理论指导构建Cu-O-Ti-O_(v)活性位点及其高效电催化还原硝酸根研究

面向国家绿色低碳战略目标,变革化石资源合成氨技术路线变得尤为迫切,开发可再生能源制“绿氨”将成为合成氨领域未来的重要发展方向.将工业废水中的硝酸根(NO_(3)-)电催化还原为氨(NO_(3)RR),既可有效回收氨,又能消除硝酸根污染影响.然而,NO_(3)RR涉及缓慢的八电子转移过程,含有多种反应中间体,其反应机理复杂不明.此外,水系电解液中存在的析氢竞争反应也为高效NO_(3)RR催化剂的开发设计带来了巨大的挑战.为突破高效催化剂的发展瓶颈,本文通过理论模拟,在低成本的催化剂上设计了高效的NO_(3)RR催化活性位点,并利用简单的制备策略合成了目标催化剂.同时,结合原位表征技术,阐明了NO_(3)RR的反应路径及催化机理.本文通过密度泛函理论(DFT)计算发现,Cu/TiO_(2)催化剂上的Cu-O-Ti-O_(v)结构具有较好的NO_(3)-还原活性,该结构不仅能够促进反应中间体NOx-的吸附和活化,还能有效抑制竞争析氢反应,从而降低NO_(3)RR的反应能垒.在该结构上,NO_(3)RR的反应路径为:NO_(3)^(*)→NO_(2)^(*)→HONO^(*)→NO^(*)→*NOH→*N→^(*)NH→*NH2→*NH_(3)→NH_(3).基于理论计算结果,分别采用浸渍法和尿素水解法制备了系列富含Cu-O-Ti-O_(v)结构的Cu/TiO_(2)催化剂.氮气等温吸附-脱附曲线、拉曼光谱(Raman)、电子顺磁共振波谱、X射线光电子能谱(XPS)和傅立叶红外光谱等结果发现,相比于采用浸渍法制备的系列Cu/TiO_(2)催化剂,采用尿素水解法制备的Cu/TiO_(2)(CT-U)催化剂具有更大的比表面积以及更多的Cu-O-Ti-O_(v)位点,说明尿素水解法可提高Cu颗粒在TiO_(2)载体表面的分散度,增强Cu颗粒与TiO_(2)载体之间的相互作用,提高Cu/TiO_(2)催化剂表面的Cu-O-Ti-O_(v)位点含量.将以上制备出的催化剂应用于催化NO_(3)RR中,结果表明,在-1.0 V vs.RHE还原电位下,CT-U催化剂上氨产率可达3046.5μg h^(-1) mgcat^(-1),高于大多数文献报道结果.循环稳定性测试结果表明,在Cu/TiO_(2)催化剂上构建Cu-O-Ti-O_(v)位点还能显著抑制电催化反应过程中Cu物种从Cu/TiO_(2)催化剂上溶出,从而显著增强催化剂的稳定性.此外,设计制备了不含氧空位的Cu/TiO_(2),TiO_(2)-x,Cu,Cu_(2)O以及CuO催化剂,并将其用于催化NO_(3)RR.结果发现,上述催化剂上的氨产率皆明显低于CT-U催化剂,说明Cu,Ti以及O_(v)构成的Cu-O-Ti-O_(v)结构具有较好的催化协同作用,从而显著提升了NO_(3)RR反应活性.最后,通过原位Raman及原位XPS表征检测反应中间体,验证了由DFT模拟出的NO_(3)RR反应路径.综上,通过在Cu/TiO_(2)催化剂上理论指导构建Cu-O-Ti-O_(v)活性位点,实现了NO_(3)RR性能的有效提升.Cu-O-Ti-O_(v)结构中的多位点协同作用不仅促进了NO_(x)-的吸附和活化,而且抑制了电催化过程中Cu物种从催化剂上的溶出,从而提高了催化剂的稳定性.本研究为设计高效稳定的NO_(3)RR催化剂提供了新思路.

Efficient and reversible separation of NH_(3) by deep eutectic solvents with multiple active sites and low viscosities

The efficient separation and collection of ammonia(NH_(3))during NH_(3) synthesis process is essential to improve the economic efficiency and protect the environment.In this work,ethanolammonium hydrochloride(EtOHACl)and phenol(PhOH)were used to prepare a novel class of deep eutectic solvents(DESs)with multiple active sites and low viscosities.The NH_(3) separation performance of EtOHACl+PhOH DESs was analyzed completely.It is figured out that the NH_(3) absorption rates in EtOHACl+PhOH DESs are very fast.The NH_(3) absorption capacities are very high and reach up to 5.52 and 10.74 mol·kg1 at 11.2 and 100.4 kPa under 298.2 K,respectively.In addition,the EtOHACl+PhOH DESs present highly selective absorption of NH_(3) over N_(2) and H_(2) and good regenerative properties after seven cycles of absorption/desorption.The intrinsic separation mechanism of NH_(3) by EtOHACl+PhOH DESs was further revealed by spectroscopic analysis and quantum chemistry calculations.

Fractional-order heterogeneous memristive Rulkov neuronal network and its medical image watermarking application

This article proposes a novel fractional heterogeneous neural network by coupling a Rulkov neuron with a Hopfield neural network(FRHNN),utilizing memristors for emulating neural synapses.The study firstly demonstrates the coexistence of multiple firing patterns through phase diagrams,Lyapunov exponents(LEs),and bifurcation diagrams.Secondly,the parameter related firing behaviors are described through two-parameter bifurcation diagrams.Subsequently,local attraction basins reveal multi-stability phenomena related to initial values.Moreover,the proposed model is implemented on a microcomputer-based ARM platform,and the experimental results correspond to the numerical simulations.Finally,the article explores the application of digital watermarking for medical images,illustrating its features of excellent imperceptibility,extensive key space,and robustness against attacks including noise and cropping.

ⅠA期肺腺癌手术方式的研究进展

目前,早期肺癌的标准术式以各类指南推荐的解剖性肺叶切除联合系统性淋巴结清扫术为主。随着人们健康意识的提高以及低剂量螺旋CT(low-dose computed tomography,LDCT)的普及,越来越多的外周型小结节被发现,这些结节的病理组织学多为肺腺癌。近年来,外科治疗技术不断向精准化、微创化方向发展。针对外周型小结节,外科手术方式也在不断发展,其目的在于保留更多肺组织和肺功能的同时,达到对肿瘤的精准切除。本文针对ⅠA期肺腺癌术前影像学、手术方式、淋巴结清扫方式、术中冰冻、病理亚型及新的病理分级系统对ⅠA期肺腺癌的诊断、治疗及预后影响进行综述。

Effect of whisker alignment on microstructure,mechanical and thermal properties of Mg-SiC_(w)/Cu composite fabricated by a combination of casting and severe plastic deformation(SPD)

In this research,microstructure evaluation,mechanical properties and thermal conductivity of the Mg-SiC_(w)/Cu composite with laminar structure were investigated.For this purpose,SiC whiskers were added to magnesium alloy by using stir-casting,then the Mg-SiC_(w)composite was bonded to copper layers by warm accumulative roll bonding(ARB).Based on the results of optical microscopy(OM)and scanning electron microscopy(SEM),SiC whiskers were well distributed in the magnesium matrix and they were aligned parallelly when the composites were plastically deformed at higher rolling passes.Furthermore,all layers remained continuous with localized necking sites.Also,no intermetallic compounds and phases were detected by XRD and EDS analyzes.Apart from the significant effect of severe plastic deformation on mechanical properties,the findings of mechanical tests point to the usefulness of reinforcements in improving up to 60%microhardness,Young’s modulus,yield,and up to 41%tensile strengths.Further,thermal conductivities of composites increased by adding reinforcement and above all by increasing the number of rolling passes.This growth is attributed to the higher thermal diffusivity of copper and whiskers as well as the increased number of conductive layers within composite.

Quasi-synchronization of fractional-order complex networks with random coupling via quantized control

We investigate the quasi-synchronization of fractional-order complex networks(FCNs) with random coupling via quantized control. Firstly, based on the logarithmic quantizer theory and the Lyapunov stability theory, a new quantized feedback controller, which can make all nodes of complex networks quasi-synchronization and eliminate the disturbance of random coupling in the system state, is designed under non-delay conditions. Secondly, we extend the theoretical results under non-delay conditions to time-varying delay conditions and design another form of quantization feedback controller to ensure that the network achieves quasi-synchronization. Furthermore, the error bound of quasi-synchronization is obtained.Finally, we verify the accuracy of our results using two numerical simulation examples.

Genetic dissection of N use efficiency using maize inbred lines and testcrosses

Although the use of heterosis in maize breeding has increased crop productivity,the genetic causes underlying heterosis for nitrogen(N) use efficiency(NUE) have been insufficiently investigated.In this study,five N-response traits and five low-N-tolerance traits were investigated using two inbred line populations(ILs) consisting of recombinant inbred lines(RIL) and advanced backcross(ABL) populations,derived from crossing Ye478 with Wu312.Both populations were crossed with P178 to construct two testcross populations.IL populations,their testcross populations,and the midparent heterosis(MPH)for NUE were investigated.Kernel weight,kernel number,and kernel number per row were sensitive to N level and ILs showed higher N response than did the testcross populations.Based on a highdensity linkage map,138 quantitative trait loci(QTL) were mapped,each explaining 5.6%–38.8% of genetic variation.There were 52,34 and 52 QTL for IL populations,MPH,and testcross populations,respectively.The finding that 7.6% of QTL were common to the ILs and their testcross populations and that 11.7% were common to the MPH and testcross population indicated that heterosis for NUE traits was regulated by non-additive and non-dominant loci.A QTL on chromosome 5 explained 27% of genetic variation in all of the traits and Gln1-3 was identified as a candidate gene for this QTL.Genome-wide prediction of NUE traits in the testcross populations showed 14%–51% accuracy.Our results may be useful for clarifying the genetic basis of heterosis for NUE traits and the candidate gene may be used for genetic improvement of maize NUE.

Cloning of a new allele of ZmAMP1 and evaluation of its breeding value in hybrid maize

Gene resources associated with plant stature and flowering time are invaluable for maize breeding.In this study,using an F2:3population derived from a natural semi-dwarf mutant grmm and a normal inbred line Si 273,we identified a major pleiotropic QTL on the distal long arm of chromosome 1(qPH1_dla),and found that qPH1_dla controlled plant height,flowering time,ear and yield traits.qPH1_dla was finemapped to a 16 kb interval containing ZmAMP1,which was annotated as a glutamate carboxypeptidase.Allelism tests using two independent allelic mutants confirmed that ZmAMP1 was the causal gene.Realtime quantitative PCR and genomic sequence analysis suggested that a nonsynonymous mutation at the598th base of ZmAMP1 gene was the causal sequence variant for the dwarfism of grmm.This novel ZmAMP1 allele was named ZmAMP1_grmm.RNA sequencing using two pairs of near isogenic lines(NILs)showed that 84 up-regulated and 68 down-regulated genes in dwarf NILs were enriched in 15metabolic pathways.Finally,introgression of ZmAMP1_grmm into Zhengdan 958 and Xianyu 335 generated two improved F1lines.In field tests,they were semi-dwarf,early-flowering,lodging-resistant,and high-yielding under high-density planting conditions,suggesting that ZmAMP1_grmm is a promising Green Revolution gene for maize hybrid breeding.

One Method to Derivate Coulomb’s Law between Two Charges

In electromagnetics, Coulomb’s law is a very classic formula. Almost all textbooks give this formula, but none of them give a detailed corresponding theoretical derivation. In order for beginners of physics to better understand the physical meaning of this formula, we explored the source, the physical model and mechanism of this formula. Based on the principle that the interaction between two different fields can generate energy density, which is equal to the pressure, we analyzed the distribution of the electric field energy density as well as the corresponding pressure on the charged surface. Through the rigorous mathematical derivation, we give the theoretical derivation of this formula.

Modelling and Simulation of an Ohmic Heating Process

Ohmic Heating (OH) is one of the emerging thermal technologies used in food processing which can produce rapid and uniform heating with close to 100% energy transfer efficiency. Although mathematical modelling for OH processes has been studied by many researchers in recent years, systematic simulations of OH have not been developed for model-based control of the processes. In this paper, mathematical model for a Colinear Ohmic Heater is presented, analyzed, and studied based on the selected configuration. A numerical solution for the mathematical equations has been defined and proposed. MATLAB/Simulink model is hence developed and validated against the available data. Simulation results have shown that MATLAB/Simulink model can produce robust outputs at low computational costs with an accuracy of up to 99.6% in comparison to the analytical solution. This model can be used in further studies for analysis of the OH processes and development of advanced controllers.

Constraint-induced movement therapy promotes brain functional reorganization in stroke patients with hemiplegia

Stroke patients with hemiplegia exhibit flexor spasms in the upper limb and extensor spasms in the lower limb, and their movement patterns vary greatly. Constraint-induced movement therapy is an upper limb rehabilitation technique used in stroke patients with hemiplegia; however, studies of lower extremity rehabilitation are scarce. In this study, stroke patients with lower limb hemiplegia underwent conventional Bobath therapy for 4 weeks as baseline treatment, followed by constraint-induced movement therapy for an additional 4 weeks. The 10-m maximum walking speed and Berg balance scale scores significantly improved following treatment, and lower extremity motor function also improved. The results of functional MRI showed that constraint-induced movement therapy alleviates the reduction in cerebral functional activation in patients, which indicates activation of functional brain regions and a significant increase in cerebral blood perfusJon. These results demonstrate that constraint-induced movement therapy promotes brain functional reorganization in stroke patients with lower limb hemiplegia.

QTL analysis across multiple environments reveals promising chromosome regions associated with yield-related traits in maize under drought conditions

Drought is one of the most critical abiotic stresses influencing maize yield. Improving maize cultivars with drought tolerance using marker-assisted selection requires a better understanding of its genetic basis. In this study, a doubled haploid(DH) population consisting of 217 lines was created by crossing the inbred lines Han 21(drought-tolerant) and Ye 478(drought-sensitive). The population was genotyped with a 6 K SNP assay and 756 SNP(single nucleotide polymorphism) markers were used to construct a linkage map with a length of 1344 c M. Grain yield(GY), ear setting percentage(ESP), and anthesis–silking interval(ASI) were recorded in seven environments under well-watered(WW) and water-stressed(WS) regimes. High phenotypic variation was observed for all traits under both water regimes. Using the LSMEAN(least-squares mean) values from all environments for each trait, 18 QTL were detected, with 9 associated with the WW and 9 with the WS regime. Four chromosome regions,Chr. 3: 219.8–223.7 Mb, Chr. 5: 191.5–194.7 Mb, Chr. 7: 132.2–135.6 Mb, and Chr. 10: 88.2–89.4 Mb, harbored at least 2 QTL in each region, and QTL co-located in a region inherited favorable alleles from the same parent. A set of 64 drought-tolerant BC_3F_6 lines showed preferential accumulation of the favorable alleles in these four regions, supporting an association between the four regions and maize drought tolerance. QTL-by-environment interaction analysis revealed 28 ed QTL(environment-dependent QTL) associated with the WS regime and 22 associated with the WW regime for GY, ESP, and ASI. All WS QTL and55.6% of WW QTL were located in the ed QTL regions. The hotspot genomic regions identified in this work will support further fine mapping and marker-assisted breeding of drought-tolerant maize.

Tuning the properties of Ni-based catalyst via La incorporation for efficient hydrogenation of petroleum resin

The hydrogenation of petroleum resin(PR)is an effective process to prepare high value-added hydrogenated PR(HPR).However,the preparation of non-noble metal-based catalysts with high catalytic activity for PR hydrogenation still remains a challenge.Herein,a La promoted Ni-based catalyst is reported through the thermal reduction of quaternary Ni La Mg Al-layered double hydroxides(Ni La Mg Al-LDHs).The incorporation of La is beneficial to the reduction and stability of Ni particles with reduced particle size,and the increased alkalinity effectively mitigates the breakage of molecular chains of PR.As a result,the La promoted Ni-based catalyst exhibits high catalytic activity and excellent stability for PR hydrogenation.A hydrogenation degree of 95.4%and 96.1%can be achieved for HC_(5)PR and HC_(9) PR with less reduced softening point,respectively.Notably,the hydrogenation degree still maintains at 92.7%even after 100 hours’reaction,much better than that without La incorporation or prepared using conventional impregnation method.

聚苯乙烯非均相催化加氢研究进展

随着国民经济发展和人民生活水平的不断提高,聚苯乙烯(PS)产品的多样化、专业化成为了市场竞争和用户需求的发展趋势。聚合物催化加氢工艺作为提高PS专用料性能的重要改性手段,近几年来已成为不饱和聚合物化学改性领域的研究热点。文中主要综述了国内外PS非均相催化加氢制备聚环己烷基乙烯(PCHE)体系中加氢工艺的改进、加氢催化剂的设计优化及反应机理研究的新进展。阐述了催化剂的结构设计、物化性能以及反应过程中传质扩散阻力等对PS加氢活性的影响,探讨了PS非均相催化加氢体系中的"Blocky"加氢机理,提出未来PS非均相加氢催化剂研究重点应该放在催化剂的结构设计上,既要保证聚合物分子与活性中心高接近性,又要实现在加氢体系中的传质扩散与催化剂载体上活性位点高分散的最佳平衡。同时,为进一步提高加氢催化剂的综合性能,需要加强对聚合物加氢反应机理和催化剂合成改性技术的基础性研究。

5G ENABLED VEHICULAR COMMUNICATIONS AND NETWORKING

Vehicular communications and networking(VCN)is considered a billion-dollar industry.Its development not only possesses economic value,but also has enormous social potential.The earliest vehicular network started from the dedicated short range networks,such as the IEEE 802.11p standard established at the beginning of this century.In recent years,the public access network based VCN has been rapidly advanced.For example,LTE-V based on 4G LTE is under standardization。

Regional cerebral blood flow imaging assessment of brain function reconstruction in elderly hemiplegia patients by body weight support treadmill training

The mechanism underlying body weight support treadmill training in elderly hemiplegic stroke patients is largely unknown. This study aimed to elucidate the changes of cortical blood flow in seven elderly patients with post-stroke hemiplegia before and after body weight support treadmill training by semi-quantitative analysis of regional cerebral blood flow assessed by single photon emission computed tomography. Body weight support treadmill training for 6 months was effective in improving cerebral blood flow and promoting the walking speed and balance recovery in elderly patients with post-stroke hemiplegia.

Protein-derived nitrogen and sulfur co-doped carbon for efficient adsorptive removal of heavy metals

A nitrogen and sulfur co-doped carbon has been synthesized employing egg white as a sustainable protein-rich precursor.According to CHNS elemental analysis,N,S and O heteroatoms accounted for mass fractions of 3.66%,2.28%and 19.29%respectively,and the types of surface functionalities were further characterized by FT-IR and XPS measurements.Although the carbon possessed a smaller surface area(815 m2·g-1)compared to a commercial activated carbon(1100 m2·g-1),its adsorption capacity towards Co2+reached 320.3 mg·g-1,which was over 8 times higher compared to the limited 34.0 mg·g-1 over the activate carbon.Furthermore,the carbon was found to be an efficient adsorbent towards a series of metal ions including VO2+,Cr3+,Ni2+,Cu2+and Cd2+.Combined with its environmental merits,the protein derived carbon may be a promising candidate for heavy metal pollution control.

Effects of pre-oxidant(KMnO4)on structure and performance of PVDF and PES membranes

The structure and performance of membrane materials are very important to the efficient and stable operation in membrane drinking water purification technology. Potassium permanganate(KMnO_4), which can change the characteristics of organic matters and control membrane surface fouling, has been widely used as pre-oxidant in the front of membrane drinking water process. This study investigates the evolution of membrane surface structure and performance when polyvinylidene fluoride(PVDF) and polyethersulfone(PES) were exposed to10, 100 and 1000 mg·L^(-1) KMnO_4 solution for 6 and 12 d, respectively. The aged membrane physicochemical characteristics such as membrane surface morphology, chemical composition, hydrophilicity, porosity and zeta potential were evaluated by modern analytical and testing instruments. The anti-fouling property of membrane surface was also investigated by the filtration-backwash experiment. The results indicated that the different concentrations and exposure time of KMnO_4 led to a different variation on PVDF and PES membrane surface structure and performance, which could further affect the membrane separation performance and the membrane fouling behaviors. The membrane surface pore size and porosity increased due to the dislodgment and degradation of membrane additive(PVP), which improved membrane permeability and enhanced the adsorption and deposition of pollutants in the membrane pores. With the increase of exposure time, the membrane surface pore size and porosity reduced for the reactions of chain scission and crosslinking on membrane materials, and the backwashing efficiency declined, leading to a more serious irreversible fouling. Compared with PVDF membranes, the formation of sulfonic group for PES membranes increased the negative charge on membrane surface due to the oxidation of KMnO_4. The present study provides some new insights for the regulation of the pre-oxidant dose and the selection of the membrane materials in KMnO_4 pre-oxidation combined with membrane filtration system.

Redistributing Cu species in Cu-SSZ-13 zeolite as NH3-SCR catalyst via a simple ion-exchange

The nature and distribution of Cu species in Cu-SSZ-13 play a vital role in selective catalytic reduction of NO by NH3(NH3-SCR),but existing methods for adjusting the Cu distribution are complex and difficult to control.Herein,we report a simple and effective ion-exchange approach to regulate the Cu distribution in the one-pot synthesized Cu-SSZ-13 that possesses sufficient initial Cu species and thus provides a“natural environment”for adjusting Cu distribution precisely.By using this proposed strategy,a series of Cu-SSZ-13x zeolites with different Cu contents and distributions were obtained.It is shown that the dealumination of the as-synthesized Cu-SSZ-13 during the ion-exchange generates abundant vacant sites in the double six-membered-rings of the SSZ-13 zeolite for relocating Cu2+species and thus allows the redistribution of the Cu species.The catalytic results showed that the ion-exchanged Cu-SSZ-13 zeolites exhibit quite different catalytic performance in NH3-SCR reaction but superior to the parent counterpart.The structure–activity relationship analysis indicates that the redistribution of Cu species rather than other factors(e.g.,crystallinity,chemical composition,and porous structure)is responsible for the improved NH3-SCR performance and SO_(2) and H_(2)O resistance.Our work offers an effective method to precisely adjust the Cu distribution in preparing the industrial SCR catalysts.

SHARP BOUNDS FOR TOADER-TYPE MEANS IN TERMS OF TWO-PARAMETER MEANS

In the article,we prove that the double inequalities Gp[λ1a+(1-λ1)b,λ1 b+(1-λ1)a]A1-p(a,b)<T[A(a,b),G(a,b)]<Gp[μ1 a+(1-μ1)b,μ1b+(1-μ1)a]A1-p(a,b),Cs[λ^(2) a+(1-λ2)b,λ2 b+(1-λ2)a]A1-s(a,b)<T[A(a,b),Q(a,b)]<Cs[μ2 a+(1-μ2)b,μ2 b+(1-μ2)a]A1-p(a,b)hold for all a,b>0 with a≠b if and only ifλ1≤1/2-(1-(2/π)2/p)1/2/2,μ1≥1/2-(2p)1/2/(4 p),λ2≤1/2+(2(3/(2 s)(E(21/2/2)/π)1/s)-1)1/2/2 andμ2≥1/2+s1/2/(4 s)ifλ1,μ1∈(0,1/2),λ2,μ2∈(1/2,1),p≥1 and s≥1/2,where G(a,b)=(ab)1/2,A(a,b)=(a+b)/2,T(a,b)=∫0π/2(a2 cos2 t+b2 sin2)1/2 tdt/π,Q(a,b)=((a2+b2)/2)1/2,C(a,b)=(a2+b2)/(a+b)and E(r)=∫0π/2(1-r^(2) sin^(2))1/2 tdt.