一种阴离子浸出策略合成金属羟基氧化物用于电催化甘油氧化

亲核氧化反应在可持续生产增值化学品中扮演着重要角色。电催化甘油氧化反应作为亲核氧化反应的一种重要类型,可以制得包括甲酸在内的C_(1)至C_(3)衍生产物。非贵金属氢氧化物/羟基氧化物被广泛应用于甘油氧化反应,但在中等电位下难以达到工业级电流密度(大于300 mA·cm^(-2))。研究表明,氢氧化物/羟基氧化物催化的甘油氧化反应通过间接氧化机理进行,即通过电生成的含有亲电吸附氧的羟基氧化物氧化亲核试剂(甘油)。因此,理解甘油氧化反应中电催化剂的演变至关重要。在本文中,通过循环伏安法活化钼酸镍(NiMoO_(4)),开发了一种钼掺杂的羟基氧化镍(Mo-NiOOH)催化剂。通过多种表征方法对Mo-NiOOH进行了系统表征,结果显示,Mo-NiOOH继承了NiMoO_(4)前驱体的纳米片阵列形貌,但Mo含量降低,证明循环伏安法活化后实现了从氧化物到羟基氧化物的相重构。此外,Mo-NiOOH中Ni^(3+)/Ni^(2+)的比例高于循环伏安法活化制备的NiOOH。在活化过程中,Mo物种从NiMoO_(4)中浸出,制备得到的Mo-NiOOH保留了NiMoO_(4)前驱体的纳米片阵列形貌。与氢氧化镍(Ni(OH)_(2))经循环伏安法活化合成的NiOOH相比,Mo-NiOOH具有更高的Ni^(3+)/Ni^(2+)比例以及更高的电化学比表面积(ECSAs),且促进了Ni^(2+)氧化为Ni^(3+)。因此,Mo-NiOOH达到高电流密度(400mA·cm^(-2))的电位(1.51V vs.RHE)低于NiOOH(1.84 V vs.RHE)。此外,Mo-NiOOH表现出高于NiOOH的甲酸盐法拉第效率(84.7%vs.59.6%),表明钼掺杂加速了碳-碳键断裂。多电位阶跃实验显示,NiOOH和Mo-NiOOH催化的甘油电氧化通过类似的羟基氧化物介导的间接氧化机理进行。原位电化学阻抗谱和原位拉曼光谱证实,Mo掺杂促进了甘油氧化反应动力学以及Ni^(2+)氧化为Ni^(3+)的过程,导致Mo-NiOOH比NiOOH具有更高的活性和甲酸选择性。本研究通过可溶性阴离子浸出策略来调节羟基氧化物表面结构,为设计高性能亲核氧化反应电催化剂提供了指导。

Facile synthesis of Cu-doped manganese oxide octahedral molecular sieve for the efficient degradation of sulfamethoxazole via peroxymonosulfate activation

Advanced processes for peroxymonosulfate(PMS)-based oxidation are efficient in eliminating toxic and refractory organic pol-lutants from sewage.The activation of electron-withdrawing HSO_(5)^(-)releases reactive species,including sulfate radical(·SO_(4)^(-)),hydroxyl radical(·OH),superoxide radical(·O_(2)^(-)),and singlet oxygen(1O_(2)),which can induce the degradation of organic contaminants.In this work,we synthesized a variety of M-OMS-2 nanorods(M=Co,Ni,Cu,Fe)by doping Co^(2+),Ni^(2+),Cu^(2+),or Fe^(3+)into manganese oxide oc-tahedral molecular sieve(OMS-2)to efficiently remove sulfamethoxazole(SMX)via PMS activation.The catalytic performance of M-OMS-2 in SMX elimination via PMS activation was assessed.The nanorods obtained in decreasing order of SMX removal rate were Cu-OMS-2(96.40%),Co-OMS-2(88.00%),Ni-OMS-2(87.20%),Fe-OMS-2(35.00%),and OMS-2(33.50%).Then,the kinetics and struc-ture-activity relationship of the M-OMS-2 nanorods during the elimination of SMX were investigated.The feasible mechanism underly-ing SMX degradation by the Cu-OMS-2/PMS system was further investigated with a quenching experiment,high-resolution mass spec-troscopy,and electron paramagnetic resonance.Results showed that SMX degradation efficiency was enhanced in seawater and tap water,demonstrating the potential application of Cu-OMS-2/PMS system in sewage treatment.

机制砂对喷射混凝土强度影响试验研究

以金山店铁矿机制砂为研究对象,对2种不同种类母岩机制砂分别开展X射线衍射试验、筛分试验和抗压强度试验,并与黄砂进行对比。试验结果表明,母岩为火成岩的机制砂喷射混凝土抗压强度最高,黄砂次之,沉积岩最低;长石含量是影响机制砂混凝土强度的主要因素,其次矿物的结晶结构和晶粒大小也影响机制砂强度;沉积岩机制砂母岩强度高、细度模数大,机制砂混凝土抗压强度与黄砂混凝土相比降低了14.4%;建议选用长石含量高,抗压强度适中的岩石制备的机制砂来作为井下喷浆用砂。

Expediting^(*)OH accumulation kinetics on metal-organic frameworks-derived CoOOH with CeO_(2) “accelerator” for electrocatalytic 5-hydroxymethylfurfural oxidation valorization

In this work,nickel foam supported CeO_(2)-modified CoBDC(BDC stands for terephthalic acid linker)metal-organic frameworks(NF/CoBDC@CeO_(2)) are prepared by hydrothermal and subsequent impregnation methods,which can be further transformed to NF/CoOOH@CeO_(2) by reconstruction during the electrocatalytic test.The obtained NF/CoOOH@CeO_(2) exhibits excellent performance in electrocatalytic oxidation of 5-hydroxymethylfurfural(HMF) because the introduction of CeO_(2) can optimize the electronic structure of the heterointerface and accelerate the accumulation of ^(*)OH.It requires only a potential of 1.290 V_(RHE) to provide a current density of 50 mA cm^(-2) in 1.0 M KOH+50 mM HMF,which is 222 mV lower than that required in 1,0 M KOH(1.512 V_(RHE)).In addition,density-functional theory calculation results demonstrate that CeO_(2) biases the electrons to the CoOOH side at the heterointerface and promotes the adsorption of ^(*)OH and ^(*)HMF on the catalyst surface,which lower the reaction energy barrier and facilitate the electrocata lytic oxidation process.

Retinal ischemia-reperfusion injury and pretreatment with Lycium barbarum glycopeptide

AIM:To investigate the antioxidant protective effect of Lycium barbarum glycopeptide(LbGP)pretreatment on retinal ischemia-reperfusion(I/R)injury(RIRI)in rats.METHODS:RIRI was induced in Sprague Dawley rats through anterior chamber perfusion,and pretreatment involved administering LbGP via gavage for 7d.After 24h of reperfusion,serum alanine aminotransferase(ALT),aspartate aminotransferase(AST),and creatinine(CREA)levels,retinal structure,expression of Caspase-3 and Caspase-8,superoxide dismutase(SOD)activity,and malondialdehyde(MDA)in the retina were measured.RESULTS:The pretreatment with LbGP effectively protected the retina and retinal tissue from edema and inflammation in the ganglion cell layer(GCL)and nerve fiber layer(NFL)of rats subjected to RIRI,as shown by light microscopy and optical coherence tomography(OCT).Serum AST was higher in the model group than in the blank group(P=0.042),but no difference was found in ALT,AST,and CREA across the LbGP groups and model group.Caspase-3 expression was higher in the model group than in the blank group(P=0.006),but no difference was found among LbGP groups and the model group.Caspase-8 expression was higher in the model group than in the blank group(P=0.000),and lower in the 400 mg/kg LbGP group than in the model group(P=0.016).SOD activity was lower in the model group than in the blank group(P=0.001),and the decrease was slower in the 400 mg/kg LbGP group than in the model group(P=0.003).MDA content was higher in the model group than in the blank group(P=0.001),and lower in the 400 mg/kg LbGP group than in the model group(P=0.016).The pretreatment with LbGP did not result in any observed liver or renal toxicity in the model.CONCLUSION:LbGP pretreatment exhibits dosedependent anti-inflammatory,and antioxidative effects by reducing Caspase-8 expression,preventing declines of SOD activity,and decreasing MDA content in the RIRI rat model.

An Efficient and Provably Secure SM2 Key-Insulated Signature Scheme for Industrial Internet of Things

With the continuous expansion of the Industrial Internet of Things(IIoT),more andmore organisations are placing large amounts of data in the cloud to reduce overheads.However,the channel between cloud servers and smart equipment is not trustworthy,so the issue of data authenticity needs to be addressed.The SM2 digital signature algorithm can provide an authentication mechanism for data to solve such problems.Unfortunately,it still suffers from the problem of key exposure.In order to address this concern,this study first introduces a key-insulated scheme,SM2-KI-SIGN,based on the SM2 algorithm.This scheme boasts strong key insulation and secure keyupdates.Our scheme uses the elliptic curve algorithm,which is not only more efficient but also more suitable for IIoT-cloud environments.Finally,the security proof of SM2-KI-SIGN is given under the Elliptic Curve Discrete Logarithm(ECDL)assumption in the random oracle.

An Updated Lagrangian Particle Hydrodynamics (ULPH)-NOSBPD Coupling Approach forModeling Fluid-Structure Interaction Problem

A fluid-structure interaction approach is proposed in this paper based onNon-Ordinary State-Based Peridynamics(NOSB-PD)and Updated Lagrangian Particle Hydrodynamics(ULPH)to simulate the fluid-structure interaction problem with large geometric deformation and material failure and solve the fluid-structure interaction problem of Newtonian fluid.In the coupled framework,the NOSB-PD theory describes the deformation and fracture of the solid material structure.ULPH is applied to describe the flow of Newtonian fluids due to its advantages in computational accuracy.The framework utilizes the advantages of NOSB-PD theory for solving discontinuous problems and ULPH theory for solving fluid problems,with good computational stability and robustness.A fluidstructure coupling algorithm using pressure as the transmission medium is established to deal with the fluidstructure interface.The dynamic model of solid structure and the PD-ULPH fluid-structure interaction model involving large deformation are verified by numerical simulations.The results agree with the analytical solution,the available experimental data,and other numerical results.Thus,the accuracy and effectiveness of the proposed method in solving the fluid-structure interaction problem are demonstrated.The fluid-structure interactionmodel based on ULPH and NOSB-PD established in this paper provides a new idea for the numerical solution of fluidstructure interaction and a promising approach for engineering design and experimental prediction.

Updated Lagrangian Particle Hydrodynamics (ULPH)Modeling of Natural Convection Problems

Natural convection is a heat transfer mechanism driven by temperature or density differences,leading to fluid motion without external influence.It occurs in various natural and engineering phenomena,influencing heat transfer,climate,and fluid mixing in industrial processes.This work aims to use the Updated Lagrangian Particle Hydrodynamics(ULPH)theory to address natural convection problems.The Navier-Stokes equation is discretized using second-order nonlocal differential operators,allowing a direct solution of the Laplace operator for temperature in the energy equation.Various numerical simulations,including cases such as natural convection in square cavities and two concentric cylinders,were conducted to validate the reliability of the model.The results demonstrate that the proposed model exhibits excellent accuracy and performance,providing a promising and effective numerical approach for natural convection problems.

Advances in endoscopic diagnosis and management of colorectal cancer

Colorectal cancer(CRC)is a leading global health concern,and early identification and precise prognosis play a vital role in enhancing patient results.Endoscopy is a minimally invasive imaging technique that is crucial for the screening,diagnosis,and treatment of CRC.This editorial discusses the importance of advances in endoscopic techniques,the integration of artificial intelligence,and the potential of novel technologies in enhancing the diagnosis and management of CRC.

Assessment of the Influence of Tunnel Settlement on Operational Performance of Subway Vehicles

In the realm of subway shield tunnel operations,the impact of tunnel settlement on the operational performance of subway vehicles is a crucial concern.This study introduces an advanced analytical model to investigate rail geometric deformations caused by settlement within a vehicle-track-tunnel coupled system.The model integrates the geometric deformations of the track,attributed to settlement,as track irregularities.A novel“cyclic model”algorithm was employed to enhance computational efficiency without compromising on precision,a claim that was rigorously validated.The model’s capability extends to analyzing the time-history responses of vehicles traversing settlement-affected areas.The research primarily focuses on how settlement wavelength,amplitude,and vehicle speed influence operational performance.Key findings indicate that an increase in settlement wavelength can improve vehicle performance,whereas a rise in amplitude can degrade it.The study also establishes settlement thresholds,based on vehicle operation comfort and safety.These insights are pivotal for maintaining and enhancing the safety and efficiency of subway systems,providing a valuable framework for urban infrastructure management and long-term maintenance strategies in metropolitan transit systems.

The Influence of Acid on the RockMechanical Characteristics of Deep Shale in theWujiaping Formation

The microscopic characteristics and mechanical properties of rocks change after the action of acid on deep shale,which affects the fracturing effect.Accordingly,we designed and conducted indoor experiments related to the changes in macro and microscopic characteristics after the interaction of acid with the shale of Wujiaping Formation,based on which the characteristic law of fracture volume modification after acid fracturing was studied using numerical simulation.The results demonstrate that the pores and fractures are enlarged and the structure is significantly loosened after the acid immersion.And a 15%concentration of hydrochloric acid can effectively dissolve shale.Furthermore,the degree of acid-etching reaction is highly variable because of the different carbonate content,which reveals the strong inhomogeneity of the shale system in the Wujiaping Group reservoir section.After the acid interacted with the shale rock samples,the triaxial compressive strength,elastic modulus,and Poisson’s ratio of shale decreased.Moreover,the evaluation of the effect after acid fracturing simulated by fracturing software revealed that the smaller the value of elastic modulus in shale-based reservoirs,the more favorable the fracture volume modification.This discovery not only provides a theoretical basis for the expansion and extension patterns of acid-fracturing in carbonaceous shale formations but also offers research methods and theoretical insights for the fundamental exploration of other deep-seated oil and gas resources.

Reproducibility study of intravoxel incoherent motion and apparent diffusion coefficient parameters in normal pancreas

BACKGROUND The consistency of pancreatic apparent diffusion coefficient(ADC)values and intravoxel incoherent motion(IVIM)parameter values across different magnetic resonance imaging(MRI)devices significantly impacts the patient’s diagnosis and treatment.AIM To explore consistency in image quality,ADC values,and IVIM parameter values among different MRI devices in pancreatic examinations.METHODS This retrospective study was approved by the local ethics committee,and informed consent was obtained from all participants.In total,22 healthy volunteers(10 males and 12 females)aged 24-61 years(mean,28.9±2.3 years)underwent pancreatic diffusion-weighted imaging using 3.0T MRI equipment from three vendors.Two independent observers subjectively scored image quality and measured the pancreas’s overall ADC values and signal-to-noise ratios(SNRs).Subsequently,regions of interest(ROIs)were delineated for the IVIM parameters(true diffusion coefficient,pseudo-diffusion coefficient,and perfusion fraction)using post-processing software.These ROIs were on the head,body,and tail of the pancrease.The subjective image ratings were assessed using the kappa consistency test.Intraclass correlation coefficients(ICCs)and mixed linear models were used to evaluate each device’s quantitative parameter values.Finally,a pairwise analysis of IVIM parameter values across each device was performed using Bland-Altman plots.RESULTS The Kappa value for the subjective ratings of the different observers was 0.776(P<0.05).The ICC values for interobserver and intra-observer agreements for the quantitative parameters were 0.803[95% confidence interval(CI):0.684-0.880]and 0.883(95%CI:0.760-0.945),respectively(P<0.05).The ICCs for the SNR between different devices was comparable(P>0.05),and the ICCs for the ADC values from different devices were 0.870,0.707,and 0.808,respectively(P<0.05).Notably,only a few statistically significant inter-device agreements were observed for different IVIM parameters,and among those,the ICC values were generally low.The mixed linear model results indicated differences(P<0.05)in the f-value for the pancreas head,D-value for the pancreas body,and D-value for the pancreas tail obtained using different MRI machines.The Bland-Altman plots showed significant variability at some data points.CONCLUSION ADC values are consistent among different devices,but the IVIM parameters’repeatability is moderate.Therefore,the variability in the IVIM parameter values may be associated with using different MRI machines.Thus,caution should be exercised when using IVIM parameter values to assess the pancreas.

Temperature field calculation of rail flash welding

The forging stage of rail flash welding has a decisive influence on joint strength,and the study of the temperature distribution in the process has an important role in further improving joint strength.In this paper,three calculation methods for the temperature field are given.First,the finite element model of the temperature field before forging rail flash welding is established by using the transient heat module of Ansys software and verified by infrared temperature measurement.Second,the temperature distribution of different parts of the rail before flash welding is obtained by using infrared thermal imaging equipment.Third,Matlab software is used to calculate the temperature of the non-measured part.Finally,the temperature distribution function along the rail axis is fitted through the temperature measurement data.The temperature distribution before the top forging of the rail flash welding can be used to analyze the joint and heat-affected zone organization and properties effectively and to guide the parameter setting and industrial production.

Research on Rotating Machinery Fault Diagnosis Based on Improved Multi-target Domain Adversarial Network

Aiming at the problems of low efficiency,poor anti-noise and robustness of transfer learning model in intelligent fault diagnosis of rotating machinery,a new method of intelligent fault diagnosis of rotating machinery based on single source and multi-target domain adversarial network model(WDMACN)and Gram Angle Product field(GAPF)was proposed.Firstly,the original one-dimensional vibration signal is preprocessed using GAPF to generate the image data including all time series.Secondly,the residual network is used to extract data features,and the features of the target domain without labels are pseudo-labeled,and the transferable features among the feature extractors are shared through the depth parameter,and the feature extractors of the multi-target domain are updated anatomically to generate the features that the discriminator cannot distinguish.The modelt through adversarial domain adaptation,thus achieving fault classification.Finally,a large number of validations were carried out on the bearing data set of Case Western Reserve University(CWRU)and the gear data.The results show that the proposed method can greatly improve the diagnostic efficiency of the model,and has good noise resistance and generalization.

Extraction of Liver Capsule from High-Frequency Ultrasound Images via Drift Iterative Search Algorithm

Aiming at the prior medical knowledge that hepatic ascites only occurs in the severe period of liver cirrhosis, and the severe rupture of the liver capsule curve, when ascites occurs visually, can easily lead to the wrong location of the liver capsule, a transposed grayscale statistical threshold method is proposed to solve the problem. Realize the identification of liver ascites. By analyzing the visual characteristics of the liver image, the gray value of the upper half of the ultrasound image is counted column by column from a mathematical point of view, the gray distribution curve is drawn, and the relevant threshold is set for corresponding judgment. At the same time, the gray value above the ascites detection boundary is set to zero. The ablation experiment proved that the ascites detection method and post-processing operation proposed in this paper provide effective support for the precise positioning of the liver capsule curve, quantitative analysis and diagnosis of liver cirrhosis in the later stage. The Hessian matrix is sensitive to linear structure to achieve image enhancement. In view of the low accuracy of the existing liver envelope curve detection method and the incomplete quantitative evaluation of liver cirrhosis, it is proposed to use drift iteration under the synergistic effect of multiple filters. A search algorithm extracts the liver capsule.

“On-off”switch for H_(2)and O_(2)generation from HCOOH resp.H_(2)O_(2)

In spite of the numerous advances in the development of H_(2)and O_(2)evolutions upon water splitting,the separation of H_(2)from O_(2)still remains a severe challenge.Herein,the novel dual-functional nanocatalysts Pd/carbon nanosphere(CNS),obtained via immobilization of ultrafine Pd nanoparticles onto CNS,are developed and employed for both selective H_(2)generation from HCOOH dehydrogenation and O_(2)evolution from H_(2)O_(2)decomposition.In these reactions,the highest activities for Pd/CNS-800(i.e.,calcinated at 800℃)are 2478 h−1 and 993 min^(−1)for H_(2)and O_(2)evolution,respectively.The highly efficient and selective“on-off”switch for selective H_(2)generation from HCOOH is successfully realized by pH adjustment.This novel and highly efficient nanocatalyst Pd/CNS-800 not only provides new approaches for the promising application of HCOOH and H_(2)O_(2)as economic and safe H_(2)and O_(2)carriers,respectively,for fuel cells,but also promotes the development of“on-off”switch for on-demand H_(2)evolution.

近零碳排放园区建设思路和对策建议

近零碳排放园区是在碳达峰碳中和新形势下,推动园区可持续、高质量发展的一种新模式,开展近零碳排放园区建设是积极应对气候变化、促进减污降碳协同增效的有效抓手,是有序推动碳达峰碳中和的重要体现。通过分析国家对于近零碳排放园区的政策要求、梳理总结国内外近零碳排放园区典型实践案例的经验、识别近零碳排放园区建设存在的问题,最终政策体系、建设路径、技术支撑、体制机制等方面提出体现四川特色的近零碳排放园区建设思路和对策建议。对于四川省开展近零碳排放园区建设、推动园区经济发展绿色转型具有重要的理论指导意义。

Manufacturing N,O-carboxymethyl chitosan-reduced graphene oxide under freeze-dying for performance improvement of Li-S battery

Lithium-sulfur(Li-S) batteries can provide far higher energy density than currently commercialized lithium ion batteries, but challenges remain before it they are used in practice.One of the challenges is the shuttle effect that originates from soluble intermediates, like lithium polysulfides. To address this issue, we report a novel laminar composite, N,O-carboxymethyl chitosan-reduced graphene oxide(CC-rGO), which is manufactured via the self-assembly of CC onto GO and subsequent reduction of GO under an extreme condition of 1 Pa and-50°C. The synthesized laminar CC-rGO composite is mixed with acetylene black(AB) and coated on a commercial polypropylene(PP) membrane, resulting in a separator(CC-rGO/AB/PP) that can not only completely suppress the polysulfides penetration, but also can accelerate the lithium ion transportation, providing a Li-S battery with excellent cyclic stability and rate capability. As confirmed by theoretic simulations, this unique feature of CC-rGO is attributed to its strong repulsive interaction to polysulfide anions and its benefit for fast lithium ion transportation through the paths paved by the heteroatoms in CC.

Multiscale strain alleviation of Ni-rich cathode guided by in situ environmental transmission electron microscopy during the solid-state synthesis

Ni-rich layered oxides are one of the most promising cathode materials for Li-ion batteries due to their high energy density.However,the chemomechanical breakdown and capacity degradation associated with the anisotropic lattice evolution during lithiation/delithiation hinders its practical application.Herein,by utilizing the in situ environmental transmission electron microscopy(ETEM),we provide a real time nanoscale characterization of high temperature solid-state synthesis of LiNi_(0.8)CO_(0.1)Mn_(0.1)O_(2)(NCM811) cathode,and unprecedentedly reveal the strain/stress formation and morphological evolution mechanism of primary/second ary particles,as well as their influence on electrochemical performance.We show that stress inhomogeneity during solid-state synthesis will lead to both primary/secondary particle pulverization and new grain boundary initiation,which are detrimental to cathode cycling stability and rate performance.Aiming to alleviate this multiscale strain during solid-state synthesis,we introduced a calcination scheme that effectively relieves the stress during the synthesis,thus mitigating the primary/secondary particle crack and the detrimental grain boundaries formation,which in turn improves the cathode structural integrity and Li-ion transport kinetics for long-life and high-rate electrochemical performance.This work remarkably advances the fundamental understanding on mechanochemical properties of transition metal oxide cathode with solid-state synthesis and provides a unified guide for optimization the Ni-rich oxide cathode.

碳达峰目标下的四川应对气候变化路径研究

面对日益突出的全球气候变化风险,减缓和适应气候变化紧迫性上升。四川是全球气候变化的敏感脆弱区之一,应对气候变化不仅面临多样影响和风险凸显等问题,同时叠加在碳达峰目标下低碳转型约束条件较多、耗能载能产业加速聚集等问题和挑战。采用“现状评估—问题诊断—措施优化”的方法,按照减缓与适应并重的思路,从气候变化风险管理、能源绿色高效转型、绿色发展动能培育、分区精准施策等方面探索差异化路径,因地制宜构建应对气候变化治理体系。