Effects of anions on the structural regulation of Zn‑salen‑modified metal‑organic cage

By virtue of a 3∶1 complementary coordination strategy,a chiral heteroleptic metal-organic cage that con-tains divergent functional units,Pd‑R(Zn),was precisely constructed via self-assembly of monodentate variational Zn-salen ligands RZn and NADH(reduced nicotinamide adenine dinucleotide)mimic modified tridentate ligands with square-planar Pd ions.UV-Vis and luminescence spectra experiments reveal that different anions could selec-tively interact with different sites of Zn-salen modified metal-organic cages to achieve the structural regulation of cage compound,by using the differentiated host-guest electrostatic interactions of counter ions with metal-organic hosts.Compared to other anions,the presence of chloride ions caused the most significant fluorescence emission enhancement of Pd‑R(Zn),meanwhile,the UV-Vis absorption band attributed to the salen aromatic backbone showed an absorption decrease,and the metal-to-ligand induced peak displayed a blue shift effect.Circular dichro-ism and ^(1)H NMR spectra further demonstrate that the introduction of chloride anions is beneficial to keeping a more rigid scaffold.

Tar formation characteristic of integrated process of coal pyrolysis with dry reforming of low carbon alkane over Ni/La_(2)O_(3)-ZrO_(2)

Coal pyrolysis integrated with dry reforming of low-carbon alkane(CP-DRA)is an effective way to improve tar yield.Ni/La_(2)O_(3)-ZrO_(2) with a La/Zr ratio of 4 was a good catalyst for DRA to inhibit carbon deposition and obtain high tar yield in CP-DRA.In this study,the fraction distribution and component of tars from CP-DRA and coal pyrolysis in N_(2) atmosphere(CP-N_(2))were characterized by using several methods to understand the effect of DRA on coal pyrolysis.The isotope trace method was also used to discuss the role of low-carbon alkane in CP-DRA.The results showed that the tar from CP-N_(2)is mainly composed of aliphatic compounds with more C_(al),H_(al) and CH+CH_(2),and the tar from CP-DRA contains more Car,Har,and CH_(3),and has lower weight-average molecular weight and more light tar content than CP-N_(2).A small amount of C_(2)H_(6) addition in CP-DRA will raise the ratio of H_(β) and CH+CH_(2).Electron paramagnetic resonance(EPR)analysis shows that the tar from CP-DRA has a higher radical concentration while the corresponding char has a lower radical concentration.The isotope trace experiment showed that alkanes provide·H,·CH_(3),etc.to stabilize the radicals from coal pyrolysis and result in more alkyl aromatic compounds during CP-DRA.

Structures and magnetism of dinuclear Co complexes based on imine derivatives

This study presents the synthesis of three dinuclear cobalt complexes based on three imine derivatives:bis-[4-(2-pyridylmethyleneamino)-phenyl]thioether(L1),bis-[4-(2-pyridylmethyleneamino)-phenyl]ether(L2),and bis-[4-(2-pyridylmethyleneamino)-phenyl]methane(L3).Single-crystal X-ray diffraction analysis reveals that the complexes[Co_(2)(L1)3](ClO_(4))4·2CH_(3)CN(1),[Co_(2)(L2)3](ClO_(4))4·2CH_(3)OH(2),and[Co_(2)(L3)3](ClO_(4))4·2CH_(3)OH(3)all exhibit a dinuclear structure.Magnetic test results show that complex 3 exhibited irreversible SCO behavior induced by loss of solvent at 300 K,with the average Co-N bond length increasing from 0.2139(3)to 0.2153(3)nm.Meanwhile,the desolvated complex 3 exhibited paramagnetic behavior similar to that of complexes 1 and 2.Variable-temperature UV-Vis spectroscopic studies also indicate that complex 3 undergoes a solvent-loss-induced spin-state transition.CCDC:2347354,1(120 K);2347355,2(120 K);2347356,3(120 K);2347357,3(400 K).

Cryogenic springback of 2219-W aluminum alloy sheet through V-shaped bending

A V-shaped bending device was established to evaluate the effects of temperature and bending fillet radius on springback behavior of 2219-W aluminum alloy at cryogenic temperatures.The cryogenic springback mechanism was elucidated through mechanical analyses and numerical simulations.The results indicated that the springback angle at cryogenic temperatures was greater than that at room temperature.The springback angle increased further as the temperature returned to ambient conditions,attributed to the combined effects of the “dual enhancement effect” and thermal expansion.Notably,a critical fillet radius made the springback angle zero for 90° V-shaped bending.The critical fillet radius at cryogenic temperatures was smaller than that at room temperature,owing to the influence of temperature variations on the bending moment ratio between the forward bending section at the fillet and the reverse bending section of the straight arm.

Dynamic Characteristics of Irregular Ice Floes Based on Polyhedral Discrete Element Method

In polar regions, floating ice exhibits distinct characteristics across a range of spatial scales. It is well recognized that the irregular geometry of these ice formations markedly influences their dynamic behavior. This study introduces a polyhedral Discrete Element Method (DEM) tailored for polar ice, incorporating the Gilbert-Johnson-Keerthi (GJK) and Expanding Polytope Algorithm (EPA) for contact detection. This approach facilitates the simulation of the drift and collision processes of floating ice, effectively capturing its freezing and fragmentation. Subsequently, the stability and reli ability of this model are validated by uniaxial compression on level ice fields, focusing specifically on the influence of compression strength on deformation resistance. Additionally, clusters of ice floes nav igating through narrow channels are simulated. These studies have qualitatively assessed the effects of Floe Size Distribution (FSD), initial concentration, and circularity on their flow dynamics. The higher power-law exponent values in the FSD, increased circularity, and decreased concentration are each as sociated with accelerated flow in ice floe fields. The simulation results distinctly demonstrate the con siderable impact of sea ice geometry on the movement of clusters, offering valuable insights into the complexities of polar ice dynamics.

Visualizing Language and Aging From 2013-2022

Declining cognitive abilities can be a concomitant of advanced age.As language is closely associated with cognitive abilities,changes in language abilities can be an important marker of changes in cognitive abilities.The current study is to review cognitive studies of language and aging by first identifying and exploring the major clusters and pivotal articles and then detecting emerging trends.Data of 3,266 articles on language and aging from 2013 to 2022 were collected from the Web of Science Core Collection database.Adopting Document Co-citation Analysis,Freeman’s betweenness centrality metric(Freeman,2002)and Kleinberg’s burst detection algorithm(Kleinberg,2002),we explored major clusters,pivotal articles and emerging trends in this field.Cognition appears to be the most remarkable cluster.Bilingualism,speech production,listening effort,and reading comprehension are other major active clusters in a certain period.The most recent active cluster concerns the studies of Alzheimer’s disease.Articles serving as pivotal points concentrate on cognitive studies of the Framework for Understanding Effortful Listening(FUEL),the new Ease of Language Understanding model(EUL)and a hierarchical multi-representational generative framework of language comprehension.The progress in statistical methods,the relationship between language and cognitive impairment and the relationship between language abilities and cognition are the emerging trends.These emerging trends will provide some insights into how cognitive abilities influence language abilities in aging.

A Framework of LSTM Neural Network Model in Multi-Time Scale Real-Time Prediction of Ship Motions in Head Waves

Ship motions induced by waves have a significant impact on the efficiency and safety of offshore operations.Real-time prediction of ship motions in the next few seconds plays a crucial role in performing sensitive activities.However,the obvious memory effect of ship motion time series brings certain difficulty to rapid and accurate prediction.Therefore,a real-time framework based on the Long-Short Term Memory(LSTM)neural network model is proposed to predict ship motions in regular and irregular head waves.A 15000 TEU container ship model is employed to illustrate the proposed framework.The numerical implementation and the real-time ship motion prediction in irregular head waves corresponding to the different time scales are carried out based on the container ship model.The related experimental data were employed to verify the numerical simulation results.The results show that the proposed method is more robust than the classical extreme short-term prediction method based on potential flow theory in the prediction of nonlinear ship motions.

Cu-based heterojunction catalysts for electrocatalytic nitrate reduction to ammonia

Copper-based catalysts have garnered wide attention in the field of electrocatalytic nitrate reduction for ammonia production due to their low hydrogen precipitation activity and high ammonia selectivity.However,they still face challenges pertaining of poor stability and low activity,which hinder their further application.Herein,we present a Cu_(2)O/Cu heterojunction catalyst supported on nitrogen-doped porous carbon for nitrate reduction.High resolution transmission electron microscopy(HRTEM)and X-ray Diffraction(XRD)results confirm the presence of Cu_(2)O/Cu heterojunctions,which serve as an active phase in catalysis.The nitrogen-doped porous carbon as a carrier not only enhances the catalyst’s stability,but also facilitates the exposure and dispersion of active sites.At-1.29 V(vs.RHE),the maximum production rate of ammonia reaches 8.8 mg/(mg·h)with a Faradaic efficiency of 92.8%.This study also elucidates the effect of Cu_(2)O-to-Cu ratio in the heterojunction on catalytic performance,thereby providing valuable insights for designing efficient nitrate reduction catalysts for ammonia production.

Embodied Meaning in Comprehending Abstract Chinese Counterfactuals

Embodied cognition theories propose that language comprehension triggers a sensorimotor system in the brain.However,most previous research has paid much attention to concrete and factual sentences,and little emphasis has been put on the research of abstract and counterfactual sentences.The primary challenges for embodied theories lie in elucidating the meanings of abstract and counterfactual sentences.The most prevalent explanation is that abstract and counterfactual sentences are grounded in the activation of a sensorimotor system,in exactly the same way as concrete and factual ones.The present research employed a dual-task experimental paradigm to investigate whether the embodied meaning is activated in comprehending action-related abstract Chinese counterfactual sentences through the presence or absence of action-sentence compatibility effect(ACE).Participants were instructed to read and listen to the action-related abstract Chinese factual or counterfactual sentences describing an abstract transfer word towards or away from them,and then move their fingers towards or away from them to press the buttons in the same direction as the motion cue of the transfer verb.The action-sentence compatibility effect was observed in both abstract factual and counterfactual sentences,in line with the embodied cognition theories,which indicated that the embodied meanings were activated in both action-related abstract factuals and counterfactuals.

Efficient Inverse Analysis for Solving a Coupled Conduction,Convection and Radiation Problem Involving Non⁃gray Participating Media

The presence of non-gray radiative properties in a reheating furnace’s medium that absorbs,emits,and involves non-gray creates more complex radiative heat transfer problems.Furthermore,it adds difficulty to solving the coupled conduction,convection,and radiation problem,leading to suboptimal efficiency that fails to meet real-time control demands.To overcome this difficulty,comparable gray radiative properties of non-gray media are proposed and estimated by solving an inverse problem.However,the required iteration numbers by using a least-squares method are too many and resulted in a very low inverse efficiency.It is necessary to present an efficient method for the equivalence.The Levenberg-Marquardt algorithm is utilized to solve the inverse problem of coupled heat transfer,and the gray-equivalent radiative characteristics are successfully recovered.It is our intention that the issue of low inverse efficiency,which has been observed when the least-squares method is employed,will be resolved.To enhance the performance of the Levenberg-Marquardt algorithm,a modification is implemented for determining the damping factor.Detailed investigations are also conducted to evaluate its accuracy,stability of convergence,efficiency,and robustness of the algorithm.Subsequently,a comparison is made between the results achieved using each method.

Structure and Vibrational Spectroscopy of 2-Methylallyl Alcohol

The intramolecular O−H…πhydrogen bond has garnered significant research interest in recent decades.In this work,we utilized the infrared(IR)-vacuum-ultraviolet(VUV)nonresonant ionization detected IR spectroscopy(NRID-IR)method to study the molecular structure of neutral and cationic 2-methylallyl alcohol(MAA,CH_(2)=C(CH_(3))−CH_(2)−OH).Density functional theory calculations revealed five stable neutral and three stable cationic MAA conformers,respectively.Two neutral MAA conformers are expected to have an O−H…πintramolecular hydrogen bond interaction,based on the structural characterization that the OH group is directed toward the C=C double bond.The IR spectra of both neutral(2700−3700 cm^(−1))and cationic MAA(2500−7200 cm^(−1))were measured,and the anharmonic IR spectra were calculated at the B3LYP-D3(BJ)/def2-TZVPP level.The OH stretching vibration frequency of neutral MAA was observed at 3656 cm−1,slightly lower than those of methanol and ethanol.In contrast,the OH stretching vibration of cationic MAA was red-shifted by about 140 cm^(−1)compared to neutral MAA.The interaction region indicator and natural bond orbital analysis suggest that the O−H…πinteraction in neutral MAA is weak,and may not play a major role in stabilizing the neutral MAA.

Assessment of Contemporary Theoretical Methods for Bond Dissociation Enthalpies

The density functional theory （DFT） is the most popular method for evaluating bond dis- sociation enthalpies （BDEs） of most molecules. Thus, we are committed to looking for alternative methods that can balance the computational cost and higher precision to the best for large systems. The performance of DFT, double-hybrid DFT, and high-level com- posite methods are examined. The tested sets contain monocyclic and polycyclic aromatic molecules, branched hydrocarbons, small inorganic molecules, etc. The results show that the mPW2PLYP and G4MP2 methods achieve reasonable agreement with the benchmark val- ues for most tested molecules, and the mean absolute deviations are 2.43 and 1.96 kcal/mol after excluding the BDEs of branched hydrocarbons. We recommend the G4MP2 is the most appropriate method for small systems （atoms number≤20）; the double-hybrid DFT methods are advised for large aromatic molecules in medium size （20≤atoms number≤50）, and the double-hybrid DFT methods with empirical dispersion correction are recommended for long-chain and branched hydrocarbons in the same size scope; the DFT methods are ad- vised to apply for large systems （atoms number〉50）, and the M06-2X and B3P86 methods are also favorable. Moreover, the differences of optimized geometry of different methods are discussed and the effects of basis sets for various methods are investigated.

Effect of Nb additions on microstructure and properties of γ-TiAl based alloys fabricated by selective laser melting

The γ-TiAl based Ti.Al.Mn.Nb alloys with different Nb additions were fabricated by selective laser melting (SLM) on the TC4 substrate. The effects of Nb content on microstructure and properties of the alloys were investigated. The results reveal that the alloys consist of γ-TiAl phase with tetragonal lattice structure and α2-Ti3Al phase with hcp lattice structure, and show a sequential structure change from near full dendrite to near lamellar structure with the increase of Nb addition. Owing to the higher Nb content in γ-TiAl phase and the formation of near lamellar structure, the alloy with 7.0 at.% Nb addition has the best combination of properties among the studied alloys, namely, not only a high hardness of HV 2000, a high strength of 1390 MPa and a plastic deformation of about 24.5%, but also good tribological properties and high-temperature oxidation resistance.

Rod-shaped porous alumina-supported Cr_2O_3 catalyst with low acidity for propane dehydrogenation

Direct catalytic propane dehydrogenation(PDH)to obtain propylene is a more economical and environmentally friendly route for propylene production.In particular,alumina-supported Cr2O3 catalysts can have better potential applications if the acidic properties could be tuned.Herein,a series of rod-shaped porous alumina were prepared through a hydrothermal route,followed by calcination.It was found that the acidity of the synthesized alumina was generally lower than that of the commercial alumina and could be adjusted well by varying the calcination temperature.Such alumina materials were used as supports for active Cr2O3,and the obtained catalysts could enhance the resistance to coke formation associated with similar activity in PDH reaction compared to the commercial alumina.The amount of coke deposited on a self-made catalyst(Cr-Al-800)was 3.6%,which was much lower than that deposited on the reference catalyst(15.7%).The lower acidity of the catalyst inhibited the side reactions and coke formation during the PDH process,which was beneficial for its high activity and superior anti-coking properties.

Ceria-modified hierarchical Hβ zeolite as a robust solid acid catalyst for alkenylation of p-xylene with phenylacetylene

A ceria‐modified hierarchical Hβzeolite was prepared by a desilication‐dealumination procedure followed by ceria modification.The catalytic performance of the ceria‐modified and unmodified hierarchical Hβzeolite catalysts for alkenylation of p‐xylene with phenylacetylene was investigated.Various characterization techniques,including X‐ray diffraction,X‐ray fluorescence,nitrogen adsorption‐desorption,and NH3temperature‐programmed desorption,were used to examine the structure‐performance relationships.Our results show that the optimized ceria‐modified hierarchical Hβzeolite catalyst demonstrated higher catalytic activity,selectivity,and stability for alkenylation of p‐xylene with phenylacetylene than those of pristine Hβzeolite.This performance was attributed to more acidic sites and improved accessibility to active sites through larger pores,together with a higher mesoporous surface area and volume resulting from the hierarchical pore architecture and ceria modification.Thus,our5wt%CeO2‐Hβ‐B0.2A0.2catalyst shows great potential for producing alkenyl aromatics through solid acid catalyzed alkenylation.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved

Hot compressive deformation behavior and microstructure evolution of HIPed FGH96 superalloy

Hot deformation behavior and microstructure evolution of hot isostatically pressed FGH96 P/M superalloy were studied using isothermal compression tests. The tests were performed on a Gleeble-1500 simulator in a temperature range of 1000-1150 °C and strain rate of 0.001-1.0 s-1, respectively. By regression analysis of the stress—strain data, the constitutive equation for FGH96 superalloy was developed in the form of hyperbolic sine function with hot activation energy of 693.21 kJ/mol. By investigating the deformation microstructure, it is found that partial and full dynamical recrystallization occurs in specimens deformed below and above 1100 °C, respectively, and dynamical recrystallization （DRX） happens more readily with decreasing strain rate and increasing deformation temperature. Finally, equations representing the kinetics of DRX and grain size evolution were established.

Interfacial features of TiAl alloy/316L stainless steel joint brazed with Zr−Cu−Ni−Al amorphous filler metal

TiAl alloy and 316L stainless steel were vacuum-brazed with Zr−50.0Cu−7.1Ni−7.1Al(at.%)amorphous filler metal.The influence of brazing time and temperature on the interfacial microstructure and shear strength of the resultant joints was investigated.The brazed seam consisted of three layers,including two diffusion layers and one residual filler metal layer.The typical microstructure of brazed TiAl alloy/316L stainless steel joint was TiAl alloy substrate/α2-(Ti3Al)/AlCuTi/residual filler metal/Cu9Zr11+Fe23Zr6/Laves-Fe2Zr/α-(Fe,Cr)/316L stainless steel substrate.Discontinuous brittle Fe2Zr layer formed near the interface between the residual filler metal layer andα-(Fe,Cr)layer.The maximum shear strength of brazed joints reached 129 MPa when brazed at 1020℃ for 10 min.The diffusion activation energies ofα2-(Ti3Al)andα-(Fe,Cr)phases were−195.769 and−112.420 kJ/mol,respectively,the diffusion constants for these two phases were 3.639×10^(−6) and 7.502×10^(−10)μm^(2)/s,respectively.Cracks initiated at Fe2Zr layer and propagated into the residual filler metal layer during the shear test.The Laves-Fe2Zr phase existing on the fracture surface suggested the brittle fracture mode of the brazed joints.

Enhancing hydrothermal stability of nano-sized HZSM-5 zeolite by phosphorus modification for olefin catalytic cracking of full-range FCC gasoline

In this study, phosphorus modification by trimethyl phosphate impregnation was employed to enhance the hydrothermal stability of nano‐sized HZSM‐5 zeolites. A parallel modification was studied by ammonium dihydrogen phosphate impregnation. The modified zeolites were subjected to steam treatment at 800 °C for 4 h (100% steam) and employed as catalysts for olefin catalyticcracking (OCC) of full‐range fluid catalytic cracking (FCC) gasoline. X‐ray diffraction, N2 physicaladsorption and NH3 temperature‐programmed desorption analysis indicated that, although significantimprovements to the hydrothermal stability of nano‐sized HZSM‐5 zeolites can be observedwhen adopting both phosphorus modification strategies, impregnation with trimethyl phosphatedisplays further enhancement of the hydrothermal stability. This is because higher structural crystallinityis retained, larger specific surface areas/micropore volumes form, and there are greaternumbers of surface acid sites. Reaction experiments conducted using a fixed‐bed micro‐reactor(catalyst/oil ratio = 4, time on stream = 4 s) showed OCC of full‐range FCC gasoline-under a fluidized‐bed reaction mode configuration-to be a viable solution for the olefin problem of FCC gasoline.This reaction significantly decreased the olefin content in the full‐range FCC gasoline feed, andspecifically heavy‐end olefins, by converting the olefins into value‐added C2–C4 olefins and aromatics.At the same time, sulfide content of the gasoline decreased via a non‐hydrodesulfurization process.Nano‐sized HZSM‐5 zeolites modified with trimethyl phosphate exhibited enhanced catalytic performance for OCC of full‐range FCC gasoline.

Promotion effects of nickel-doped Al2O3-nanosheet-supported Au catalysts for CO oxidation

Supported gold catalysts show high activity toward CO oxidation, and the nature of the support significantly affects the catalytic activity. Herein, serial Ni doping of thin porous Al2 O3 nanosheets was performed via a precipitation-hydrothermal method by varying the amount of Ni during the precipitation step. The prepared nanosheets were subsequently used as supports for the deposition of Au nanoparticles(NPs). The obtained Au/Nix Al catalysts were studied in the context of CO oxidation to determine the effect of Ni doping on the supports. Enhanced catalytic performances were obtained for the Au/Nix Al catalysts compared with those of the Au supported on bare Al2 O3. The Ni content and pretreatment atmosphere were both shown to influence the catalytic activity. Pretreatment under a reducing atmosphere was beneficial for improving catalytic activity. The highest activity was observed for the catalysts with a Ni/Al molar ratio of 0.05, achieving complete CO conversion at 20 °C with a gold loading of 1 wt%. The in-situ FTIR results showed that the introduction of Ni strengthened CO adsorption on the Au NPs. The H2-TPR and O2-TPD results indicated that the introduction of Ni produced new oxygen vacancies and allowed the oxygen molecules to be adsorbed and activated more easily. The improved catalytic performance after doping Ni was attributed to the smaller size of the Au NPs and more active oxygen species.

Single-atom catalysis: Bridging the homo-and heterogeneous catalysis

Single-atom catalysis,the catalysis by single-atom catalysts(SACs),has attracted considerable attention in recent years as a new frontier in the heterogeneous catalysis field.SACs have the advantages of both homogeneous catalysts(isolated active sites)and heterogeneous catalysts(stable and easy to separate),and are thus predicted to be able to bridge the homo-and heterogeneous catalysis.This prediction was first experimentally demonstrated in 2016.In this mini-review,we summarize the few homogeneous catalysis progresses reported recently where SACs have exhibited promising application:a)Rh/ZnO and Rh/CoO SAC have been used successfully in hydroformylation of olefin of which the activity are comparable to the homogeneous Wilkinson’s catalyst;b)a Pt/Al2O3 SAC has shown excellent performance in hydrosilylation reaction;and c)M-N-C SACs(M=Fe,Co etc.)have been applied in the activation of C–H bonds.All of these examples suggest that fabrication of suitable SACs could provide a new avenue for the heterogenization of homogeneous catalysts.These pioneering works shed new light on the recognition of single-atom catalysis in bridging the homo-and heterogeneous catalysis.