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ABSTRACTBilateral primary breast cancer (BPBC) patients have a worse prognosis. Tools for accurately predicting mortality risk in patients with BPBC are lacking in clinical practice. We aimed to develop a clinically useful prediction model for the death of BPBC patients. A total of 19,245 BPBC patients from the Surveillance, Epidemiology, and End Results (SEER) database between 2004 and 2015 were randomly divided into the training set (n = 13,471) and test set (5,774). Models for predicting the 1-, 3- and 5-year death risk of BPBC patients were developed. Multivariate Cox regression analysis was used to develop the all-cause death prediction model, and competitive risk analysis was used to establish the cancer-specific death prediction model. The performance of the model was assessed by calculating the area under the receiver operating characteristic curve (AUC) with 95% confidence interval (CI), sensitivity, specificity and accuracy. Age, married status, interval time and first and second tumor’s status were associated with both all-cause death and cancer-specific death (all P < 0.05). The AUC of Cox regression models predicted 1-, 3- and 5-year all-cause death was 0.854 (95% CI, 0.835–0.874), 0.838 (95% CI, 0.823–0.852) and 0.799 (95% CI, 0.785–0.812), respectively. The AUC of competitive risk models to predict 1-, 3- and 5-year cancer-specific death was 0.878 (95% CI, 0.859–0.897), 0.866 (95% CI, 0.852–0.879) and 0.854 (95% CI, 0.841–0.867), respectively. Nomograms were developed to predict all-cause death and cancer-specific death in BPBC patients, which may provide tools for clinicians to predict the death risk of BPBC patients.

The electrochemical CO2reduction reaction (CO2RR) using renewable electricity is one of the most promising strategies for reaching the goal of carbon neutrality. Multicarbonous (C2+) products have broad applications, and ethanol is a valuable chemical and fuel. Many Cu-based catalysts have been reported to be efficient for the electrocatalytic CO2RR to C2+products, but they generally offer limited selectivity and current density toward ethanol. Herein, we proposed a silica-mediated hydrogen-bonded organic framework (HOF)-templated approach to preparing ultrahigh-density Cu single-atom catalysts (SACs) on thin-walled N-doped carbon nanotubes (TWN). The content of Cu in the catalysts prepared by this method could be up to 13.35 wt %. It was found that the catalysts showed outstanding performance for the electrochemical CO2RR to ethanol, and the Faradaic efficiency (FE) of ethanol increased with the increase in Cu–N3site density. The FE of ethanol over the catalysts with 13.35 wt % Cu could reach ∼81.9% with a partial current density of 35.6 mA cm–2using an H-type cell, which is the best result for electrochemical CO2RR to ethanol to date. In addition, the catalyst could be stably used for more than 25 h. Experimental and density functional theory (DFT) studies revealed that the adjacent Cu–N3active sites (one Cu atom coordinates with three N) were the active sites for the reaction, and their high density was crucial for the high FE of ethanol because the adjacent Cu–N3sites with a short distance could promote the C–C coupling synergistically.

Ammonia is an effective feedstock for chemicals, fertilizers, and energy storage. The electrocatalytic nitrogen reduction reaction (NRR) is an alternative, efficient, and clean technology for ammonia production, relative to the traditional Haber–Bosch method. Single-metal catalysts are widely studied in the field of NRR. However, very limited conclusions have been made on how to precisely modulate the coordination environment of the single-metal-atom sites to boost catalytic NRR performance. Herein, we report a 5,7-membered carbon ring-involved porous carbon (PC) preparation toward single-atom Ru-embedded PCs. As electrocatalysts, such materials exhibit surprisingly promising catalytic NRR properties with an NH3yield rate of up to 67.8 ± 4.9 μg h–1mgcat–1and a Faradaic efficiency of 19.5 ± 0.6%, exceeding those of most of the reported single-atom NRR catalysts. Extended X-ray absorption fine structure demonstrates that the presence of topological defects increases the Ru–N bond from 1.48 to 1.56 Å, modulating the coordination environment of the single-atom Ru active sites. Density functional theory-calculated results demonstrate that the adsorption of N2onto single-atom Ru surrounded by topological defects extends the N≡N bond to 1.146 Å, weakening the strength of N≡N and making it susceptible to the NRR. All in all, this work provides a new design strategy by involving topological defects and corresponding large polarization around the Ru single atom to boost the catalytic NRR performance. Such a concept can also be applied to many other kinds of catalysts for energy storage and conversion.

The deactivation behavior of titanosilicates is the basis and key to developing high-performance epoxidation catalysts. Herein, we present an intensive study on the deactivation mechanism of titanosilicates in the HPPO process. In addition to the generally accepted physical deactivation of titanosilicates caused by pore blocking, we found that PO also chemisorbs on Ti–OH and adjacent Si–OH (Si–OH (Ti)) groups in titanosilicates under the induction of the Brønsted acid sites, forming bidentate ether species. Combining XPS, 13C solid-state MAS NMR, in situFT-IR, and BET technologies, we confirmed that the bidentate ether species lead to selective chemical deactivation of Ti active sites. The Brønsted acid sites are associated with the formation of bidentate ether species, and their influence decreased in the order Ti–OOH > Si–OH (Ti) > Ti–OH. By introducing an appropriate amount of KH2PO4in the Ti-MWW/H2O2system, both shielding Si–OH (Ti) acid centers by ion exchange and stabilizing the reactive intermediate Ti–OOH by H-bond interactions to suppress Brønsted acid catalysis, a highly efficient and super long-lifetime HPPO process (H2O2conversion >99%, PO selectivity >99.9%, lifetime >3000 h) was achieved, which is significantly more than 75 h reported in the literature. This finding clarifies that the chemical deactivation of titanosilicates caused by PO in the HPPO process is key to determining its long-period stable operation, which will guide the design and development of high-performance titanosilicate catalysts.

The green synthesis of oxime in a titanosilicates/H2O2(TS/H2O2) system is based on the synergistic effect of the in situ synthesis of hydroxylamine (NH2OH) by the oxidation of NH3and the subsequent noncatalytic oximation reaction. However, NH2OH has a highly unstable character, leading to its easy decomposition to release greenhouse gas N2O. Herein a comprehensive investigation was carried out to clarify the mechanism of NH2OH decomposition in the -TS/H2O2system. The reaction pathway network with NH2OH oxidation decomposition was established, and effective ways to inhibit the formation of byproduct N2O were proposed. We proposed that the oxidative decomposition of NH2OH was divided into two main competitive pathways: (a) by H2O2and the free radicals formed by the activation of H2O2with nonframework titanium species to produce N2O and N2and (b) by active intermediate Ti-OOH species formed by the activation of H2O2with framework titanium species to product only inert N2. We found that promoting the formation Ti-OOH species by enhancing the Lewis acidity strength of the titanosilicates could significantly inhibit the pathway of NH2OH oxidation decomposition to N2O. Meanwhile, proper additives to stabilize Ti-OOH species through hydrogen bonding would achieve the same effect. The reaction behavior of H2O2determines the types of products of NH2OH oxidation decomposition. By analyzing the decomposition pathways of NH2OH deeply, we could realize clearly how the products of NH2OH oxidation decomposition were generated, which can be applied to the actual industrial production of the TS/H2O2ammoximation system to achieve a greener chemical process.

Over the past 100 years, technological reforms in energy and chemicals have promoted the economic and social development. Due to the depletion of natural resources and the environment and climate changes, the future development of society will inevitably show the trend of green, low-carbon, and circular economy, offering an opportunity for catalysis technology to continue to play a leading role. This Perspective focuses on the novel processes of efficient thermal catalysis and electrocatalysis, as well as the disruptive innovation of photocatalysis, the key to which lies in creating functional catalysis routes to maximize the retention of functional groups. Furthermore, rational design of catalysis routes and systems for energy molecules, alkenes, and aromatics should lead to 11 revolutionary breakthroughs in catalytic science and technology from resource driven to ecology driven.

Methanol-to-olefins (MTO) technology presently serves as a key to convert coal or natural gas to valuable hydrocarbons, in particular lower olefins. This work focuses on developing a low cost and environmentally benign MTO catalyst from low-silica CHA zeolite. Its moderate acidity and reaction space have been balanced by tuning the residual K+cations in the cavity viacontrolled ammonium ion-exchange. The structure-dependent catalytic performances have been assessed, summarized and discussed by using various characterization techniques. The crystalline structure and crystal morphology of CHA were well preserved during the NH4+exchange. N2physisorption demonstrated that the pore volume and specific surface area increased substantially after K+cations were exchanged as a result of pore opening. NH3temperature-programmed desorption (TPD) and NH3-adsorption IR spectra showed that the amount and strength of acid sites were regulated by the exchange level of K+with NH4+, which was closely related to the K+location according to NO and acetonitrile adsorption IR spectra. The completely exchanged CHA (>98% K+exchange level) deactivated rapidly in MTO at 400 °C, whereas CHA (65% K+exchange level) with moderate acidity showed the best catalytic performance. The moderate acidity in the open cage facilitated the formation of higher methylbenzene intermediates, giving propylene (45%) as the predominant product.

TS-2 microspheres, consisting of intergrown primary nanocrystals, was prepared by controlling the synthetic parameters. The effects of the amount of quaternary ammonium cations as structure-directing agent, H2O/Si ratio, the presence of alcohol and the temperature were carefully investigated on the crystallization process. The high alkalinity was proved to be highly important for the preservation of the microsphere morphology initially formed, due to the unique intergrown stacking style. An alkali treatment with the aqueous solution of structure-directing agent, organic amine and ammonium salt and subsequent Na+ion-exchange were performed to enhance the catalytic activity of TS-2 microsphere in the cyclohexanone ammoximation reactions, with both the conversion and selectivity higher than 99%. In the continuous reaction, the TS-2 microspheres exhibited to be durable catalyst with potential application in industrial ammoximation processes.

A thorough investigation of the nature of the Ti species in the boron-containing Ti-MWW zeolite has been carried out. It was found that the inactive extra-framework TiO6species can cover up the zeolite Lewis-acid property through the weak atomic binding forces between the “Ti(iv)” atom and “O” atom (TiO6species). The nitric acid treatment could remove these TiO6species easily from the as-synthesized Ti-MWW(P), followed by exposure of the zeolite Lewis acidity. Importantly, the formation of new Ti(OSi)3OH species with a strong Lewis-acid strength, is facilitated in the modification process. Thereby, the modified Ti-MWW zeolite has an improved catalytic activity in alkene epoxidation reactions. The removal of framework B(iv) species around the TiO4species is an essential step because it can accelerate the transformation of perfect Ti(OSi)4species to the defective Ti(OSi)3OH species in zeolites. Moreover, the strategy to construct Ti(OSi)3OH species was also applied successfully in boron-containing Ti-MCM-56 zeolites. Considering active species environment can be modulated effectively with the removal of framework tetra-coordinate boron, this strategy could also be beneficial for the preparation of other high-performance titanosilicates.

The effects of various alkali metal promoters on the structure–performance relationship of cobalt–manganese (CoMn) catalysts for the Fischer–Tropsch synthesis (FTS) reaction have been investigated. The electronic promotion effects are correlated with the ionic potential (IP) of the alkali metals, which represents their electronic polarizability. The presence of alkali metal promoters in the CoMn catalysts is beneficial for the formation and stabilization of the Co2C phase. With an increase in the IP of the alkali metal promoters, the active phase was found to transition from Co2C nanospheres to Co2C nanoprisms and then to a mixture of fcc Co0and Co2C nanospheres. In addition, the catalytic performance also changed with the transition in the active phase. For the Co2C nanospheres, high CH4selectivity and low activity were observed. A promising catalytic performance for Fischer–Tropsch to olefins (FTO) with low CH4selectivity and high C2–4=selectivity was achieved for the Co2C nanoprisms. However, low C2–4=selectivity with high activity was found for a mixture of fcc Co0and Co2C nanospheres. It is suggested that the alkali metal promoters in the CoMn catalysts have two different promotion effects that are enhanced with IP: (1) the electronic effect to enhance the CO dissociation probability and benefit the formation of Co2C and (2) the facet stabilization effect to stabilize the Co2C nanoprisms with specific exposed (101) and (020) facets under the FTO reaction conditions.

The mass production of polymeric microdevices using microinjection molding or nanoimprinting necessitates high-performance micro/nano Ni-Co molds. However, the achievement of a synergistic enhancement of the mechanical and lubricating properties of Ni-Co mold through general electrodeposition process remains challenging. This study for the first time proposes a gradient ultrasonic-assisted electrodeposition process to investigate its impact on the microstructural, mechanical, and tribological properties of Ni-Co coatings. Meanwhile, wear simulations are also conducted to elucidate the deterministic relationship of microstructure-process-properties by integrating surface topography and dynamically changing the coefficient of friction (COF) in the wear model. Our findings show that a high Co content (Ni:Co = 5:5) along with gradient-increased ultrasonic power (30–100 W) achieves maximum hardness (approximately 489 HV) and minimum COF (approximately 0.17), indicating a 1.73-fold hardness increase and 72% COF decrease relative to Ni coating. Such improvements result from grain refinement, reduced lattice distortion, and increased hydrophobicity, driven by the synergistic enhancement of high Co content and gradient ultrasonic power. Wear simulations highlight the undeniable impact of surface roughness and dynamic COF, which is vitally important for micro/nanomolds applications. This study realizes the integration of wear model–ultrasonic-process–microstructure–properties of Ni-Co coatings, offering valuable insights into the development of high-performance micro/nano Ni-Co molds based on gradient ultrasonic-assisted electrodeposition process.

Cu-based catalysts are optimal for the electroreduction of CO2to generate hydrocarbon products. However, controlling product distribution remains a challenging topic. The theoretical investigations have revealed that the coordination number (CN) of Cu considerably influences the adsorption energy of *CO intermediates, thereby affecting the reaction pathway. Cu catalysts with different CNs were fabricated by reducing CuO precursors via cyclic voltammetry (Cyc-Cu), potentiostatic electrolysis (Pot-Cu), and pulsed electrolysis (Pul-Cu), respectively. High-CN Cu catalysts predominantly generate C2+products, while low-CN Cu favors CH4production. For instance, over the high-CN Pot-Cu, C2+is the main product, with the Faradaic efficiency (FE) reaching 82.5% and a partial current density (j) of 514.3 mA cm–2. Conversely, the low-CN Pul(3)-Cu favors the production of CH4, achieving the highest FECH4value of 56.7% with a jCH4value of 234.4 mA cm–2. In situ X-ray absorption spectroscopy and Raman spectroscopy studies further confirm the different *CO adsorptions over Cu catalysts with different CN, thereby directing the reaction pathway of the CO2RR.

Highly dispersed metallic silver nanoparticles (AgNPs) are promising heterogeneous catalysts for carboxylative coupling of terminal alkynes with CO2under mild conditions. Yet, their size-controlled synthesis is very challenging because of the high surface energy. Here, we prepared a series of amino-functionalized ordered mesoporous polymers as hosts for anchoring AgNPs. Control experiments and computations showed that electron-rich amines were confined in mesochannels with varying electron density and steric hindrance, creating “localized active zones (LAZ)” to control the growth of AgNPs. The particle size of AgNPs grows along with the increased volume of LAZ around nitrogen species. We also revealed that the catalytic activity of Ag-based catalysts is size-dependent and increases with decreasing particle size. Building on these findings, we report a facile one-pot synthesis strategy for preparing an amine-incorporated ordered mesoporous polymer (NOMP) with a high specific surface area, small LAZ volume, and uniform amine sites with controllable loading. These features result in the formation of ultrasmall and monodispersed Ag nanoparticles. Remarkably, Ag@NOMP gave a quantitative target yield under the conditions of 1 atm CO2pressure and 50 °C, showing superior catalytic activity in CO2carboxylation compared to other mesoporous analogues.

With the booming of non-noble-metal electrocatalysts for efficient oxygen reduction reaction under alkaline conditions, corresponding anodic catalysts for methanol oxidation are urgently needed especially for direct methanol fuel cells with alkaline membranes. Here, we report the facile synthesis of a CuO/Co(OH)2-nanosheet composite as a novel kind of high-performance electrochemical methanol oxidation reaction (MOR) catalyst. The obtained material with an optimized Cu/Co ratio shows much enhanced mass activity and area-specific activity, as well as excellent stability. The electronic structure interaction between Cu and Co, which results in the Co ion binding-energy elevation, is considered to be the origin of high MOR performance. This work promises the great potential of cobalt hydroxide as a novel kind of MOR catalyst and may arouse much interest in exploring more hydroxides as efficient nonprecious-metal electrocatalysts for MOR.

The reaction between titanium alkoxides, [Ti(OR)4], and surface silanol groups is widely used to generate grafted oxo-hydroxo titanium species, whose size is difficult to control. Partial capping of the surface silanols in the presence of the masking pattern of self-repelling tetramethylammonium ions allows us to isolate surface silanol islets, on which isolated titanium ions and dimeric oxo titanium species can be generated up to 2 Ti/Si mol %. Above this loading, and up to ∼8 Ti/Si mol %, higher oligomers (trimers, hexamers, octamers, and so on) are formed, reaching the size obtained at much lower loadings (<1 Ti/Si mol %) on a nonmodified silica surface. The downsizing effect produced on our organically modified surface is monitored from the blue-shift of the charge-transfer band of the Ti(IV) ions, measured by reflectance UV–visible spectroscopy. It is also mirrored by a higher catalytic activity in cyclohexene epoxidation, revealing that it is not only the isolated Ti species that are active but also the oligomers. Regarding the latter, the smaller they are, the more active they are.

The common existence of hypoxia in solid tumors has been heavily researched because it renders tumors more resistant to most standard therapeutic methods, such as radiotherapy (RT), chemotherapy, and photodynamic therapy (PDT), and is associated with a more malignant phenotype and poor survival in patients with tumors. The development of hypoxia modulation methods for advanced therapeutic activity is therefore of great interest but remains a considerable challenge. Since the significant development of nanotechnology and nanomedicine, functionalized nanomaterials can be exploited as adjuvant “drugs” for these oxygen-dependent standard therapies or as hypoxia initiators for advanced new therapies to solid tumors.

X-ray-induced photodynamic therapy (X-PDT) has high depth of penetration and has considerable potential for applications in cancer therapy. Scintillators and heavy metals have been adopted to absorb X-rays and transmit the energy to photosensitizers. However, the low efficiency of converting X-rays to reactive oxygen species (ROS) presents a challenge for the use of X-PDT to cure cancer. In this study, a new method based on LiLuF4:Ce@SiO2@Ag3PO4@Pt(IV) nanoparticles (LAPNP) is presented that could be used to enhance the curative effects of X-PDT. To make full use of the fluorescence produced by nanoscintillators (LiLuF4:Ce), a cisplatin prodrug Pt(IV) was utilized as a sacrificial electron acceptor to increase the yield of hydroxyl radicals (·OH) by increasing the separation of electrons and holes in photosensitizers (Ag3PO4). Additionally, cisplatin is produced upon the acceptance of electrons by Pt(IV) and further enhances the damage caused by ·OH. Via two-step amplification, the potential of LAPNP to enhance the effects of X-PDT has been demonstrated.

Carbon energy has contributed to the creation of human civilization, and it can be considered that the configuration of the carbon energy system is one of the important laws that govern the operation of everything in the universe. The core of the carbon energy system is the opposition and unity of two aspects: oxidation and reduction. The operation of oxidation and reduction is based on the ternary elemental system composed of the three elements of carbon, hydrogen and oxygen. Its operation produces numerous reactions and reaction products. Ancient Chinese philosophy helps us to understand in depth the essence of green carbon science, to explore its scientific basis, and to identify the related platforms for technology development.There is no life without carbon and no life can survive without carbon dioxide. The key factors are balance and recycling. The essence in chemistry for carbon energy system and carbon neutrality is the opposition and unity of two aspects: oxidation and reduction.

Engineering thermochemistry is the science and technology that studies, innovates, and engineers heat-induced or heat-driven thermochemical reactions and can potentially lead to reductions of five-plus billion tons of CO2emissions effectively and economically.

Extreme events have become more frequent in the Northern Hemisphere mid‐latitudes in recent decades, hugely impacting the ecosystem and society. The quasi‐resonance amplification (QRA) of planetary waves is considered one of the dynamic mechanisms leading to extreme weather. However, the specific impact of resonant waves caused by QRA on surface heat extremes is still an open issue. Here we show that the QRA of planetary waves leading to heat extremes is closely related to double jets, accompanied by the enhancement of atmospheric blocking and the weakening of planetary wave escaping into the stratosphere. Our results illustrate the important role of mid‐latitude planetary waves with zonal wavenumber m= 6–8 caused by QRA in the increasingly frequent heat waves in recent years, as it can increase the coverage area and occurrence frequency of heat extremes in mid‐latitudes and show a significant impact on preferred regions, especially in Eurasia. In the summer of 2022, the Northern Hemisphere mid‐latitudes were affected by widespread, intense heat waves that developed more quickly than climatologists had expected, hugely impacting the ecosystem and society. Understanding the extent and causes of extreme heat can help local authorities better prepare for the extreme weather that may occur in the near future. Planetary wave, also known as Rossby wave, manifested as a large‐scale oscillation of the midlatitude atmospheric flow, usually forms a snaking shape over the Earth, leading to persistent surface weather systems and often resulting in extreme events. Existing studies have shown that, planetary wave is one of the important dynamic mechanism behind heat waves. At certain frequencies and wavelengths (short‐wavelength), this circumglobal waves disturbance can be significantly amplified through resonance, resulting in heat extremes. Our work indicates that resonant wave plays an increasingly important role in heat events over Northern Hemisphere mid‐latitudes. The long‐term changes in resonant wave trend deserve continuous attention, because an improved understanding of planetary waves behind extreme events can help assess future wave activity's potential social and economic effects. The influence of resonant waves on heat extremes in the Northern Hemisphere mid‐latitude summer is increasing, especially in EurasiThe occurrence of resonant waves is closely related to double jets, accompanied by the enhancement of atmospheric blockingThe occurrence of resonant waves is accompanied by the weakening of the upward‐propagating planetary waves The influence of resonant waves on heat extremes in the Northern Hemisphere mid‐latitude summer is increasing, especially in Eurasi The occurrence of resonant waves is closely related to double jets, accompanied by the enhancement of atmospheric blocking The occurrence of resonant waves is accompanied by the weakening of the upward‐propagating planetary waves

Two-photon (TP) absorption nanomaterials are highly desirable for deep-tissue clinical diagnostics and orthotopic disease treatment. Here, a well-designed core/shell nanostructure was successfully synthesized with a ZnTPyP self-assembly nanocrystal (ZSN) inner core coated by a homogeneous TiO2layer outside (ZSN–TO). The ZSN is a good photosemiconductor, showing both one-photon (OP) and TP absorption properties for red fluorescence emission and electron–hole pair generation; TiO2with good biocompatibility acts as the electron acceptor, which can transfer photoelectron from ZSN to TiO2for highly effective electron–hole separation, favoring the production of long-life superoxide anion (O2•–) by electrons and oxygen and strong oxidizing hydroxyl radical (•OH) by holes and surrounding H2O. Once pretreated with ZSN–TO, the simultaneous OP-405 nm or TP-800 nm laser stimulation and fluorescent imaging of reactive oxygen species (ROS) showed dynamical and continuous generation of ROS in HeLa cells, with cytotoxicity significantly increasing via the type-1-like photodynamic therapy process. The results demonstrated that the combination of organic ZSN with inorganic TiO2has great applications as an excellent photosensitizer for deep-tissue fluorescent imaging and noninvasive disease treatment via TP photodynamic therapy.

Hierarchically porous ZSM-5 (SiO2/Al2O3≈ 120) containing phosphorus was prepared by a one-step post-synthesis treatment involving controlled desilication and phosphorous modification. The hierarchically porous ZSM-5 featured high thermal and hydrothermal stability. The obtained ZSM-5 zeolites were systematically characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2adsorption-desorption, NH3temperature-programmed desorption, and 27Al and 31P magic-angle spinning nuclear magnetic resonance spectroscopy. The prepared ZSM-5 displayed enhanced activity and prolonged lifetime toward hydrocarbon cracking. The high activity was attributed to improved coke tolerance owing to the presence of the highly stable mesoporous network of ZSM-5 and acid sites introduced upon phosphorus modification. Additionally a mechanism of the stabilization of the zeolites by phosphorus was proposed and discussed.

Using bulk metals as catalysts to get high efficiency in electro-reduction of CO2is ideal but challenging. Here, we report the coupling of bulk metal electrodes and a ternary ionic-liquid-based electrolyte, 1-butyl-3-methylimidazolium tetrafluoroborate/1-dodecyl-3-methylimidazolium tetrafluoroborate/MeCN to realize highly efficient electro-reduction of CO2to CO. Over various bulk metal electrodes, the ternary electrolyte not only increases the current density but also suppresses the hydrogen evolution reaction to obtain a high Faradaic efficiency (FE) toward CO. FECOcould maintain ∼100% over a wide potential range, and metal electrodes showed very high stability in the ternary electrolyte. It is demonstrated that the aggregation behavior of the ternary electrolyte and the arrangement of two kinds of IL cations with different chain lengths in the electrochemical double layer not only increase the wettability to electrode and CO2adsorption but also extend the diffusion channel of H+, rendering the high current density and FECO.

The epoxidation of methallyl chloride (MAC) to 2-methyl epichlorohydrin (MECH) with H2O2using TS-1 microsphere catalysts (TS-1-MS) in a continuous slurry reactor was investigated. The reaction parameters, which governed the effective conversion of hydrogen peroxide, selectivity to MECH epoxide and catalyst deactivation, were studied in detail by simulating the operating conditions of its industrial process. Under the most beneficial conditions, the process was successfully run for 257 h at a high MECH selectivity (>95%) as well as a high effective conversion of hydrogen peroxide (>97%). The microsphere morphology and particle size were highly maintained for the deactivated TS-1-MS catalyst, which was regenerated readily by a combination of hydrogen peroxide washing and calcination. This research verified that it was possible to develop a green, safe and efficient route for producing MECH by direct epoxidation of MAC with hydrogen peroxide in a slurry reactor. Employing TS-1 microsphere aggregates as a catalyst exhibits the advantage of easy solid–liquid separation.

The statistical characteristics of inertia‐gravity waves (IGWs) in the troposphere (2–14 km) and lower stratosphere (18–28 km) are analyzed using daily radiosonde observations over six stations in the Western Pacific from 2013 to 2018. Stokes parameter method is used to extract the characteristic parameters of gravity waves (GWs), which are divided into upward and downward propagating waves, and compared with the results of hodograph analysis. In the stratosphere, due to the filtering effect of the background wind field, the IGWs generated in the troposphere mainly propagate eastward with lower frequency range. The tropospheric IGWs have obvious seasonal variation in spectral amplitude and energy, with the maximum in winter and the minimum in monsoon from 2013 to 2018. The stratospheric IGWs are enhanced during phase transition of the quasi‐biennial oscillation, when the enhanced easterly wind appears in the lowest stratosphere, accompanied by enhanced wave energy in the troposphere. During the quasi‐biennial oscillation disruption in late 2015 and early 2016, the tropospheric wave source excites more intense IGWs propagating upward. After reaching the stratosphere, IGWs with slower phase speed are absorbed by the mean flow, dissipating momentum to the lower stratosphere and generating additional enhanced westward forcing, which may have contributed to the development of the easterly wind within the westerly quasi‐biannual oscillation phase. Stokes parameter method shows an obvious discrepancy from hodograph analysis when calculating the vertical wave numberOver the western Pacific, a large amount of eastward‐propagating inertia‐gravity waves (IGWs) still exist in the stratosphere due to prevailing easterly windDuring 15/16D, stratospheric IGWs with lower phase velocity dissipate momentum and produce westward forcing to the mean flow Stokes parameter method shows an obvious discrepancy from hodograph analysis when calculating the vertical wave number Over the western Pacific, a large amount of eastward‐propagating inertia‐gravity waves (IGWs) still exist in the stratosphere due to prevailing easterly wind During 15/16D, stratospheric IGWs with lower phase velocity dissipate momentum and produce westward forcing to the mean flow

Ammonia is a zero‑carbon, and high-energy storage feedstock. The Haber-Bosch process of industrial ammonia synthesis is the predominant method of ammonia synthesis worldwide. However, the shortages of high energy consumption and high pollution of Haber-Bosch process affect the global environment. The electrochemical nitrogen reduction reaction (ENRR), which is environmentally friendly and can be carried out at room temperature and pressure, may be an alternative method. In recent years, researchers have used different materials such as noble metal, non-noble metal, single-atom, and defect materials to obtain higher NH3yield rates and better Faradaic efficiency. With the continued efforts of the researchers, it is believed that the industrialization of ENRR will be achieved in the future.

Small-crystal TS-1 was synthesized via a seed-induced approach using ammonia as the alkali source and tetrapropylammonium bromide as an auxiliary structure-directing agent. The TS-1 samples were characterized using X-ray diffraction, N2adsorption-desorption, Fourier-transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscopy, scanning electron microscopy, and ultraviolet-visible spectroscopy. The use of the colloidal seed reduced the crystal size, and an appropriate amount of silicalite-1 seed assisted Ti incorporation into the TS-1 framework. This method reduces the cost of TS-1 synthesis because a significantly smaller amount of tetrapropylammonium hydroxide is used. The catalytic performance of the synthesized small-crystal TS-1 samples in cyclohexanone ammoximation was better than that of bulk TS-1 as a result of improved diffusion and a larger number of active tetrahedral Ti centers.

•γ-Irradiation induced bystander effects between hepatoma cells and hepatocyte cells.•SirT1 played a protective role in regulating this bystander effect.•SirT1 contributed to the protective effects viaelimination the accumulation of ROS.•The activity of c-Myc is critical for maintaining the protective role of SirT1.

•α-Irradiation induced reciprocal effects between macrophage and hepatocyte cells.•cAMP played a protective role in regulating the reverse bystander effect.•cAMP communication contributed to the reciprocal effects via membrane signaling.•p53 was required for cAMP-regulated bystander effect in the recipient cells.

High LET particle irradiation has several potential advantages over γ-rays such as p53-independent response. The purpose of this work is to disclose the effect of p53 on the bystander effect induced by different LET irradiations and underlying mechanism. Lymphocyte cells of TK6 (wild type p53) and HMy2.CIR (mutated p53) were exposed to either low or high LET irradiation, then their mitochondrial dysfunction and ROS generation were detected. The micronuclei (MN) induction in HL-7702 hepatocytes co-cultured with irradiated lymphocytes was also measured. It was found that the mitochondrial dysfunction, p66Shcactivation, and intracellular ROS were enhanced in TK6 but not in HMy2.CIR cells after γ-ray irradiation, but all of them were increased in both cell lines after carbon and iron irradiation. Consistently, the bystander effect of MN formation in HL-7702 cells was only triggered by γ-irradiated TK6 cells but not by γ-irradiated HMy2.CIR cells. But this bystander effect was induced by both lymphocyte cell lines after heavy ion irradiation. PFT-μ, an inhibitor of p53, only partly inhibited ROS generation and bystander effect induced by 30 keV/μm carbon-irradiated TK6 cells but failed to suppress the bystander effect induced by the TK6 cells irradiated with either 70 keV/μm carbon or 180 keV/μm iron. The mitochondrial inhibitors of rotenone and oligomycin eliminated heavy ion induced ROS generation in TK6 and HMy2.CIR cells and hence diminished the bystander effect on HL-7702 cells. These results clearly demonstrate that the bystander effect is p53-dependent for low LET irradiation, but it is p53-independent for high LET irradiation which may be because of p53-independent ROS generation due to mitochondrial dysfunction.

► α-Particle induced MN had a biphasic dose–response followed by a bystander model. ► MN dose–response of α- and γ-combination IR was similar to that of α-particle. ► α-Particles followed by γ-rays yielded a synergistic effect on MN induction. ► Low dose γ-rays triggered antagonistic and adaptive responses against α-particle.

Aluminosilicates with different Si/Al ratios and showing a structure similar to MCM-56 were postsynthesized from fully crystallized lamellar MWW-type precursors under controlled acid treatment. The effects of pretreatment conditions on the construction of MCM-56 analogue structure were investigated, and the physicochemical properties of the resulting materials were characterized by means of various techniques. When the precursors were treated in HNO3solution with a concentration ≤2 M at temperatures lower than 353 K, a structure analogous to MCM-56 was formed favorably even after further calcination, whereas the treatment at higher temperatures or with 5 M HNO3resulted in conventional three-dimensional MWW topology. The formation of MCM-56-like structure was closely related to the reorientation of the interlayer H-bond moieties as a result of a partial removal of occluded structure directing agent. Compared with MCM-22, the MCM-56 analogues possessed a structural disorder along the layer stacking direction but had a larger external surface, which mitigated effectively the steric restrictions imposed by the intracrystal micropores to bulky molecules. The MCM-56 zeolites, maintaining the basic structure units of the MWW zeolite, turned out to serve as promising solid acid catalysts for processing larger molecules.

Cyclohexanols are widely used chemicals, which are mainly produced by oxidation of fossil feedstocks. Selective hydrodeoxygenation of lignin derivatives has great potential for producing these chemicals but is challenging to obtain high yields. Here, we report that CeO2-supported Ru single-atom catalysts (SACs) enabled the hydrogenation of the benzene ring and catalyzed etheric C–O(R) bond cleavage without changing the C–O(H) bond, which could afford 99.9% yields of cyclohexanols. As far as we know, this is the first to report that SACs catalyze hydrogenation of the aromatic ring. The reaction mechanism was studied by control experiments and density functional theory calculations. In the catalysts, the Ru–O–Ce sites were formed and one Ru atom was coordinated with about four O atoms. These catalytic sites could realize both the hydrogenation and deoxygenation reactions efficiently, and thus desired cyclohexanols were generated. This work pioneers the single-atom catalysis in aromatic transformation and provides a novel route for synthesis of cyclohexanols.

Cleaning up their act: Sulfur compounds in fuels can be selectively converted into SO2by mixing the fuel with a small amount of air at around 300 °C at ambient pressure in a continuous‐flow reactor packed with catalysts such as Pt/CeO2, Cu/CeO2, and CuO/ZnO/Al2O3. The aerobic oxidative desulfurization process opens up a cost‐effective new technology for cleaning fuels.

The postsynthesis treatment of Ti−MWW having the three-dimensional (3D) MWW structure with aqueous amine solutions has been carried out with the purpose to improve its hydrophobicity and catalytic activity in the liquid-phase oxidations. The treatment with piperidine (PI) or hexamethyleneimine (HMI) converted the 3D MWW structure into the corresponding lamellar precursor, which returned reversibly to the 3D MWW structure by further calcination. The treatments with other amines, however, caused a structural collapse or crystalline transfer to other phases. In the case of PI treatment, the structural conversion from 3D MWW to the MWW lamellar precursor occurred readily at 443 K at a PI/SiO2molar ratio of >0.1 within 1 day for the Ti−MWW samples with various Si/Ti ratios. The structural interchange did not alter the amount as well as the coordination states of the Ti active sites, but removed the internal silanols by ca. 40%, leading to a defectless Ti−MWW catalyst with a more rigid and hydrophobic framework. This kind of structural rearrangement improved the catalytic activity by up to 20% in the ammoximation of ketones and also in the epoxidation of a wide range of alkenes with various molecular dimensions.

A novel microfibrous composite bed reactor was developed and was demonstrated for high efficiency hydrogen production by the decomposition of ammonia at moderate temperatures in portable fuel cell power system applications. By using a high-speed and low-cost papermaking technology combined with a subsequent sintering process, sinter-locked three-dimensional microfibrous networks consisting of ∼3 vol% 8 µm (dia.) nickel microfibers were utilized to entrap ∼35 vol% 100–200 µm dia. porous Al2O3 support particulates. A CeO2 promoter and active Ni component were then dispersed onto the pore surface of the entrapped Al2O3 support particulates by a stepwise incipient wetness impregnation method. The microfibrous structure took advantage of a large void volume, entirely open structure, high heat/mass transfer, high permeability, good thermal stability, and unique form factors. Addition of ceria significantly promoted the low-temperature activity of Ni/Al2O3 catalyst particulates incorporated into the micorfibrous structure. The use of fine particles of catalyst significantly attenuated the intraparticle mass transport limitations. As a result, the present novel microfibrous composite bed reactor provided excellent activity and structure stability in ammonia decomposition, as well as low pressure drop and high efficiency reactor design. At a 90% conversion of a 145 sccm ammonia feed rate, the microfibrous entrapped Ni/CeO2–Al2O3 catalyst composite bed could provide a 4-fold reduction of catalytic bed volume and a 5-fold reduction of catalytic bed weight (or 9-fold reduction of catalyst dosage), while leading to a reduction of reaction temperature of 100 °C, compared to a packed bed with 2 mm dia. Ni/CeO2–Al2O3 catalyst pellets. This composite bed was capable of producing roughly 22 W of hydrogen power, with an ammonia conversion of 99% at 600 °C in a bed volume of 0.5 cm3 throughout a 100 h continuous test. These initial and promising results established that the microfibrous nickel-based catalyst composites were effective for high efficiency production of hydrogen by ammonia decomposition, while achieving a significant reduction of overall catalytic bed weight and volume. We anticipate our assay to be a new point for small-scale hydrogen production, where the microfibrous catalytic reactors considered in isolation can satisfy several of the most fundamental criteria needed for useful operation.

A much greener synthesis method is discovered for the synthesis of 3,4-epoxytetrahydrofuran (ETHF), an important synthetic intermediate for stereo-controllable synthesis of complex organic compounds. 3,4-ETHF is synthesized with a conversion >95% and a selectivity >99% through a heterogeneous epoxidation of 2,5-dihydrofuran (DHF) with hydrogen peroxide in the liquid phase over a novel titanosilicate catalyst, Ti-MWW.

A novel sol–gel process is used to synthesize mesoporous silica–alumina catalysts with controlled pore size distribution without using templates or pore-regulating agents. The nitrogen sorption analysis shows that the synthesized materials have high specific surface area in the range 587–692 m$^2$/g and similar mesoporous distribution within 2–11 nm. Ultrasound is applied to prepare precursor silica–alumina sol with narrow particle diameter distribution. By calculation, it is found that ultrasonic treatment is able to provide 22.94 kJ/mol energy, which is just in accordance with the weak bond's bonding energy. Based on the calculation result, it is proposed that the role of ultrasonic treatment followed by acid peptization is to provide energy to break down the weak bonds. After gelation, the regular and close packing of similar-sized sol particles is capable of formation of controlled-sized interstices which are the precursors of mesopores. Solid-state $^27$Al MAS NMR and TEM are used to characterize the samples' structure and particle morphology. They show that most of the aluminum is located in the tetrahedral position in the present materials. According to TEM results, it is shown that the synthesized materials have spherical particles with size of about 15 nm.

The characteristics of gravity wave activity in tropical areas have been extensively explored, but at present, less attention has been paid to the activity of inertial gravity waves (IGWs) in the Western Pacific based on in‐situ detection data. Based on the radiosonde data over Guam (13.3°N, 144.4°E) for 6 years (2013–2018), the hodograph method and spectrum analysis are used to analyze the statistical characteristics of IGWs in the troposphere (2–14 km) and stratosphere (18–28 km). The gravity wave (GW) energy in the troposphere has clear annual cycle, with the strongest activity in winter and the weakest in monsoon. In the stratosphere, the periodic variation of wave energy is interrupted due to the 2016 quasi‐biennial oscillation (QBO) disruption reflected in the zonal wind field. In the troposphere, the quantity of up‐propagating GWs is close to that of the down‐propagating GWs, while in the stratosphere, they are almost up‐propagating GWs. The horizontal propagation direction of GWs is mainly northeast and southwest in both the troposphere and the stratosphere, since the weak background wind field does not produce significant filtering effect. The spectral amplitude based on the normalized temperature perturbation has clear uniform annual variations in the troposphere and stratosphere, which are the largest in winter and the smallest in monsoon. Due to the “saturation” process in the up‐propagating process of GWs, the spectral slope is more negative in the stratosphere. Detailed parameters of inertial gravity waves revealed in the radiosonde data at Guam Station are discussedGravity wave activity in the stratosphere has obvious 2016 quasi‐biennial oscillation (QBO) disruption, which is consistent with the zonal wind fieldThe result is compared with Gadanki at the same latitude, showing some regional differences Detailed parameters of inertial gravity waves revealed in the radiosonde data at Guam Station are discussed Gravity wave activity in the stratosphere has obvious 2016 quasi‐biennial oscillation (QBO) disruption, which is consistent with the zonal wind field The result is compared with Gadanki at the same latitude, showing some regional differences

Heteroatoms determine the functionalities of zeolites. Facile and effective incorporation of heteroatoms into the framework of zeolites remains an important and challenging goal. We report a strategy for efficient and simple synthesis of crystalline metallosilicates with spatially homogeneous distribution of heteroatoms and free of extra-framework metal species via the crystal dissolution and crystallization process (CDC process). This method succeeds in the synthesis of a wide range of crystalline metallosilicates with the MFI topology including TS-1, Al-MFI, Fe-MFI, Sn-MFI, and Nb-MFI zeolites as well as with other topologies such as TS-2, Ti–Al–beta zeolite, and so forth. The gripper-like silicon species, which is condensed matter of silicon species in Q2and Q3states (detected by 29Si NMR), was identified for the first time to be the key to the effective incorporation and spatially homogeneous distribution of heteroatoms during the CDC process. Such silicon species could bond heteroatoms efficiently to form stable and isolated Si–O–M structural units in the synthetic sol, and such structural units remain unchanged under the “protection” of silicon species during the whole liquid-phase transformation and crystallization process. In addition, the gripper-like silicon species could be obtained not only by dissolving the crystal under high basicity but also by dissolving/polymerizing amorphous silicon species under the same conditions. The CDC process for synthesizing crystalline metallosilicates with spatially homogeneous distribution of heteroatoms in the framework by controlling the state of silicon species opens up a new perspective for the synthesis of heteroatomic zeolites.

Furfuryl ethers have been considered to be a promising fuel additive. One step reduction etherification of furfural over supported Pd catalysts provides a facile way for the preparation of furfuryl ether. However, the preparation of a reusable Pd catalyst for reductive etherification remains to be a great challenge. In this study, a series of SiO2supported Pd catalysts with particle size ranging from 2.2 to 28 nm were prepared. Their textural properties and catalytic performance in furfural reductive etherification have been systematically studied. The results herein shed light on the particle size effect on the competition between hydrogenation/hydrogenolysis of C=O in furfural over Pd surface. We found out that Pd nanoparticles larger than 3 nm are preferred for one step reductive etherification. Based on this finding, we prepared a Pd/ZSM-5 bifunctional catalyst comprising Pd nanoparticles larger than 3 nm and decreased acidity in presence of amino organosilane, which served as a bifunctional catalyst succeeding in one-pot synthesis of ether via reductive-etherification and direct-etherification. This strategy showed significant advantage in efficiently converting furfuryl acohol, a major side-product, into ether, while suppressing the undesired side-reactions.

The CuO/CeO2composites with strong metal-support interaction were synthesised, which can efficiently electroreduct CO2to C2H4. The Faradaic efficiency (FE) of C2H4could reach 50.5% with a current density of 18 mA cm−2. The strong metal-support interaction could not only enhance the adsorption and activation of CO2, but also can stablize the CuO.

Fluorine species were successfully implanted into a MWW-type titanosilicate viapost-treatment, which generates the SiO3/2F units in the zeolite framework. The incorporated fluorine species significantly improved the catalytic performance in the epoxidation of alkenes as a result of enhancing the Lewis acid strength and the hydrophobicity of the zeolite.

Based on the round‐trip intelligent sounding system, the structure function and spectrum analysis method were carried out to analyze the scale interactions between the small‐scale gravity wave and turbulence in the middle stratosphere. The result showed that the generation of turbulence was closely related to the Kelvin‐Helmholtz (KH) billows. An upscale energy cascade occurred on the spatial scale of KH billows, while a downscale energy cascade occurred on a larger spatial scale (gravity wave scale), which resulted in the breaking of the gravity wave and generation of turbulence. From the multilevel signal measurement, the obvious interactions between turbulence and gravity can be found. The two‐dimensional turbulence that the inverse energy cascade in 2‐D exists simultaneously with a direct enstrophy cascade to the small scales was found, which is considered to be the first‐hand observation result of relevant height. The two‐dimensional turbulence is found with bidirectional energy transmissionKH billows are considered to be an important factor in the excitation of turbulenceConvergence and divergence on different scales cause instability within the wave