Enhanced selectivity of catalytic hydrogenation of halogenated nitroaromatics by interfacial effects

The highly selective catalytic hydrogenation of halogenated nitroaromatics was achieved by employing Pd‑based catalysts that were co‑modified with organic and inorganic ligands.It was demonstrated that the catalysts contained Pd species in mixed valence states,with high valence Pd at the metal‑support interface and zero valence Pd at the metal surface.While the strong coordination of triphenylphosphine(PPh3)to Pd0 on the Pd surface prevents the adsorption of halogenated nitroaromatics and thus dehalogenation,the coordination of sodium metavanadate(NaVO3)to high‑valence Pd sites at the interface helps to activate H2 in a heterolytic pathway for the selective hydrogenation of nitro‑groups.The excellent catalytic performance of the interfacial active sites enables the selective hydrogenation of a wide range of halogenated nitroaromatics.

Low‑Temperature Fabrication of Stable Black‑Phase CsPbI_(3) Perovskite Flexible Photodetectors Toward Wearable Health Monitoring

Flexible wearable optoelectronic devices fabricated fromorganic–inorganic hybrid perovskites significantly accelerate the developmentof portable energy,biomedicine,and sensing fields,but their poor thermal stabilityhinders further applications.Conversely,all-inorganic perovskites possessexcellent thermal stability,but black-phase all-inorganic perovskite filmusually requires high-temperature annealing steps,which increases energy consumptionand is not conducive to the fabrication of flexible wearable devices.In this work,an unprecedented low-temperature fabrication of stable blackphaseCsPbI3perovskite films is demonstrated by the in situ hydrolysis reactionof diphenylphosphinic chloride additive.The released diphenyl phosphateand chloride ions during the hydrolysis reaction significantly lower the phasetransition temperature and effectively passivate the defects in the perovskitefilms,yielding high-performance photodetectors with a responsivity of 42.1 AW−1 and a detectivity of 1.3×10^(14)Jones.Furthermore,high-fidelity imageand photoplethysmography sensors are demonstrated based on the fabricated flexible wearable photodetectors.This work provides a newperspective for the low-temperature fabrication of large-area all-inorganic perovskite flexible optoelectronic devices.

Defects‑Rich Heterostructures Trigger Strong Polarization Coupling in Sulfides/Carbon Composites with Robust Electromagnetic Wave Absorption

Defects-rich heterointerfaces integrated with adjustable crystalline phases and atom vacancies,as well as veiled dielectric-responsive character,are instrumental in electromagnetic dissipation.Conventional methods,however,constrain their delicate constructions.Herein,an innovative alternative is proposed:carrageenan-assistant cations-regulated(CACR)strategy,which induces a series of sulfides nanoparticles rooted in situ on the surface of carbon matrix.This unique configuration originates from strategic vacancy formation energy of sulfides and strong sulfides-carbon support interaction,benefiting the delicate construction of defects-rich heterostructures in M_(x)S_(y)/carbon composites(M-CAs).Impressively,these generated sulfur vacancies are firstly found to strengthen electron accumulation/consumption ability at heterointerfaces and,simultaneously,induct local asymmetry of electronic structure to evoke large dipole moment,ultimately leading to polarization coupling,i.e.,defect-type interfacial polarization.Such“Janus effect”(Janus effect means versatility,as in the Greek two-headed Janus)of interfacial sulfur vacancies is intuitively confirmed by both theoretical and experimental investigations for the first time.Consequently,the sulfur vacancies-rich heterostructured Co/Ni-CAs displays broad absorption bandwidth of 6.76 GHz at only 1.8 mm,compared to sulfur vacancies-free CAs without any dielectric response.Harnessing defects-rich heterostructures,this one-pot CACR strategy may steer the design and development of advanced nanomaterials,boosting functionality across diverse application domains beyond electromagnetic response.

Effects of cryogenic treatment on the thermal physical properties of Cu_(76.12) Al_(23.88) alloy

The thermal diffusion coefficient, heat capacity, thermal conductivity, and thermal expansion coefficient of Cu76.12Al23.88 alloy before and after cryogenic treatment in the heating temperature range of 25℃ to 600℃ were measured by thermal constant tester and thermal expansion instrument. The effects of cryogenic treatment on the thermal physical properties of CU76,12A123,88 alloy were investigated by comparing the variation of the thermal parameters before and after cryogenic treatment. The results show that the variation trend of the thermal diffusion coefficient, heat capacity, thermal conductivity, and thermal expansion coefficient of CU76.12Al23.88 alloy after cryogenic treatment was the same as before. The cryogenic treatment can increase the thermal diffusion coefficient, thermal conductivity, and thermal expansion coeffi- cient of Cu76.12Al23.88 alloy and decrease its heat capacity. The maximum difference in the thermal diffusion coefficient between the before and after cryogenic treatment appeared at 400℃. Similarly, thermal conductivity was observed at 200℃.

Structures and physical properties of R_2TX_3 compounds

Rare-earth compounds have been an attractive subject based on the unique electronic structures of the rare-earth elements. Novel ternary intermetallic compounds R2TX3 （R = rare-earth element or U, T = transition-metal element, X = Si, Ge, Ga, In） are a significant branch of this research field due to their complex and intriguing physical properties, such as magnetic order at low temperature, spin-glass behavior, Kondo effect, heavy fermion behavior, and so on. The unique physical properties of R2TX3 compounds are related to distinctive electronic structures, crystal structures, micro- interaction, and external environment. Most R2TX3 compounds crystallize in A1B2-type or derived A1B2-type structures and exhibit many similar properties. This paper gives a concise review of the structures and physical properties of these compounds. Spin glass, magnetic susceptibility, resistivity, and specific heat of R2 TX3 compounds are discussed.

Regulating local chemistry in ZrCo-based orthorhombic hydrides via increasing atomic interference for ultra-stable hydrogen isotopes storage

Developing a universal and reliable strategy for the modulation of composition and structure of energy storage materials with stable cycling performance is vital for hydrogen and its isotopes storage advanced system,yet still challenging.Herein,an ultra-stable lattice structure is designed and verified to increase atomic chaos and interference for effectively inhibiting disproportionation reaction and improving cycling stability in ZrCo-based hydrogen isotopes storage alloy.After screening in terms of configuration entropy calculation,we construct Zr_(1-2)Nb_(x)Co_(1-2x)Cu_(x)Ni_(x)(x=0.15,0.2,0.25) alloys with increased atomic chaos,and successfully achieve stable isostructural de-/hydrogenation during 100 cycles,whose cycling capacity retentions are above 99%,much higher than 22.4%of pristine ZrCo alloy.Both theoretical analysis and experimental evidences indicate the high thermo-stability of orthorhombic lattice in Zr_(0.8)Nb_(0.2)Co_(0.6)Cu_(0.2)Ni_(0.2) alloy.Notably,the increased atomic chaos and interference in Zr_(0.8)Nb_(0.2)Co_(0.6)Cu_(0.2)Ni_(0.2) alloy causes regulation in hydrogen local chemical neighborhood,thereby confusing the hydrogen release order,which effectively eliminates lattice distortion and unlocks an ultrastable lattice structure.This study provides a new and comprehensive inspiration for hydrogen atoms transport behaviors and intrinsic reason of stable orthorhombic transformation,which can contribute to paving the way for other energy storage materials modulation.

A new horizontal in C1 chemistry: Highly selective conversion of syngas to light olefins by a novel OX-ZEO process

The most challenging goal of C1 chemistry is the control of C–C coupling to produce chemicals or fuels from C1 feedstocks,in particular syngas（H2/CO）,which can be derived from various carbon resources such as coal,natural gas or shale gas,and biomass.

Advances in selective conversion of carbohydrates into 5-hydroxymethylfurfural

Converting carbohydrates into 5-hydroxymethylfurfural(5-HMF) is an attractive and promising route for value-added utilization of agricultural and forestry biomass resource. As an important platform compound, 5-HMF possesses high active furan structure with hydroxymethyl and aldehyde group for production of various bio-chemicals and materials, meanwhile, which suffer from low stability and poor yield during the industrial biorefinery process. Hence, selective production of 5-HMF with high-yield and low-cost has attracted extensive attention from scientific and industrial researchers. This review sorted and described the latest advanced research on solvent and catalyst system, as well as energy field effect for production of 5-HMF with different feedstock in detail, emphatically discussing the solvent effect and its synergistic effect with other aspects. Besides, the future prospects and challenges for production of 5-HMF from carbohydrates were also presented, which provide a profound insight into industrial 5-HMF process with economic and environmental feature.

Preliminary discussion on the ignition mechanism of exploding foil initiators igniting boron potassium nitrate

Exploding foil initiator(EFI)is a kind of advanced device for initiating explosives,but its function is unstable when it comes to directly igniting pyrotechnics.To solve the problem,this research aims to reveal the ignition mechanism of EFIs directly igniting pyrotechnics.An oscilloscope,a photon Doppler velocimetry,and a plasma spectrum measurement system were employed to obtain information of electric characteristics,impact pressure,and plasma temperature.The results of the electric characteristics and the impact pressure were inconsistent with ignition results.The only thing that the ignition success tests had in common was that their plasma all had a relatively long period of high-temperature duration(HTD).It eventually concludes that the ignition mechanism in this research is the microconvection heat transfer rather than the shock initiation,which differs from that of exploding foil initiators detonating explosives.Furthermore,the methods for evaluating the ignition success of semiconductor bridge initiators are not entirely applicable to the tests mentioned in this paper.The HTD is the critical parameter for judging the ignition success,and it is influenced by two factors:the late time discharge and the energy of the electric explosion.The longer time of the late time discharge and the more energy of the electric explosion,the easier it is to expand the HTD,which improves the probability of the ignition success.

Synthesis of Various Types of Silver Nanoparticles Used as Physical Developing Nuclei in Photographic Science

Ag nanoparticles used as physical developing nuclei in photographic science were prepared by reduction method. The as-formed Ag nanoparticle colloid was characterized by UV-Vis absorption spectrum, Atomic Force Microscopy(AFM) and Charge Coupled Device (CCD) technique. It is found that the source of Ag ions, the addition of surfactant and polymer, all have great influence on the size, topography and catalytic activity of Ag nanoparticles.

Linear paired electrolysis of furfural to furoic acid at both anode and cathode in a multiple redox mediated system

Implementing a new energy-saving electrochemical synthesis system with high commercial value is a strategy of the sustainable development for upgrading the bulk chemicals preparation technology in the future.Here,we report a multiple redox-mediated linear paired electrolysis system,combining the hydrogen peroxide mediated cathode process with the I2 mediated anode process,and realize the conversion of furfural to furoic acid in both side of the dividedflow cell simultaneously.By reasonably controlling the cathode potential,the undesired water splitting reaction and furfural reduction side reactions are avoided.Under the galvanostatic electrolysis,the two-mediated electrode processes have good compatibility,which reduce the energy consumption by about 22%while improving the electronic efficiency by about 125%.This system provides a green electrochemical synthesis route with commercial prospects.

Surface-modified Ag@Ru-P25 for photocatalytic CO_(2) conversion with high selectivity over CH_(4) formation at the solid–gas interface

Systematic optimization of the photocatalyst and investigation of the role of each component is important to maximizing catalytic activity and comprehending the photocatalytic conversion of CO_(2) reduction to solar fuels.A surface-modified Ag@Ru-P25 photocatalyst with H_(2)O_(2) treatment was designed in this study to convert CO_(2) and H_(2)O vapor into highly selective CH4.Ru doping followed by Ag nanoparticles(NPs)cocatalyst deposition on P25(TiO_(2))enhances visible light absorption and charge separation,whereas H_(2)O_(2) treatment modifies the surface of the photocatalyst with hydroxyl(–OH)groups and promotes CO_(2) adsorption.High-resonance transmission electron microscopy,X-ray photoelectron spectroscopy,X-ray absorption near-edge structure,and extended X-ray absorption fine structure techniques were used to analyze the surface and chemical composition of the photocatalyst,while thermogravimetric analysis,CO_(2) adsorption isotherm,and temperature programmed desorption study were performed to examine the significance of H_(2)O_(2) treatment in increasing CO_(2) reduction activity.The optimized Ag1.0@Ru1.0-P25 photocatalyst performed excellent CO_(2) reduction activity into CO,CH4,and C2H6 with a~95%selectivity of CH4,where the activity was~135 times higher than that of pristine TiO_(2)(P25).For the first time,this work explored the effect of H_(2)O_(2) treatment on the photocatalyst that dramatically increases CO_(2) reduction activity.

Dilute Aqueous-Aprotic Electrolyte Towards Robust Zn-Ion Hybrid Supercapacitor with High Operation Voltage and Long Lifespan

With the merits of the high energy density of batteries and power density of supercapacitors,the aqueous Zn-ion hybrid supercapacitors emerge as a promising candidate for applications where both rapid energy delivery and moderate energy storage are required.However,the narrow electrochemical window of aqueous electrolytes induces severe side reactions on the Zn metal anode and shortens its lifespan.It also limits the operation voltage and energy density of the Zn-ion hybrid supercapacitors.Using'water in salt'electrolytes can effectively broaden their electrochemical windows,but this is at the expense of high cost,low ionic conductivity,and narrow temperature compatibility,compromising the electrochemical performance of the Zn-ion hybrid supercapacitors.Thus,designing a new electrolyte to balance these factors towards high-performance Zn-ion hybrid supercapacitors is urgent and necessary.We developed a dilute water/acetonitrile electrolyte(0.5 m Zn(CF_(3)SO_(3))_(2)+1 m LiTFSI-H_(2)O/AN)for Zn-ion hybrid supercapacitors,which simultaneously exhibited expanded electrochemical window,decent ionic conductivity,and broad temperature compatibility.In this electrolyte,the hydration shells and hydrogen bonds are significantly modulated by the acetonitrile and TFSI-anions.As a result,a Zn-ion hybrid supercapacitor with such an electrolyte demonstrates a high operating voltage up to 2.2 V and long lifespan beyond 120,000 cycles.

Synthesis and Photochemistry of Diphenylchlorin and Diphenylbacteriochlorin

Diphenylchlorin (DPC) and diphenylbacteriochlorin (DPBC) were synthesized for the first time from reduction of 5,10-diphenylporphyrin (DPP). As photosensitizers they have sizable absorption in the red region of the visible spectrum. The high yield of DPC.-photosensitized generation Of O-1(2), and the EPR studies in homogenerous solution showed that the photodynamic action of DPP-based photosensitizers may proceed via type I and type II machanisms.

Hot electron electrochemistry at silver activated by femtosecond laser pulses

A silver microelectrode with a diameter of 30μm in an aqueous K_(2)SO_(4) electrolyte was irradiated with 55 fs and 213 fs laser pulses.This caused the emission of electrons which transiently charged the electrochemical double layer.The two applied pulse durations were significantly shorter than the electron-phonon relaxation time.The laser pulse durations had negligible impact on the emitted charge,which is incompatible with multiphoton emission.On the other hand,the ob-served dependence of emitted charge on laser fluence and electrode potential supports the thermionic emission mechanism.

Stereochemistry Control in Direct 1α-Hydroxylation of 5,6-trans-Vitamin D_(3) by Solid Support

A solid-phase synthesis of 1α-hydroxylation of 5,6-trans-vitamin D3 8 is described.The solid phase resin acts as a special protecting group, which gives a higher stereoselectivity in oxidation step than classical protecting groups. The stereochemistry control is favored by using high crosslinkage polymer support in a poor solvent. This work may be of benefit to the synthesis of vitamin D system.

Radiation effects on physically cross-linked agarose hydrogels

As a potential matrix of three-dimensional gel dosimeter, agarose hydrogels will be used for measuring radiation doses, hence the importance of studying their radiation resistance and radiolysis mechanism. Physical property and chemical structure of physically cross-linked agarose hydrogel samples irradiated to 0–200 k Gy by60 Co γ-rays were analyzed by universal testing machine, gel permeation chromatography, fourier transform infrared spectrometer, ultraviolet visible spectroscopy, nuclear magnetic resonance, and gas chromatography. The results showed that agarose hydrogels had good radiation stability below 25 k Gy, and the maximum compression strength of sample was ca. 0.1 MPa at 25 k Gy. The irradiated samples degraded obviously and liquefied gradually with increasing doses. Compared with unirradiated sample, carbonyl groups, which generated from the molecular chains of agarose hydrogels, were observed at 25 k Gy and increased gradually with dose. The main gas products evolved from irradiated agarose hydrogels were H2, CO2, CO and CH4. Based on the analysis of radiolytic products, the radiolysis mechanism of agarose hydrogels under γ-radiation was proposed.

Lightweight Dual‑Functional Segregated Nanocomposite Foams for Integrated Infrared Stealth and Absorption‑Dominant Electromagnetic Interference Shielding

Lightweight infrared stealth and absorption-dominant electromagnetic interference(EMI)shielding materials are highly desirable in areas of aerospace,weapons,military and wearable electronics.Herein,lightweight and high-efficiency dual-functional segregated nanocomposite foams with microcellular structures are developed for integrated infrared stealth and absorption-dominant EMI shielding via the efficient and scalable supercritical CO_(2)(SC-CO_(2))foaming combined with hydrogen bonding assembly and compression molding strategy.The obtained lightweight segregated nanocomposite foams exhibit superior infrared stealth performances benefitting from the synergistic effect of highly effective thermal insulation and low infrared emissivity,and outstanding absorption-dominant EMI shielding performances attributed to the synchronous construction of microcellular structures and segregated structures.Particularly,the segregated nanocomposite foams present a large radiation temperature reduction of 70.2℃ at the object temperature of 100℃,and a significantly improved EM wave absorptivity/reflectivity(A/R)ratio of 2.15 at an ultralow Ti_(3)C_(2)T_(x) content of 1.7 vol%.Moreover,the segregated nanocomposite foams exhibit outstanding working reliability and stability upon dynamic compression cycles.The results demonstrate that the lightweight and high-efficiency dual-functional segregated nanocomposite foams have excellent potentials for infrared stealth and absorption-dominant EMI shielding applications in aerospace,weapons,military and wearable electronics.

Ionic Liquid-Enhanced Assembly of Nanomaterials for Highly Stable Flexible Transparent Electrodes

The controlled assembly of nanomaterials has demon-strated significant potential in advancing technological devices.However,achieving highly efficient and low-loss assembly technique for nanomate-rials,enabling the creation of hierarchical structures with distinctive func-tionalities,remains a formidable challenge.Here,we present a method for nanomaterial assembly enhanced by ionic liquids,which enables the fabrication of highly stable,flexible,and transparent electrodes featuring an organized layered structure.The utilization of hydrophobic and non-volatile ionic liquids facilitates the production of stable interfaces with water,effectively preventing the sedimentation of 1D/2D nanomaterials assembled at the interface.Furthermore,the interfacially assembled nanomaterial monolayer exhibits an alternate self-climbing behavior,enabling layer-by-layer transfer and the formation of a well-ordered MXene-wrapped silver nanowire network film.The resulting composite film not only demonstrates exceptional photoelectric performance with a sheet resistance of 9.4Ωsq^(-1) and 93%transmittance,but also showcases remarkable environmental stability and mechanical flexibility.Particularly noteworthy is its application in transparent electromagnetic interference shielding materials and triboelectric nanogenerator devices.This research introduces an innovative approach to manufacture and tailor functional devices based on ordered nanomaterials.

Synthesis,Crystal Structure and Photophysical Properties of Cu(Ⅰ) Complexes Containing 2,5-Bis(pyridyl)-1,3,4-oxadiazole

Four novel Cu（Ⅰ） complexes,[Cu（o-PYO）（PPh3）2]BF4（1）,[Cu（o-PYO）（DPEphos）]BF4（2）,[Cu2 （o-PYO）（PPh3）3（CH3CN）]（BF4）2（3） and [Cu2（o-PYO）（DPEphos）2 ]（BF4）2（4） （o-PYO=2,5bis（pyridyl）-1,3,4-oxadiazole,PPh 3=triphenylphosphine,DPEphos=bis（2-（diphenylphosphanyl）phenyl）ether）,have been synthesized and characterized by 1 H NMR,elemental analysis and single-crystal X-ray diffraction.The central cuprous ions in all complexes are surrounded by N and P atoms to form a distorted tetrahedral geometry,although one of the cuprous ions in complex 3 is coordinated by a PPh3 and an acetonitrile molecule due to the steric hindrance and weak coordination ability from monodentate PPh3 ligand.The UV-vis absorption spectra in CH2Cl2 show the characteristic metal-to-ligand charge transfer （MLCT） absorption bands in the region of 360-480nm.Four Cu（I） complexes exhibit yellow to orange-red phosphorescence with the emission maximum at 572,577,562 and 597nm,respectively in the solid state.