,但是,对于具有冗余配置的复杂系统,随着组件数量的增加,系统的中间状态数量快速增长,用户难以构建马尔可夫模型,即便借助计算机来建模运算也较为耗时。提出了一种同型“K oo N”简并状态的马尔可夫建模的通用方法,首先是根据降级状态进行判断,将符合条件的状态进行简并,然后对标记为危险失效状态的概率进行计算。通过严格的理论推导,该简并状态方法可以在不损失精度的前提下简化马尔可夫建模。     

Rip currents near coastal structures in Lake Michigan: Characterization and assessment for warnings

Rip currents near coastal structures commonly occur in Lake Michigan in the Great Lakes region of the United States. Lack of timely warning due to undocumented characteristics of rip currents and no assessment tool can contribute to tragic drownings incidents. In this paper, we characterized rip current occurrences near breakwater structures and developed an assessment tool for providing timely rip current warnings to beachgoers at the study site, City of Port Washington, WI. Characteristics of rip currents near the structure were observed from field measurements or visual images. Deflection rip currents had speeds of ～ 0.2 m/s and lasted for several hours. The rip current occurrences were associated with environmental proxies. It was found that rip currents can occur even when the water appears calm near the structure. A Structure Rip Checklist and Assessment Matrix (SRiCAM) with a four-tiered risk was developed and validated using observations. Furthermore, the SRiCAM was integrated into cyberinfrastructure with a data contingency plan to provide real-time warnings to the public. The applicability of the SRiCAM to other locations across Lake Michigan was further tested and results are promising. Overall, the SRiCAM has the potential to be widely extended to foster recreational water safety and resilience to rip current hazards in the Great Lakes.     

Influence of high energy ball milling on structural,microstructural and optical properties of TiO2 nanoparticles

The influence of high-energy ball milling on structural, microstructural, and optical properties of TiO₂ by modifying the nanoparticle size was studied. Five samples were extracted at different milling times (0, 2, 4, 8, and 13 h). The average particle sizes estimated by dynamic light scattering (DLS) were 205, 155.8, 116.8, 82.9, and 82.7 nm at 0, 2, 4, 8, and 13 h, respectively. X-ray diffraction analysis confirmed progressive broadening of the peaks as the milling time elapsed. Besides, a correlation was found between d spacing and the average crystal size. The UV–Vis diffuse reflectance spectra of TiO₂ revealed a decrease in reflectance due to particle size reduction. Similarly, an alteration of the bandgap transition energy was presented, whose values gradually decreased from 2.966 eV to 2.861 eV for the sample without and with the maximum duration milling performed (13 h), respectively. Likewise, the SEM analysis showed a distribution in nanoparticle size that became more homogeneous and smaller average grain size as the milling duration was longer.     

Isostructural phase transition (IPT) in CaMoO4 with Scheelite structure

The ceramic compound CaMoO₄ is synthesized via a solid-state reaction technique. Rietveld refinement studies were done on the powder X-ray diffraction data of CaMoO₄ and revealed that the compound is crystallized in the tetragonal Scheelite structure with I4₁/a space group. The differential scanning calorimetry (DSC) studies on CaMoO₄ divulged an anomaly around 440 °C. This anomaly is further probed using the temperature-dependent Raman and dielectric spectroscopic measurements and are corroborating with the results obtained from DSC. A detailed investigation on the temperature-dependent Raman spectroscopic data revealed that the A_1g mode of CaMoO₄ showed a soft phonon behavior up to the phase transition temperature. It is observed that the A_1g mode displayed phonon hardening behavior with further increasing the temperature. The anomaly is attributed to an isostructural phase transition (IPT), a rarely observed phenomenon in the compounds with Scheelite structure. The IPT in CaMoO₄ is elucidated with a phonon softening mechanism.     

水力空化改质对重质原油沥青质及性质的影响

利用水力空化过程产生局部的高温、高压、高射流以及强大的剪切力等极端化学物理条件改质处理沙特重质原油，试验结果表明：沙特重质原油经过水力空化改质后粘度由13.61降低至7.22mm2/s，残碳由7.16%降低至6.48%，实沸点蒸馏后减压渣油降低1个百分点。进一步采用APPI FT-IR MS、XRD、FT-IR、SEM和粒度分布等技术研究了水力空化改质对沙重原油分子组成，沥青质团聚体微晶结构、沥青质胶束粒径分布、沥青质官能团、沥青质形貌等方面的影响，从分子角度阐述空化改质重油的机理。研究结果表明：水力空化改质后沙重原油分子量分布、芳烃类化合物缔合作用变小；沥青质对低DBE化合物吸附性能降低；沥青质团聚体微晶结构更加松散；沥青质胶束粒度分布降低；沥青质分子相互团聚作用力减弱。进一步考察了水力空化改质前后减压渣油延迟焦化性能，改质处理后焦炭产率降低1.85个百分点，液体收率和气体产率分别增加1.52和0.33个百分点，水力空化改质对沥青质性质、结构特点的改善能够有效的提高其加工性能。