Progress and key challenges in catalytic combustion of lean methane

As a primary type of clean energy,methane is also the second most important greenhouse gas after CO_(2)due to the high global warming potential.Large quantities of lean methane(0.1–1.0 vol%)are emitted into the atmosphere without any treatment during coal mine,oil,and natural gas production,thus leading to energy loss and greenhouse effect.In general,it is challenging to utilize lean methane due to its low concentration and flow instability,while catalytic combustion is a vital pathway to realize an efficient utilization of lean methane owing to the reduced emissions of polluting gases(e.g.,NOxand CO)during the reaction.In particular,to efficiently convert lean methane,it necessitates both the designs of highly active and stable heterogeneous catalysts that accelerate lean methane combustion at low temperatures and smart reactors that enable autothermal operation by optimizing heat management.In this review,we discuss the in-depth development,challenges,and prospects of catalytic lean methane combustion technology in various configurations,with particular emphasis on heat management from the point of view of material design combined with reactor configuration.The target is to describe a framework that can correlate the guiding principles among catalyst design,device innovation and system optimization,inspiring the development of groundbreaking combustion technology for the efficient utilization of lean methane.

Prediction of rockhead using a hybrid N-XGBoost machine learning framework

The spatial information of rockhead is crucial for the design and construction of tunneling or underground excavation.Although the conventional site investigation methods(i.e.borehole drilling) could provide local engineering geological information,the accurate prediction of the rockhead position with limited borehole data is still challenging due to its spatial variation and great uncertainties involved.With the development of computer science,machine learning(ML) has been proved to be a promising way to avoid subjective judgments by human beings and to establish complex relationships with mega data automatically.However,few studies have been reported on the adoption of ML models for the prediction of the rockhead position.In this paper,we proposed a robust probabilistic ML model for predicting the rockhead distribution using the spatial geographic information.The framework of the natural gradient boosting(NGBoost) algorithm combined with the extreme gradient boosting(XGBoost)is used as the basic learner.The XGBoost model was also compared with some other ML models such as the gradient boosting regression tree(GBRT),the light gradient boosting machine(LightGBM),the multivariate linear regression(MLR),the artificial neural network(ANN),and the support vector machine(SVM).The results demonstrate that the XGBoost algorithm,the core algorithm of the probabilistic NXGBoost model,outperformed the other conventional ML models with a coefficient of determination(R2)of 0.89 and a root mean squared error(RMSE) of 5.8 m for the prediction of rockhead position based on limited borehole data.The probabilistic N-XGBoost model not only achieved a higher prediction accuracy,but also provided a predictive estimation of the uncertainty.Thus,the proposed N-XGBoost probabilistic model has the potential to be used as a reliable and effective ML algorithm for the prediction of rockhead position in rock and geotechnical engineering.

Orbital control on cyclical organic matter accumulation in Early Silurian Longmaxi Formation shales

High resolution(939 samples)total organic carbon content(TOC)analyses were conducted on the Shuanghe Section of^152.6 m in the Changning area,Sichuan Basin.The sampling section was divided into two units considering the distinct-different deposit environment and sediments accumulation rate.The lower part(Unit 1)and the peer part(Unit 2)with high resolution sample spacing(0.08–0.4 m)enables the identification of the precession cycle in two sedimentary sequences with distinct different sedimentary accumulation rate.MTM Power spectral analyses on untuned TOC series reveals significant peaks exceeding above the 95%confidence level and shows that both Unit 1 and Unit 2 have recorded Milankovitch cycles of 405 kyr long eccentricity,short eccentricity,obliquity and precession.The floating astronomical time scale(ATS)was constructed on the Shuanghe Section in the Early Silurian(~439.673–444.681 Ma),and which was calibrated by 405 kyr long eccentricity cycles.The total duration of the Wufeng and Longmaxi shales is 5.01 Myr.The floating ATS used for estimating the duration of the graptolite zones and each stage in the study interval.Finally,we postulated two models that could verify the linkage between orbital cycle and organic accumulation.To make sure whether productivity or preservation is the main factor that under long eccentricity control,the phase correlation between the obtained filtered signal and the theoretical orbital solution should be made clear in the further research.

Hydrogen production via chemical looping reforming of coke oven gas

Coke oven gas(COG)is one of the most important by-products in steel industry,and the conversion of COG to value-added products has attracted much attention from both economic and environmental views.In this work,we use the chemical looping reforming technology to produce pure H_(2) from COG.A series of La1-xSrxFeO_(3)(x?0,0.2,0.3,0.4,0.5,0.6)perovskite oxides were prepared as oxygen carriers for this purpose.The reduction behaviors of La1-xSrxFeO_(3) perovskite by different reducing gases(H_(2),CO,CH4 and the mixed gases)are investigated to discuss the competition effect of different components in COG for reacting with the oxygen carriers.The results show that reduction temperatures of H_(2) and CO are much lower than that of CH4,and high temperatures(>800℃)are requested for selective oxidation of methane to syngas.The co-existence of CO and H_(2) shows weak effect on the equilibrium of methane conversion at high temperatures,but the oxidation of methane to syngas can inhibit the consumption of CO and H_(2).The doping of suitable amounts of Sr in LaFeO_(3) perovskite(e.g.,La0.5Sr0.5FeO_(3))significantly promotes the activity for selective oxidation of methane to syngas and inhibits the formation of carbon deposition,obtaining both high methane conversion in the COG oxidation step and high hydrogen yield in the water splitting step.The La0.5Sr0.5FeO_(3) shows the highest methane conversion(67.82%),hydrogen yield(3.34 mmol g^(-1))and hydrogen purity(99.85%).The hydrogen yield in water splitting step is treble as high as the hydrogen consumption in reduction step.These results reveal that chemical looping reforming of COG to produce pure H_(2) is feasible,and an O_(2)-assistant chemical looping reforming process can further improves the redox stability of oxygen carrier.

Layered Mg-Al spinel supported Ce-Fe-Zr-O oxygen carriers for chemical looping reforming

A series of layered Mg-Al spinel supported Ce-Fe-Zr-O oxygen carriers were prepared for co-production of syngas and pure hydrogen via chemical looping steam reforming(CLSR).The presence of magnesium-aluminum layered double oxides(Mg Al-LDO)significantly increases the specific surface area of the mixed oxides,reduces the particle size of CeO2-based solid solution and promotes the dispersion of free Fe2O3.When reacting with methane,Mg Al-LDO supported oxygen carrier shows much lower temperature for methane oxidation than the pure CeFe-Zr-O sample,indicating enhanced low-temperature reactivity.Among different Ce-Fe-Zr-O(x)/Mg Al-LDO samples,the Ce-Fe-Zr-O(40 wt%)/Mg Al-LDO sample shows the best performance for the selective oxidation of methane to syngas and the H2 production by water splitting.After a long period of high temperature redox experiment,the Ce-Fe-Zr-O(40 wt%)/Mg Al-LDO oxygen carrier still shows high activity for syngas generation.The comparison on the morphology of the fresh and cycled oxygen carriers indicates that the Mg-Al spinel support still forms a stable skeleton structure with high dispersion of active components on the surface after the long-term cycling,which contributes to excellent redox stability of the Ce-Fe-Zr-O(40 wt%)/Mg Al-LDO oxygen carrier.

Large Rabi splitting obtained in Ag‐WS2 strong‐coupling heterostructure with optical microcavity at room temperature

Manipulation of light-matter interaction is critical in modern physics, especially in the strong coupling regime, where the generated half-light, half-matter bosonic quasiparticles as polaritons are important for fundamental quantum science and applications of optoelectronics and nonlinear optics. Two-dimensional transition metal dichalcogenides (TMDs) are ideal platforms to investigate the strong coupling because of their huge exciton binding energy and large absorption coefficients. Further studies on strong exciton-plasmon coupling by combining TMDs with metallic nanostructures have generated broad interests in recent years. However, because of the huge plasmon radiative damping, the observation of strong coupling is significantly limited at room temperature. Here, we demonstrate that a large Rabi splitting (~300 meV) can be achieved at ambient conditions in the strong coupling regime by embedding Ag-WS2 heterostructure in an optical microcavity. The generated quasiparticle with part-plasmon, part-exciton and part-light is analyzed with Hopfield coefficients that are calculated by using three-coupled oscillator model. The resulted plasmon-exciton polaritonic hybrid states can efficiently enlarge the obtained Rabi splitting, which paves the way for the practical applications of polaritonic devices based on ultrathin materials.

Optical spin-to-orbital angular momentum conversion in structured optical fields

We investigate the dynamic quantities:momentum,spin and orbital angular momenta(SAM and OAM),and their conversion relationship in the structured optical fields at subwavelength scales,where the spin–orbit interaction(SOI)plays a key role and determines the behaviors of light.Specifically,we examine a nanostructure of a Ag nanoparticle(Ag NP)attached on a cylindrical Ag nanowire(Ag NW)under illumination of elliptically polarized light.These dynamic quantities obey the Noether theorem,i.e.,for the Ag nanoparticle with spherical symmetry,the total angular momentum consisting of SAM and OAM conserves;for the Ag NW with translational symmetry,the orbital momentum conserves.Meanwhile,the spin-to-orbital angular momentum conversion is mediated by SOI arising from the spatial variation of the optical potential.In this nanostructure,the conservation of momentum imposes a strict restriction on the propagation direction of the surface plasmon polaritons along the Ag NW.Meanwhile,the orbital momentum is determined by the polarized properties of the excitation light and the topography of the Ag NP.Our work offers insights to comprehend the light behaviors in the structured optical fields in terms of the dynamic quantities and benefits to the design of optical nano-devices based on interactions between spin and orbital degrees of freedom.

Photosynthetic Toxicity and Oxidative Damage Induced by nano-Fe3O4 on <i>Chlorella vulgaris</i>in Aquatic Environment

With the rapid development of nanotechnology and widespread use of nanoproducts, concerns have arisen regarding the ecotoxicity of these materials. In this paper, the photosynthetic toxicity and oxidative damage induced by nano Fe3O4 on a model organism, Chlorella vulgaris (C. vulgaris) in aquatic environment, were studied. The results showed that Nano-Fe3O4 was toxic to C. vulgaris and affected its content of chlorophyll a, malonaldehyde and glutathione, CO2 absorption, net photosynthetic rate, superoxide dismutase activity and inhibition of hydroxyl radical generation. At higher concentrations, compared with the control group, the toxicity of nano-Fe3O4 was significantly different. It suggested that nano-Fe3O4 is ecotoxic to C. vulgaris in aquatic environment.

Oxygen vacancies enriched Ni-Co/SiO_(2)@CeO_(2) redox catalyst for cycling methane partial oxidation and CO_(2) splitting

Redox catalysts play a vital role in the interconversion of two significant greenhouse gases,CO_(2)and CH_(4),via chemical looping methane dry reforming technology.Herein,a series of transition metals-alloyed and core-shell structured Ni-M/SiO_(2)@CeO_(2)(M=Fe,Co,Cu,Mn,Zr)redox catalyst were fabricated and evaluated in a gas-solid fixed-bed reactor for cycling CH_(4)partial oxidation(PO_(x))and CO_(2)splitting.The catalysts are composed of spherical SiO_(2)core and CeO_(2)shell,and the highly dispersed Ni alloy nanoparticles are the interlayer between core and shell.The oxygen vacancy concentration of Ni-M/SiO_(2)@CeO_(2)followed the order of Co>Cu>Fe>Mn>Zr,and Ni alloying with transition metals significantly enhanced oxygen storage capacity(OSC).Ni-Co/SiO_(2)@CeO_(2)catalyst with abundant oxygen vacancies and a high OSC showed the lowest temperatures of CH_(4)activation(610℃)and CO_(2)decomposition(590℃),thus demonstrating excellent redox reactivity.The catalyst exhibited superior activity and structural stability in the continuous CH_(4)/CO_(2)redox cycles at 615℃,achieving 87%CH_(4)conversion and 83%CO selectivity.The proposed catalyst shows great potential for the utilization of CH_(4)and CO_(2)in a redox mode,providing a new sight for design redox catalyst in chemical looping or related fields.

Suppressing byproduct formation for high selective CO_(2) reduction over optimized Ni/TiO_(2) based catalysts

One of the challenges for catalytic CO_(2)reduction is to control product selectivity,and new findings that can modify selectivity would be transformative.Herein,two kinds of TiO_(2)(homemade and commercial)with the same crystal phase but different surface properties are chosen as supports to prepare Ni-based catalysts for CO_(2)reduction,which show distinctly different product selectivity for CO_(2)reduction to CH_(4) or CO,as well as the CO_(2)conversion.The catalysts based on the homemade TiO_(2)support are highly selective for CH_(4) formation,while the latter ones are about 100%selective for CO formation under the same reaction conditions.In addition,the former ones are much active(more than 3 times)than the latter ones.We found that the collaborative contribution of Ti^(3+)and Ni^(2+)species and the electronic metal-support interactions effect maybe the main driving force behind for determining the product selectivity.Methane is almost exclusively produced over the catalysts with abundant Ti^(3+)and Ni^(2+)species and greater electronic metal-support interaction,otherwise,it will give priority to CO generation.The addition of CeO_(2)can reduce the Ni particle size and improve the dispersion of Ni nanoparticles,as well as create more Ti^(3+)species,contributing to the enhancement of CO_(2)conversion,but shows a negligible effect on product selectivity.Furthermore,the in situ DRIFT experiments and kinetic experiments indicate that the CO route is probably involved in the CO_(2)reduction process over the homemade Ni-CeO_(2)/TiO_(2)-CO catalyst with abundant Ti^(3+)and Ni^(2+)species and a strong electronic transform effect.

Scanning cathodoluminescence microscopy： applications in semiconductor and metallic nanostructures

Cathodoluminescence （CL） as a radiative light produced by an electron beam exciting a luminescent material, has beenwidely used in imaging and spectroscopic detection of semiconductor, mineral and biological samples with an ultrahigh spatial resolution. Conventional CL spectroscopy shows an excellent performance in characterization of traditional mate-rial luminescence, such as spatial composition variations and fluorescent displays. With the development of nanotech-nology, advances of modern microscopy enable CL technique to obtain deep valuable insight of the testing sample, and further extend its applications in the material science, especially for opto-electronic investigations at nanoscale. In this article, we review the study of CL microscopy applied in semiconductor nanostructures for the dislocation, carrier diffu-sion, band structure, doping level and exciton recombination. Then advantages of CL in revealing and manipulating sur-face plasmon resonances of metallic nanoantennas are discussed. Finally, the challenge of CL technology is summa-rized, and potential CL applications for the future opto-electronic study are proposed.

Impulse Radio UWB Signal Detection Based on Compressed Sensing

The extremely high sampling rate is a challenge for ultra-wideband (UWB) communication. In this paper, we study the compressed sensing (CS) based impulse radio UWB (IR-UWB) signal detection and propose an IR-UWB signal detection algorithm based on compressive sampling matching pursuit (CoSaMP). The proposed algorithm relies on the fact that UWB received signal is sparse in the time domain. The new algorithm can significantly reduce the sampling rate required by the detection and provides a better performance in case of the low signal-to-noise ratio when comparing with the existing matching pursuit (MP) based detection algorithm. Simulation results demonstrate the effectiveness of the proposed algorithm.

A single atom photocatalyst co-doped with potassium and gallium for enhancing photocatalytic hydrogen peroxide synthesis

Polymer carbon nitride(PCN)is widely used in photocatalysis.However,pristine PCN has disadvantages such as insufficient visible light absorption and low photogenerated carrier separation efficiency that greatly limited the photocatalytic efficiency.As a non-toxic metal,gallium has the potential to solve the defects of PCN.Gallium ions coordinated with nitrogen in carbon nitride to form Ga-N active sites and improved the photocatalytic activity.The doped potassium ions form a transmission channel for charge redistribution and transfer between adjacent layers,which is beneficial for better separation of photoexcited carriers.In this study,a series of PCN co-doped with gallium and potassium(Ga-K-PCN)were prepared.The experimental results indicated photocatalytic generation of hydrogen peroxide proceeds through the 2e−oxygen reduction reaction pathway.Notably,Nyquist plots and photocurrent results further proved that the presence of Ga-N sites and potassium ion doping could significantly improve the separation/transfer of intra-planar and interlayer charge carriers and thus enhance photocatalytic efficiency.The Ga10-K3-PCN photocatalysts promoted yield of H_(2)O_(2),with reactivity at 28.2μmol/(g·h)and solar-to-chemical conversion efficiency at 0.64%,surpassed that of a typical photo-catalyst based on PCN(0.18%).

Direct observation of ultrafast plasmonic hot electron transfer in the strong coupling regime

Achieving strong coupling between plasmonic oscillators can significantly modulate their intrinsic optical properties.Here,we report the direct observation of ultrafast plasmonic hot electron transfer from an Au grating array to an MoS_(2) monolayer in the strong coupling regime between localized surface plasmons(LSPs)and surface plasmon polaritons(SPPs).By means of femtosecond pump-probe spectroscopy,the measured hot electron transfer time is approximately 40 fs with a maximum external quantum yield of 1.65%.Our results suggest that strong coupling between LSPs and SPPs has synergetic effects on the generation of plasmonic hot carriers,where SPPs with a unique nonradiative feature can act as an‘energy recycle bin’to reuse the radiative energy of LSPs and contribute to hot carrier generation.Coherent energy exchange between plasmonic modes in the strong coupling regime can further enhance the vertical electric field and promote the transfer of hot electrons between the Au grating and the MoS_(2) monolayer.Our proposed plasmonic strong coupling configuration overcomes the challenge associated with utilizing hot carriers and is instructive in terms of improving the performance of plasmonic opto-electronic devices.

Crack-free and high-strength AA2024 alloy obtained by additive manufacturing with controlled columnar-equiaxed-transition

Laser powder bed fusion(LPBF)of high-strength Al alloys is challenging due to the formation of both hot and cold cracks.In the present work,highly dense and crack-free AA2024 samples could be additively manufactured via inoculation treatment of Zr-based metallic glass(MG)powders.The columnar grains in the LPBF-fabricated AA2024 alloy were significantly refined and almost completely transformed to the equiaxed grains with a bimodal grain size distribution consisting of ultrafine grains with a size smaller than 1μm and relatively coarser grains.The grain refinement can be associated with the formation of Al3Zr particles,serving as the heterogeneous nucleation sites for theα-Al matrix.Complete routes for columnar-equiaxed-transition(CET)have been revealed by tailoring the concentration of nucleation particles and solidification conditions.CET occurs both at the melt pool boundary due to the sufficiently high concentration of Al3Zr particles and at the topmost of the melt pool due to the heterogeneous nucleation driven by constitutional undercooling.Between these two regions,columnar grains epitaxially grow with orientations determined by the thermal gradient.The as-built Zr-based MG inoculated AA2024 specimens are robust in healing hot cracks due to a more tortuous propagation path of cracks for equiaxed grains.The as-fabricated AA2024/5%MG specimens exhibit a high ultimate tensile strength of 531 MPa due to crack elimination and grain refinement,surpassing most of the reported values for the LPBF-fabricated AA2024 alloy inoculated with other inoculated powders.The present work could provide a novel inoculation agent to fabricate high-strength Al alloys and the CET can be used to precisely control the grain morphology.

Enhanced optical performance of multifocal metalens with conic shapes

A multifocal metalens,which focuses incident light at multiple foci,has many applications in imaging systems and optical communications.However,the traditional design strategy of a multifocal metalens combines several lenses that have different focal points into a planar integrated unit,resulting in low imaging quality because of the high background noise.Here we show that the defects of the traditional method can be overcome by designing a metalens with conic shapes(the ellipse and the hyperbola);this approach could improve the imaging performance and substantially decrease the background noise of multifocal metalenses.These benefits arise from the intrinsic properties of the two conic curves,which can focus incident light constructively at all of the foci of the metalens.We further demonstrate that the proposed conicshaped metalens can function well within a broadband operation wavelength that ranges from 600 to 900 nm with the dual polarity actively controlled by the incident circular polarized light.The great agreement between the experimental and simulation results demonstrates that our proposed metalens has significant potential for use in future integrated nanophotonic devices.

Temperature dependent Raman and photoluminescence of vertical WS2/MoS2 monolayer heterostructures

Heterostructures from two-dimensional transition-metal dichalcogenides MX2 have emerged as a hot topic in recent years due to their various fascinating properties. Here, we investigated the temperature dependent Raman and photoluminescence （PL） spectra in vertical stacked WS2/MoS2 monolayer heterostructures. Our result shows that both E^g and Alg modes of WS2 and MoS2 vary linearly with tem- perature increasing from 300 to 642 K. The PL measurement also reveals strong temperature dependencies of the PL intensity and peak position. The activation energy of the thermal quenching of the PL emission has been found to be equal to 69.6 meV. The temperature dependence of the peak energy well follows the band- gap shrinkage of bulk semiconductor.

Application of amphoteric polymers in the process of leather post-tanning

With the characteristics of controllable charge and environmental friendliness,amphoteric polymers can be used in post-tanning process to solve the problems that arise during leather making and are caused by the low absorption rate of single-charge chemicals,incompatibility with new tanning methods,and complex operation process.In this review,the structure,performance,and preparation of amphoteric polymers are reported.Then,the charge change of collagen during different tanning and pH treatments is introduced.Finally,the application and development of amphoteric polymers during the post-tanning process of leather making are discussed.This review has certain guiding significance to the preparation and application of amphoteric polymers for tanning system.

Sequential co-immobilization of β-glucosidase and yeast cells on single polymer support for bioethanol production

Co-immobilization of enzymes and microorganism is an effective way to enable cells to use nonmetabolizable substrates and accelerate reaction rate of overall process. Herein, a facile strategy to separately co-immobilize β-glucosidase(BG) and yeast cells on non-woven fabrics was developed. The BG was firstly in situ entrapped into poly(ethylene glycol)(PEG) network grafted on non-woven fabrics by visible light induced living/controlled graft polymerization. Then re-graft polymerization was performed on the as-formed BG loaded layer by taking advantage of living-grafting polymerization on its surface to in situ encapsulate yeast cells into the second PEG network layer. This layered structure of co-immobilization avoided possible interference between enzyme and cells. Viability assay of yeast cells demonstrated that most of cells were viable after immobilization. While immobilized BG showed decreased V_(max) compared to free BG, indicating that entrapping BG into inner PEG network layer restricted its accessibility with substrates. This co-immobilization sheet could successfully convert cellobiose to ethanol and a maximum of 98.6% bioethanol yield can be obtained after 48 h of simultaneous saccharification and fermentation(SSF). The co-immobilization sheet showed excellent reusability and could still reach more than 60% of original ethanol yield after reusing for 7 batches. Compared with the mixed co-immobilization, the sequential layered immobilization in this system showed better stability and higher ethanol yield.

Bi-channel near-and far-field optical vortex generator based on a single plasmonic metasurface

With the recent development of the metasurface,generating an optical vortex in optical far or near fields is realized in various ways.However,to generate vortices in both the near and far fields simultaneously is still a challenge,although it has great potential in the future compact and versatile photonic system.Here,a bi-channel optical vortex generator in both the near and far fields is proposed and demonstrated within a single metasurface,where the surface plasmon vortex and the far-field optical vortex can be simultancously generated under circularly polarized light.The ability of generating vortices with arbitrary topological charges is experimentally demon-strated,which agrces well with simulations.This approach provides great freedom to integrate different vortex generators in a single device and ofers new opprtunities for integrated optical communications,trapping,and other related fields.