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The pursuit of two-dimensional (2D) borides, MBenes, has proven to be challenging, not the least because of the lack of a suitable precursor prone to the deintercalation. Here, we studied room-temperature topochemical deintercalation of lithium from the layered polymorphs of the LiNiB compound with a considerable amount of Li stored in between [NiB] layers (33 at. % Li). Deintercalation of Li leads to novel metastable borides (Li similar to 0.5NiB) with unique crystal structures. Partial removal of Li is accomplished by exposing the parent phases to air, water, or dilute HCl under ambient conditions. Scanning transmission electron microscopy and solid-state Li-7 and B-1(1) NMR spectroscopy, combined with X-ray pair distribution function (PDF) analysis and DFT calculations, were utilized to elucidate the novel structures of (Li similar to 0.5NiB) and the mechanism of Li-deintercalation. We have shown that the deintercalation of Li proceeds via a "zip-lock" mechanism, leading to the condensation of single [NiB] layers into double or triple layers bound via covalent bonds, resulting in structural fragments with Li[NiB](2) and Li[NiB](3) compositions. The crystal structure of Li similar to 0.5NiB is best described as an intergrowth of the ordered single [NiB], double [NiB](2), or triple [NiB](3) layers alternating with single Li layers; this explains its structural complexity. The formation of double or triple [NiB] layers induces a change in the magnetic behavior from temperature-independent paramagnets in the parent LiNiB compounds to the spin-glassiness in the deintercalated Li similar to 0.5NiB counterparts. LiNiB compounds showcase the potential to access a plethora of unique materials, including 2D MBenes (NiB).

The European Space Agency Climate Change Initiative Land Cover data (ESA CCI-LC, from 1992 to 2015) is introduced to the National Center for Atmospheric Research Community Earth System Model version 1.2.1 (NCAR CESM1.2.1). In comparison with the original land surface data in the Community Land Model version 4 (ORG), the new data features notable land use and land cover change (LULCC) with increased forests over northeastern Asia and Alaska by decreasing shrublands and grasslands. Overestimated bare land cover over the Tibetan Plateau (TP) and the Rocky Mountains in the ORG are corrected with the replacements by grasslands and shrublands respectively in the new data. The model simulation results show that with the introduction of the ESA CCI-LC, the simulated surface albedo, surface net radiation flux, sensible and latent heat fluxes are relatively improved over the regions where significant LULCC exists, such as northeastern Asia, Alaska, the TP, and Australia. Surface air temperature, precipitation, and atmospheric circulation are improved in boreal winter but degraded in summer. The winter warming over northeastern Asia results from increased longwave downwelling flux and adiabatic heating while the notable winter cooling over Alaska is attributed to strong cold advection followed by reduced longwave downwelling flux. LULCC alters precipitation by influencing water vapor content. In winter, LULCC affects atmospheric circulation via modulating baroclinicity while in summer, it influences land-sea thermal contrast, thus affecting the intensity of East Asian summer monsoon. LULCC also alters the simulated dust burden.

Optical control of exotic properties in strongly correlated electron materials is very attractive owing to their potential applications in optical and electronic devices. Herein, we demonstrate a vertical heterojunction made of a correlated electron oxide thin film VO2 and a conductive 0.05 wt% Nb-doped TiO2 single crystal, whose metal-insulator transition (MIT) across the nanoscale heterointerface can be efficiently modulated by visible light irradiation. The magnitude of the MIT decreases from ~350 in the dark state to ~7 in the illuminated state, obeying a power law with respect to the light power density. The junction resistance is switched in a reversible and synchronous manner by turning light on and off. The optical tunability of it is also exponentially proportional to the light power density, and a 320-fold on/off ratio is achieved with an irradiance of 65.6 mW cm−2 below the MIT temperature. While the VO2 thin film is metallic above the MIT temperature, the optical tunability is remarkably weakened, with a one-fold change remaining under light illumination. These results are co-attributed to a net reduction (~15 meV) in the apparent barrier height and the photo-carrier-injection-induced metallization of the VO2 heterointerface through a photovoltaic effect, which is induced by deep defect level transition upon the visible light irradiance at low temperature. Additionally, the optical tunability is minimal, resulting from the quite weak modulation of the already metallic band structure in the Schottky-type junction above the MIT temperature. This work enables a remotely optical scheme to manipulate the MIT, implying potential uncooled photodetection and photoswitch applications.

Encapsulating metal nanoparticles (NPs) in metal–organic frameworks (MOFs) to control catalytic selectivity has recently attracted great attention; however, an understanding of the NP–MOF interface...

Tibetan Plateau (TP) summer precipitation, whose first leading mode presents a dipole oscillation between the northeastern and southeastern TP, plays important roles in the water cycle and atmospheric circulation. Using a weakly coupled data assimilation (WCDA) system to constrain the atmospheric component in a coupled model with a global atmospheric reanalysis product, this study demonstrates significant improvements in predicting the interannual variation of summer precipitation over the eastern TP, capturing the strong reversal mode between the northeastern and southeastern TP. These improvements are mainly attributed to the strong air–sea coupling over the North Atlantic (NA) and its remote impacts on the TP precipitation. This coupling allows observation-constrained atmosphere to significantly influence initial conditions (ICs) of sea surface temperature (SST) in the NA area and then obviously affect predictions of both NA SST and summer North Atlantic Oscillation (SNAO), which affects the downstream TP atmospheric circulation through the wave train of Eliassen-Palm (EP) stationary wave flux. This study highlights the importance of NA air–sea coupling in the interannual predictability of TP precipitation and suggests a new source of interannual predictability of TP precipitation.

Stability against reshaping of metallic fcc nanocrystals synthesized with tailored far-from-equilibrium shapes is key to maintaining optimal properties for applications such as catalysis. Yet Arrhenius analysis of experimental reshaping kinetics, and appropriate theory and simulation, is lacking. Thus, we use TEM to monitor the reshaping of Pd nanocubes of ∼25 nm side length between 410 °C (over ∼4.5 h) and 440 °C (over ∼0.25 h), extracting a high effective energy barrier of

The rapid decrease in Arctic sea ice cover and thickness not only has a linkage with extreme weather in the mid-latitudes but also brings more opportunities for Arctic shipping routes and polar resource exploration, both of which motivate us to further understand causes of sea-ice variations and to obtain more accurate estimates of sea-ice cover in the future. Here, a novel data-driven method, the causal effect networks algorithm, is applied to identify the direct precursors of September sea-ice extent covering the Northern Sea Route and Transpolar Sea Route at different lead times so that statistical models can be constructed for sea-ice prediction. The whole study area was also divided into two parts: the northern region covered by multiyear ice and the southern region covered by seasonal ice. The forecast models of September sea-ice extent in the whole study area (TSIE) and southern region (SSIE) at lead times of 1–4 months can explain over 65% and 79% of the variances, respectively, but the forecast skill of sea-ice extent in the northern region (NSIE) is limited at a lead time of 1 month. At lead times of 1–4 months, local sea-ice concentration and sea-ice thickness have a larger influence on September TSIE and SSIE than other teleconnection factors. When the lead time is more than 4 months, the surface meridional wind anomaly from northern Europe in the preceding autumn or early winter is dominant for September TSIE variations but is comparable to thermodynamic factors for NSIE and SSIE. We suggest that this study provides a complementary approach for predicting regional sea ice and is helpful in evaluating and improving climate models.

Multifunctional metal-organic frameworks (MOFs) that possess permanent porosity are promising catalysts in organic transformation. Herein, we report the construction of a hierarchical MOF functionalized with basic aliphatic amine groups and polyvinylpyrrolidone-capped platinum nanoparticles (Pt NPs). The postsynthetic covalent modification of organic ligands increases basic site density in the MOF and simultaneously introduces mesopores to create a hierarchically porous structure. The multifunctional MOF is capable of catalyzing a sequential Knoevenagel condensation-hydrogenation-intramolecular cyclization reaction. The unique selective reduction of the nitro group to intermediate hydroxylamine by Pt NPs supported on MOF followed by intramolecular cyclization with a cyano group affords an excellent yield (up to 92%) to the uncommon quinoline N-oxides over quinolines. The hierarchical MOF and polyvinylpyrrolidone capping agent on Pt NPs synergistically facilitate the enrichment of substrates and thus lead to high activity in the reduction-intramolecular cyclization reaction. The bioactivity assay indicates that the synthesized quinoline N-oxides evidently inhibit the proliferation of lung cancer cells. Our findings demonstrate the feasibility of MOF-catalyzed direct synthesis of bioactive molecules from readily available compounds under mild conditions.

Hyperpolarized propane produced by heterogeneous hydrogenation of cyclopropane with parahydrogen has been proposed as a safe inhalant for sensitivity-enhanced in vivo magnetic resonance imaging. Th...

Hexagonal boron nitride nanosheets (h-BNNS), the isoelectronic analog to graphene, have received interest over the past decade due to their high thermal oxidative resistance, high bandgap, catalyti...

International audience; In this study, a series of Fe-doped g-C3N4 (Fe–C3N4) samples was synthesized and characterized via X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflection spectroscopy (UV-vis DRS), and photoluminescence (PL) spectroscopy. The photocatalytic activity of the synthesized Fe–C3N4 was investigated toward methylene blue (MB) degradation with hydrogen peroxide (H2O2) assistance. The results showed that the Fe–C3N4 heterogeneous photo-Fenton-like system showed excellent catalytic performance when the pH value was varied from 3.0 to 9.0. Evaluating the effects of various inorganic anions in the Fe–C3N4 heterogeneous photo-Fenton-like system, HCO3− showed a dual effect on MB degradation, and Cl− and NO3− showed an inhibitory effect on MB degradation. Evaluating the effects of inorganic cations, Al3+, Mg2+, and Ca2+ strongly inhibited MB degradation. Recycling experiments demonstrated that Fe–C3N4 possesses good reusability and stability. Quenching experiments were carried out, and it was found that hydroxyl radicals (·OH) were the primary active species in the system. Besides, nine intermediates were identified via LC/MS, and a possible MB degradation pathway in the system was proposed. This study could promote the application of this Fe–C3N4 heterogeneous photo-Fenton-like system in realistic dye wastewater.

Heteronuclear correlation (HETCOR) spectroscopy is one of the key tools in the arsenal of the solid-state NMR spectroscopist to probe chemical and spatial proximities between two different nuclei and enhance spectral resolution. Dipolar heteronuclear multiple-quantum coherence (D-HMQC) is a powerful technique that can be potentially utilized to obtain 1H detected 2D HETCOR solid-state NMR spectra of any NMR active nucleus. A long-standing problem in 1H detected D-HMQC solid-state NMR experiments is the presence of t1-noise which reduces sensitivity and impedes spectral interpretation. In this contribution, we describe novel pulse sequences, termed t1-noise eliminated (TONE) D-HMQC, that minimize t1-noise and can provide higher sensitivity and resolution than conventional D-HMQC. Monte-Carlo and numerical simulations confirm that t1-noise in conventional D-HMQC primarily occurs because random MAS frequency fluctuations cause variations in the NMR signal amplitude from scan to scan, leading to imperfect cancellation of uncorrelated signals by phase cycling. The TONE D-HMQC sequence uses 1H π-pulses to refocus the evolution of 1H CSA across each SR421 recoupling block, improving the stability of the pulse sequence to random MAS frequency fluctuations. The 1H refocusing pulses also restore the orthogonality of in-phase and anti-phase magnetization for all crystallite orientations at the end of each recoupling block, enabling the use of 90° flip-back or LG spin-lock trim pulses to reduce the intensity of uncorrelated signals. We demonstrate the application of these methods to acquire 1H detected 2D 1H{35Cl} and 1H{13C} HETCOR spectra of histidine·HCl·H2O with reduced t1-noise. To show generality, we also apply these methods to obtain 2D 1H{17O} spectra of 20%-17O fmoc-alanine and for the first time at natural abundance, 2D 1H{25Mg} HETCOR spectra of magnesium hydroxide. The TONE D-HMQC sequences are also used to probe 1H-25Mg and 1H-27Al proximities in Mg-Al layered double hydroxides and confirm the even mixing of Mg and Al in these materials.

International audience; Owing to their diverse functional groups, antibiotics can easily form complexes with heavy metals; the complexation alters the migration and transformation behavior of both antibiotics and heavy metals. In this study, we investigated the co-adsorption mechanism of sulfamethazine (SMT) and cadmium (Cd2+) heavy metal ions and created an ideal water model containing two major contaminants: sulfamethazine and heavy metal cadmium ions. Combined with the experimental analysis of the interaction mechanism, the results indicate the heterogeneous multilayer adsorption of SMT on the surface of activated carbon (AC). The bridging role of cadmium ions promotes the adsorption of SMT through the formation of SMT-Cd2+-AC ternary complexes on the surface of activated carbon. Characterization experiments provided further insight into the adsorption behavior of Cd2+ and SMT on activated carbon, revealing a strong correlation between the Cd2+-SMT complexation and the SMT adsorption capacity. These results indicate that the effects of the coexistence of antibiotics and heavy metal ions should be fully taken into account when investigating the environmental behavior of antibiotics and heavy metal ions.

Nanoconfinement could dramatically change molecular transport and reaction kinetics in heterogeneous catalysis. Here we specifically design a core-shell nanocatalyst with aligned linear nanopores for single-molecule studies of the nanoconfinement effects. The quantitative single-molecule measurements reveal unusual lower adsorption strength and higher catalytic activity on the confined metal reaction centres within the nanoporous structure. More surprisingly, the nanoconfinement effects on enhanced catalytic activity are larger for catalysts with longer and narrower nanopores. Experimental evidences, including molecular orientation, activation energy, and intermediate reactive species, have been gathered to provide a molecular level explanation on how the nanoconfinement effects enhance the catalyst activity, which is essential for the rational design of highly-efficient catalysts., Nanoconfinement effects on changing molecular transport and reaction kinetics in heterogeneous catalysis have been widely recognized. Here, the authors design a core-shell nanocatalyst with aligned linear nanopores to uncover nanoconfinement effects on catalytic activity and adsorption strength by single molecule imaging.

Knowledge of the quantitative importance of moisture transport pathways of the Sanjiangyuan region (known as the “water tower” of China) can provide insights into the regional atmospheric branch of the hydrological cycle over the Sanjiangyuan region. A combined method with a clustering algorithm [Hierarchical Density-Based Spatial Clustering of Applications with Noise (HDBSCAN)] and a Lagrangian moisture source diagnostic is developed to identify the major moisture transport pathways and quantify their importance to three types of consecutive precipitation events—extreme precipitation (EP) events, moderate precipitation (MP) events, and extreme aridity (EA) events—for the Sanjiangyuan region during the rainy season (June–September 1960–2017). The results indicate that moisture paths from the northwest covering northwest China and central Asia (the N.W. pathway) and moisture paths from southern and southeastern China (the S.S. pathway) are stable moisture transport pathways during EP and MP events [importance (precipitation contribution in percentage): N.W. pathway, 18.4% (EP), 32.2% (MP); S.S. pathway, 25.9% (EP), 28.5% (MP)]. Affected by the western edge of a significant anticyclone anomaly centered around 35°N, 115°E, the moisture paths via the Bay of Bengal (the B.B. pathway) can reach the target region and become a supplementary moisture contributor (14.9%) to EP events. Moisture paths via the Arabian Sea and Indian peninsula (the A.I. pathway) are also active but the contributions are limited [4.9% (EP) and 5.6% (MP)]. For EA events, the fast-moving trajectories from farther western Asia (the F.W. pathway) play a dominant role and all major moisture pathways (F.W., N.W., and S.S. pathways) carry limited moisture to the target region.

Research and development in bimetallic nanoparticles have gained great interest over their monometallic counterparts because of their distinct and unique properties in a wide range of applications such as catalysis, energy storage, and bio/plasmonic imaging. Identification and characterization of these bimetallic surfaces for application in heterogeneous catalysis remain a challenge and heavily rely on advanced characterization techniques such as aberration-corrected electron microscopy and synchrotron X-ray absorption studies. In this article, we have reported a strategy to prepare sub-2 nm bimetallic Pt-Sn nanoclusters confined in the pores of a Zr-based metal-organic framework (MOF). The Pt-Sn nanoclusters encapsulated in the Zr-MOF pores show enhanced chemoselectivity from 51 to 93% in an industrially relevant reaction, furfural hydrogenation to furfuryl alcohol. The presence of bimetallic Pt-Sn surfaces was investigated by a surface-sensitive characterization technique utilizing diffuse reflectance infrared Fourier transform spectroscopy of adsorbed CO to probe the bimetallic surface of the encapsulated ultrafine Pt-Sn nanocluster. Complementary techniques such as aberration-corrected high-angle annular dark-field scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy were also used to characterize the Pt-Sn nanoclusters.

Self-assembly of supported 2D or 3D nanocrystals (NCs) by vacuum deposition and of 3D NCs by solution-phase synthesis (with possible subsequent transfer to a support) produces intrinsically nonequilibrium systems. Individual NCs can have far-from-equilibrium shapes and composition profiles. The free energy of NC ensembles is lowered by coarsening which can involve Ostwald ripening or Smoluchowski ripening (NC diffusion and coalescence). Preservation of individual NC structure and inhibition of coarsening are key, e.g., for avoiding catalyst degradation. This review focuses on postsynthesis evolution of metallic NCs. Atomistic-level modeling typically utilizes stochastic lattice-gas models to access appropriate time and length scales. However, predictive modeling requires incorporation of realistic rates for relaxation mechanisms, e.g., periphery diffusion and intermixing, in numerous local environments (rather than the use of generic prescriptions). Alternative coarse-grained modeling must also incorporate appropriate mechanisms and kinetics. At the level of individual NCs, we present analyses of reshaping, including sintering and pinch-off, and of compositional evolution in a vacuum environment. We also discuss modeling of coarsening including diffusion and decay of individual NCs and unconventional coarsening processes. We describe high-level modeling integrated with scanning tunneling microscopy (STM) studies for supported 2D epitaxial nanoclusters and developments in modeling for 3D NCs motivated by in situ transmission electron microscopy (TEM) studies.

Summary Intermetallic nanoparticles (iNPs) have yielded enormous successes in catalytic applications by the formation of ordered phases. However, atomic-level understanding of the alloying mechanism, which plays a pivotal role in controlling intermetallic phases and tailoring their catalytic properties, is still elusive. In this study, we discovered a consecutive formation of ordered Pt3Sn and PtSn phases during the growth of Pt-Sn iNP inside a well-defined nano-reactor at elevated temperature by using in situ scanning transmission electron microscopy. We found that the surface-mediated diffusion of Sn controls overall dynamics of the reaction, while the unique coherent interfacial structure is determinative for the PtSn transformation. We then further controlled the phase selection of Pt-Sn iNPs and demonstrated their distinguishable catalytic behaviors. Our findings not only provide detailed experimental evidence on the alloying mechanism in intermetallic nanoscale systems but also pave the way for mechanistic control of synthesis and catalytic properties of iNPs.

The sensitivity of solid-state NMR experiments that utilize 1H zero-quantum heteronuclear dipolar recoupling, such as D-HMQC, is compromised by poor homonuclear decoupling. This leads to a rapid decay of recoupled magnetization and an inefficient recoupling of long-range dipolar interactions, especially for nuclides with low gyromagnetic ratios. We investigated the use, in symmetry-based 1H heteronuclear recoupling sequences, of a basic R element that was principally designed for efficient homonuclear decoupling. By shortening the time required to suppress the effects of homonuclear dipolar interactions to the duration of a single inversion pulse, spin diffusion was effectively quenched and long-lived recoupled coherence lifetimes could be obtained. We show, both theoretically and experimentally, that these modified sequences can yield considerable sensitivity improvements over the current state-of-the-art methods and applied them to the indirect detection of 89Y in a metal-organic framework.

Mesoporous silica encapsulated Pt (Pt@mSiO(2)) and PtSn (PtSn@mSiO(2)) nanoparticles (NPs) are representatives of a novel class of heterogeneous catalysts with uniform particle size, enhanced catalytic properties, and superior thermal stability. In the ship-in-a-bottle synthesis, PtSn@mSiO(2) intermetallic NPs are derived from Pt@mSiO(2) seeds where the mSiO(2) shell is formed by polymerization of tetraethyl orthosilicate around a tetradecyltrimethylammonium bromide template, a surfactant used to template MCM-41. Incorporation of Sn into the Pt@mSiO(2) seeds is accommodated by chemical etching of the mSiO(2) shell. The effect of this etching on the atomic-scale structure of the mSiO(2) has not been previously examined, nor has the extent of the structural similarity to MCM-41. Here, the quaternary Q(2), Q(3) and Q(4) sites corresponding to formulas Si(O(1/2))(2)(OH)(2), Si(O(1/2))(3)(OH)(1) and Si(O(1/2))(4), in MCM-41 and the mesoporous silica of Pt@mSiO(2) and PtSn@mSiO(2) NPs were identified and quantified by conventional and dynamic nuclear polarization enhanced Si-29 Magic Angle Spinning Nuclear Magnetic Resonance (DNP MAS NMR). The connectivity of the -Si-O-Si-network was revealed by DNP enhanced two-dimensional (29)Si-(29)Si correlation spectroscopy.

Selective oxidation of olefins to α,β-unsaturated ketones under mild reaction conditions has attracted considerable interest, since α,β-unsaturated ketones can serve as synthetic precursors for various downstream chemical products. The major inherent challenges with this chemical oxidation are chemo- and regio-selectivity as well as environmental concerns, i.e. catalyst recycle, safety and cost. Using atmospheric oxygen as an environmentally friendly oxidant, we found that a metal–organic framework (MOF) constructed with Mn and a tetrazolate ligand (CPF-5) showed good activity and selectivity for the allylic oxidation of olefins to α,β-unsaturated ketones. Under the optimized conditions, we could achieve 98% conversion of cyclohexene and 87% selectivity toward cyclohexanone. The combination of a substoichiometric amount of TBHP (tert-butylhydroperoxide) and oxygen not only provides a cost effective oxidation system but significantly enhances the selectivity to α,β-unsaturated ketones, outperforming most reported oxidation methods. This catalytic system is heterogeneous in nature, and CPF-5 could be reused at least five times without a significant decrease in its catalytic activity and selectivity.

Highly dispersed Co sites in highly porous N-doped carbon (Co-NC) were synthesized by high-temperature pyrolysis of Zn/Co bimetallic zeolitic imidazolate framework-8 (CoxZn100−x-ZIF). Wide characterization indicated that the pyrolysis atmosphere and temperature play crucial roles in the metal dispersion and pore structure of the resulting materials. A hydrogen treatment at elevated temperatures is found to favour the Zn volatilization and restrict the pore shrinkage of the ZIF precursor, thus yielding efficient catalysts with highly dispersed Co, a high surface area (1090 m2 g−1) and pore volume (0.89 cm3 g−1). When used as a catalyst for aerobic oxidation of ethylbenzene (EB), Co1Zn99-ZIF-800-H2 contributes to 98.9% EB conversion and 93.1% ketone selectivity under mild conditions (60 °C, 1 atm O2), which is 41.3 times more active in comparison to the ZIF-67-derived Co catalyst. Co-NC is stable and could be reused four times without obvious deactivation. This catalyst displays good chemoselectivity to the corresponding ketones when using a broad scope of hydrocarbon compounds.

Tandem catalysis, often inspired by biological systems, offers many advantages in the synthesis of highly functionalized small molecules. NH2-grafted porous C3N4 nanosheet with rich N species and surface area of 138 m2/g was fabricated via a NH3-exfoliation method. After supporting Pd nanoparticles, the resulting bifunctional catalyst (Pd/C3N4–NH2) could catalyze a one-step tandem condensation-hydrogenation reaction between ketones and nitriles to form α-alkylated nitriles at room temperature. Under 2 MPa H2 for 8 h, Pd/C3N4–NH2 could afford 99.7% cyclohexanone conversion and 99.8% selectivity without other side reactions, which is much higher than that of bulk C3N4-supported Pd. Compared with commonly used two-step processes, this one-step tandem reaction could largely shorten reaction time and allow condensation-hydrogenation to take place at room temperature. We also found that the hydrogenation step accelerated the condensation step, which increased the overall efficiency of the tandem transformation....

A versatile and straightforward room-temperature strategy is demonstrated to synthesize boundary defect-rich ultrathin transition metal hydroxide nanosheet networks by in situ etching of a cobalt metal–organic framework (Co-MOF, ZIF-L-Co). The resultant defect-rich ultrathin Co(OH)2 (D-U-Co(OH)2) nanoarray is one of the most active monometal-based oxygen evolution catalysts to date. Its activity is 3–4 times higher than that of the commercial RuO2 and superior to that of the reported exfoliated bimetallic catalysts. Co-MOF can also be grown on various substrates, and the chemical composition of the defect-rich 2D materials is tunable by changing the metal ions in the etchants. Owing to these merits of the unique synthesis route, our work provides an opportunity for synthesizing advanced nanomaterials that are difficult to get access to by conventional methods.

Heterogeneous single-metal-site catalyst or single-atom catalyst research has grown rapidly due to the accessibility of modern characterization techniques that can provide invaluable information at the atomic-scale. Herein, we study the structural evolution of isolated single Pt sites incorporated in a metal–organic framework containing bipyridine functional groups using in situ diffuse reflectance infrared Fourier transform spectroscopy with CO as the probe molecule. The structure and electronic properties of the isolated Pt sites are further corroborated by x-ray photoelectron spectroscopy and aberration-corrected scanning transmission electron microscopy. We find the prerequisite of high temperature He treatment for Pt activation and CO insertion and inquire into the structural transformation of Pt site process by dynamic nuclear polarization-enhanced solid-state nuclear magnetic resonance spectroscopy.

The van der Waals (vdW) chromium trihalides (CrX3) exhibit field-tunable, two-dimensional magnetic orders that vary with the halogen species and the number of layers. Their magnetic ground states with proximity in energies are sensitive to the degree of ligand-metal (p-d) hybridization and relevant modulations in the Cr d-orbital interactions. We use soft X-ray absorption (XAS) and resonant inelastic X-ray scattering (RIXS) spectroscopy at Cr L-edge along with the atomic multiplet simulations to determine the key energy scales such as the crystal field 10 Dq and interorbital Coulomb interactions under different ligand metal charge transfer (LMCT) in CrX3 (X= Cl, Br, and I). Through this systematic study, we show that our approach compared to the literature has yielded a set of more reliably determined parameters for establishing a base Hamiltonian for CrX3.

Knowledge on the occurrence and distributions of organic compounds, especially PAHs, POPs and ECs, in karstic river basins is limited. This study aims to determine the depositional history and sources of PAHs, PCBs, OCPs, antibiotics, EDCs and phenolic compounds and the ecological risk they have in the Panyang River Basin, an area with a typical karstic landscape and a high-longevity population. Sediment core analysis was adopted, correlation and principal component analyses were conducted to analyze pollution sources, and lead isotope technology was implemented for dating analysis. The sediment core covered 108 years. PCBs were detected with concentrations ranging from 3.80 to 16.18 μg/kg in the core with two concentration peaks in 1950 and 2005 that were related to anthropogenic effects. Eight of the 20 targeted phenolic compounds were detected, with concentrations ranging from 0.42 to 1.10 mg/kg. All PAHs were detected in the cores, with concentrations from 12.91 to 37.80 μg/kg. They were mainly related to natural diagenetic processes and domestic and agricultural sources. The concentrations of different OCP compounds ranged from undetected to 213.43 μg/kg and were mainly related to agricultural activities and long-range transportation. These key findings can assist environmental planning and management in this river basin.

Nuclear spin hyperpolarization derived from parahydrogen can enable nuclear magnetic resonance spectroscopy and imaging with sensitivity enhancements exceeding four orders of magnitude. The NMR signal enhancement is proportional to 4 x p - 1 , where x p is the parahydrogen mole fraction. For convenience, many labs elect to carry out the ortho–para conversion at 77 K where 50% enrichment is obtained. In theory, enrichment to 100% yields an automatic three-fold increase in the NMR signal enhancement. Herein, construction and testing of a simple and inexpensive continuous-flow converter for high para-enrichment is described. During operation, the converter is immersed in liquid helium contained in a transport dewar of the type commonly found in NMR labs for filling superconducting magnets. A maximum enrichment of 97.3 ± 1.9% at 30 K was observed at 4.5 bar and 300 mL/min flow rate. The theoretically predicted 2.9-fold increase in the signal enhancement factor was confirmed in the heterogeneous hydrogenation of propene to propane over a PdIn/SBA-15 catalyst. The relatively low-cost to construct and operate this system could make high parahydrogen enrichment, and the associated increase in the parahydrogen-derived NMR signals, more widely accessible.

Nanoconfinement imposes physical constraints and chemical effects on reactivity in nanoporous catalyst systems. In the present study, we lay the groundwork for quantitative single-molecule measurements of the effects of chemical environment on heterogeneous catalysis in nanoconfinement. Choosing hydrophobicity as an exemplary chemical environmental factor, we compared a range of essential parameters for an oxidation reaction on platinum nanoparticles (NPs) confined in hydrophilic and hydrophobic nanopores. Single-molecule experimental measurements at the single particle level showed higher catalytic activity, stronger adsorption strength, and higher activation energy in hydrophobic nanopores than those in hydrophilic nanopores. Interestingly, different dissociation kinetic behaviors of the product molecules in the two types of nanopores were deduced from the single-molecule imaging data.

Knowledge Representation Learning (KRL), which is also known as Knowledge Embedding, is a very useful method to represent complex relations in knowledge graphs. The low-dimensional representation learned by KRL models makes a contribution to many tasks like recommender system and question answering. Recently, many KRL models are trained using square loss or cross entropy loss based on Closed World Assumption (CWA). Although CWA is an easy way for training, it violates the link prediction task which exploits KRL. To overcome the drawback, in this paper, we introduce a new method, Type-based Prior Possibility Assumption (TPPA). TPPA calculates type based prior possibilities for missing triplets instead of zeros in the training process of KRL to weaken the bad influence of CWA. We compare TPPA with the baseline method CWA in ConvE and TuckER, two common frameworks for knowledge representation learning. The experiment results on FB15k-237 dataset show that TPPA based training method outperforms CWA based training method in link prediction task.

Heptazine-based conjugated polymeric carbon nitrides (PCNs) are promising metal-free photocatalysts, yet their synthesis is challenging due to the electron-deficiency and insolubility of heptazine units. Indeed, heptazine-containing polymers have only been prepared through nucleophilic substitution with amines by using toxic cyameluric chloride as the starting material. Herein, we report the novel and environmentally friendly method for preparing heptazine-based mesoporous PCNs with hydrazone links formed through a simple Schiff base condensation of melem-NH2 and aldehydes. Unlike cyameluric chloride, melem-NH2 is non-toxic, stable, and can be readily obtained from melem and hydrazine in solution. We demonstrate that the hydrazone linkages and the heptazine units synergistically enhance the photocatalytic activity of PCNs in visible-light-driven aerobic oxidation of benzyl alcohol to benzaldehyde. In particular, the polymer constructed from melem-NH2 and p-phthalaldehyde shows 17 times more activity than graphitic carbon nitride (g-C3 N4 ).

Controlling the surface composition of shaped bimetallic nanoparticles could offer precise tunability of geometric and electronic surface structure for new nanocatalysts. To achieve this goal, a platform for studying the intermixing process in a shaped nanoparticle was designed, using multilayered Pd-Ni-Pt core-shell nanocubes as precursors. Under mild conditions, the intermixing between Ni and Pt could be tuned by changing layer thickness and number, triggering intermixing while preserving nanoparticle shape. Intermixing of the two metals is monitored using transmission electron microscopy. The surface structure evolution is characterized using electrochemical methanol oxidation. DFT calculations suggest that the low-temperature mixing is enhanced by shorter diffusion lengths and strain introduced by the layered structure. The platform and insights presented are an advance toward the realization of shape-controlled multimetallic nanoparticles tailored to each potential application.

International audience; The application of carboxylic acid and natural iron oxide in heterogeneous AOP systems for the treatment of organic pollutants in water has attracted extensive attention. In this work, ethylenediamine-N,N′-disuccinic acid (EDDS) was complexed with ferrihydrite to improve the photo-Fenton system for bisphenol A (BPA) degradation, and the mechanism of the system was investigated. TEM, XRD and BET were used to investigate the morphology, structure and specific surface area of ferrihydrite. The characterization results revealed that ferrihydrite was amorphous and agglomerated, its main composition was 2–2lfh, and its specific surface area was 297.5 m2 g−1. BPA degradation experiments, carried out at different influence factors including the initial concentration of EDDS, amount of ferrihydrite and initial concentration of H2O2, showed a maximum degradation rate of BPA of 85.1% under the optimal conditions (at 1.0 mmol L−1 EDDS, 0.6 g L−1 ferrihydrite and 0.5 mmol L−1 H2O2). Finally, in order to analyze the mechanism of BPA degradation, 2-propanol and chloroform were used as free radical scavengers to capture hydroxyl radicals (˙OH) and superoxide anion radicals (˙O2−) respectively. The results indicated that ˙OH radicals and 1O2 play an important role under aerobic conditions, while ˙O2− radicals produced by the reaction of H2O2 and holes are non-negligible under anaerobic conditions. Moreover, the iron dissolution also plays a promoting role in BPA degradation. Overall, Fe(III) and Fe(II) redox processes are accelerated due to the Fe(III)–EDDS complex reaction under irradiation and in the presence of ˙O2− radicals and trace iron dissolution, which increases the number of reactive species in the system. The BPA degradation is facilitated by various reactive species including ˙OH radicals, 1O2 and ˙O2− radicals.

Due to the large radius of K-ion, K-ion batteries (KIBs) involving K-ion insertion and extraction processes generally exhibit an insufficient cycle life and poor rate performance. In this work, sulphur-doped reduced graphene oxide (S-RGO) sponges, which are used as free-standing anodes for KIBs, are obtained via simple freeze-drying of graphene oxide solution and subsequent thermal treatment in sulphur steam. After sulphur doping, our S-RGO sponges deliver preeminent electrochemical performance. Such free-standing electrodes exhibit high K-ion storage capacity of 361 mAh g −1 at 50 mA g −1 over 50 cycles. Furthermore, even at a high current density of 1 A g −1 , they also display a highly stabile K-ion storage with a capacity of 229 mAh g −1 over 500 cycles, which outperforms all previously reported carbon-based materials for KIBs. Such preeminent performance is attributed to the S-RGO sponges’ unique conductive structure and the sulphur doping, which effectively enhance the insertion of large K ions. We also utilize ex-situ XPS to illuminate the reaction process of our sample during potassiation/depotassiation and highlight the role of sulphur doping in improving K-ion storage performance.

Ordered mesoporous N-doped carbon (OMNC) encapsulating Co nanoparticles (NPs) have been prepared under direct polymerization between [Co(NH2CH2CH2NH2)2]Cl2 and carbon tetrachloride through a hard template method. The catalysts (Co@OMNC) are pyrolyzed at various temperatures and characterized by elemental analysis, Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). In the quinoline transfer hydrogenation with formic acid (FA) as the hydrogen source under a base-free condition, the encapsulated Co NPs are physically isolated from the acidic reaction solution, which prevents them from poisoning or leaching. The rich mesopores and N dopants afford enhanced adsorption of quinoline. Co@OMNC-700 (pyrolyzed at 700 °C) gives the best activity (98.8% conversion) as well as >99% 1,2,3,4-tetrahydroquinoline (THQ) selectivity at 140 °C for 4 h, exhibiting significantly improved performance compared to using H2 as the hydrogenation ...

Covalent organic frameworks (COFs) as drug-delivery carriers have been mostly evaluated in vitro due to the lack of COFs nanocarriers that are suitable for in vivo studies. Here we develop a series of water-dispersible polymer-COF nanocomposites through the assembly of polyethylene-glycol-modified monofunctional curcumin derivatives (PEG-CCM) and amine-functionalized COFs (APTES-COF-1) for in vitro and in vivo drug delivery. The real-time fluorescence response shows efficient tracking of the COF-based materials upon cellular uptake and anticancer drug (doxorubicin (DOX)) release. Notably, in vitro and in vivo studies demonstrate that PEG-CCM@APTES-COF-1 is a smart carrier for drug delivery with superior stability, intrinsic biodegradability, high DOX loading capacity, strong and stable fluorescence, prolonged circulation time and improved drug accumulation in tumors. More intriguingly, PEG350-CCM@APTES-COF-1 presents an effective targeting strategy for brain research. We envisage that PEG-CCM@APTES-COF-1 nanocomposites represent a great promise toward the development of a multifunctional platform for cancer-targeted in vivo drug delivery., Despite their potential application as drug-delivery carriers, covalent organic frameworks (COF) have been only evaluated in vitro. Here the authors show by real time tracking in vivo the cell uptake of anticancer-drug loaded and water dispersible COFs.

Summary This article reports the discovery of surface-mediated parahydrogen-induced alignment of the proton magnetic moments in liquid water as well as methanol and ethanol. In this SWAMP (surface waters are magnetized by parahydrogen) effect, the spin polarization of the solvent protons is enhanced simply by the bubbling of parahydrogen through a suspension of Pt 3 Sn intermetallic nanoparticles (iNPs) encapsulated within a protectective mesoporous silica shell (Pt 3 Sn@mSiO 2 ). The conversion of singlet spin order into magnetization is mediated by symmetry-breaking interactions on the surface of the iNPs. Stimulated emission NMR signals of the exchangeable hydroxy protons are observed. Non-exchangeable methyl or methylene protons are also hyperpolarized, an observation that provides insight into the molecular mechanism. SWAMP has a myriad of potential applications, ranging from low-field MRI to drug discovery.

This study examines the formation of circulation patterns favorable to wintertime extreme precipitation events over South China between 1979 and 2013. During these extreme precipitation events, a barotropic wave train having seven centers of action was observed to extend from the Arabian Sea to the west coast of the North American continent with a maximum amplitude at 300 hPa. A center of action located over South China, comprised of cyclonic anomalies, favored powerful updrafts and large-scale moisture convergence over South China. About 77% of wintertime extreme precipitation events in South China were preceded by European blocking events. The formation mechanism for the 141 precipitation events with pre-existing European blocking highs is presented. Rossby wave energy propagation associated with the positive phase of circumglobal teleconnection enabled the European blocking event with a lead time of $$\sim$$ 10 days to generate cyclonic anomalies over South China. Moreover, significant warm anomalies were present over South China before the onset of these blocking-related extreme precipitation events. Increases in atmospheric moisture holding capacity associated with these warm anomalies enabled a buildup of precipitable water via moisture fluxes into South China through the western and southern boundaries. Onset of the extreme precipitation events was then triggered by the intrusion of cold temperature anomalies from the north, which lifted warm moist air upward from the surface and lowered the moisture holding capacity, producing large amounts of precipitation.

We report a facile strategy to synthesize intermetallic nanoparticle (iNP) electrocatalysts via one-pot pyrolysis of a zeolitic imidazolate framework, ZIF-8, encapsulating precious metal nanoparticles (NPs). ZIF-8 serves not only as precursor for N-doped carbon (NC), but also as Zn source for the formation of intermetallic or alloy NPs with the encapsulated metals. The resulting sub-4 nm PtZn iNPs embedded in NC exhibit high sintering resistance up to 1,000 °C. Importantly, the present methodology allows fine-tuning of both composition (e.g., PdZn and RhZn iNPs, as well as AuZn and RuZn alloy NPs) and size (2.4, 3.7, and 5.4 nm PtZn) of the as-formed bimetallic NPs. To the best of our knowledge, this is the first report of a metal-organic framework (MOF) with multiple functionalities, such as secondary metal source, carbon precursor, and size-regulating reagent, which promote the formation of iNPs. This work opens a new avenue for the synthesis of highly uniform and stable iNPs.

Noble metal-based bimetallic nanoparticles (NPs) synthesized using colloidal methods always contain organic capping agents. These NPs show high selectivities in many chemoselective hydrogenation reactions benefitting from both capping agents and secondary metals. However, it is challenging to separately identify the role of the secondary metal and the capping agents in the bimetallic NPs because the complete removal of the capping agents can often cause their aggregation or structural/compositional changes. Herein we report the synthesis of Pt5Fex (x = 1, 2 and 4) bimetallic NPs capped by an inorganic mesoporous silica (mSiO2) shell, which could prevent NP aggregation during high-temperature treatment to remove capping agents. Using these Pt5Fex@mSiO2 NPs with a clean surface, we could demonstrate the role played independently by the bimetallic composition in the selective hydrogenation of cinnamaldehyde and furfural. Understanding the functions of the secondary metal and the surface modifying ligands on the selectivity enhancement of bimetallic NPs is necessary for the design of high-performance chemoselective catalysts.

Understanding the fundamental catalytic principles when the catalytic centre is confined in nanoscale space that is dimensionally comparable to the reactant molecule is crucial for designing high-performance catalysts. Theoretical studies with simplified model systems and ensemble experimental measurements have shown that chemical reactions in nanoconfined environments are largely different from those in bulk solution. Here, we design a well-defined platform with catalytic centres confined in the end of nanopores with controlled lengths to study the in situ dynamic behaviour of catalytic processes under nanoconfinement at the single-molecule and single-particle level. Variable single molecular mass transport behaviour reveals the heterogeneity of the confined environment in the nanopores. With the capability of decoupling mass transport factors from reaction kinetics in the well-defined platform, we quantitatively uncovered a confinement-induced enhancement in the activity of platinum nanoparticles inside the nanopores. The combination of the unique model catalyst and the single-molecule super-localization imaging technique paves the way to understanding nanoconfinement effects in catalysis. Nanoconfinement effects are crucial in any process that involves porous materials. Here, the authors present a nanoporous catalyst platform that enables these effects to be studied in situ at the single-molecule and single-particle level with turnover resolution.

The establishment of structure–property relationships in heterogeneous catalysis is of prime importance but remains a formidable challenge. Metal–organic frameworks (MOFs) featuring excellent chemical tunability are emerging as an auspicious platform for the atomic-level control of heterogeneous catalysis. Herein, we encapsulate palladium nanoparticles (Pd NPs) in a series of isoreticular mixed-linker MOFs, and the obtained MOF-Pd NPs catalysts were used to unveil the electronic and steric effects of linker substitution on the activity of these catalysts in the Suzuki–Miyaura cross-coupling reactions. Significantly, m-6,6′-Me2bpy-MOF-Pd exhibits a remarkable enhancement in the activity compared to non-functionalized m-bpy-MOF-Pd and m-4,4′-Me2bpy-MOF-Pd. This study unambiguously demonstrates that the stereoelectronic properties of linker units are crucial to the catalytic activity of nanoparticles encapsulated in MOFs. More interestingly, the trend of activity change is consistent with our previous work on catalytic sites generated in situ from Pd(II) coordinated in MOFs bearing the same functional groups, which suggests that both MOF-Pd NPs and MOF-Pd(II) catalysts generate similar active centers during Suzuki–Miyaura coupling reactions. This work paves a new avenue to the fabrication of advanced and tunable MOF-based catalysts through rational linker engineering. We encapsulate palladium nanoparticles in a series of isoreticular mixed-linker MOFs, and the obtained Pd-doped MOFs catalysts were used to unveil the electronic and steric effects of linker substitution on the activity of these catalysts in the context of Suzuki–Miyaura cross-coupling reactions. Impressively, m-6,6′-Me2bpy-MOF-Pd exhibits a remarkable enhancement in the activity compared to non-functionalized m-bpy-MOF-Pd and m-4,4′-Me2bpy-MOF-Pd, thus implementing atomic-level controls of heterogeneous catalysis.

A metal catalyst supported on an inert substrate could consist of both metal nanoparticles and singly dispersed metal atoms. Whether these singly dispersed metal atoms are active and how different their catalytic mechanism could be in contrast to a supported metal catalyst are fundamentally important for understanding catalysis on a supported metal or oxide. By taking reduction of NO with CO on singly dispersed Rh atoms anchored on an inert support SiO2 as a probe system (Rh1/SiO2), here we demonstrated how singly dispersed metal atoms on an inert support could perform a complex multi-step catalytic cycle through a mechanism distinctly different from that for a supported metal nanoparticle with continuously packed metal sites. These singly dispersed Rh1 atoms anchored on SiO2 are active in reducing nitric oxide with carbon monoxide through two reaction pathways that are different from those of Rh nanoparticles. In situ IR studies show that a CO molecule and a NO molecule coadsorb on a singly dispersed Rh ...

Bridging the structure-properties relationship of bimetallic catalysts is essential for the rational design of heterogeneous catalysts. Different from random alloys, intermetallic compounds (IMCs) present atomically-ordered structures, which is advantageous for catalytic mechanism studies. We used Pt-based intermetallic nanoparticles (iNPs), individually encapsulated in mesoporous silica shells, as catalysts for the hydrogenation of nitroarenes to functionalized anilines. With the capping-free nature and ordered atomic structure, PtSn iNPs show >99% selectivity to hydrogenate the nitro group of 3-nitrostyrene albeit with a lower activity, in contrast to Pt3Sn iNPs and Pt NPs. The geometric structure of PtSn iNPs in eliminating Pt threefold sites hampers the adsorption/dissociation of molecular H2 and leads to a non-Horiuti-Polanyi hydrogenation pathway, while Pt3Sn and Pt surfaces are saturated by atomic H. Calculations using density functional theory (DFT) suggest a preferential adsorption of the nitro group on the intermetallic PtSn surface contributing to its high selectivity.

Nitrones are key intermediates in organic synthesis and the pharmaceutical industry. The heterogeneous synthesis of nitrones with multifunctional catalysts is extremely attractive but rarely explored. Herein, we report ultrasmall platinum nanoclusters (PtNCs) encapsulated in amine-functionalized Zr metal-organic framework (MOF), UiO-66-NH2 (Pt@UiO-66-NH2 ) as a multifunctional catalyst in the one-pot tandem synthesis of nitrones. By virtue of the cooperative interplay among the selective hydrogenation activity provided by the ultrasmall PtNCs and Lewis acidity/basicity/nanoconfinement endowed by UiO-66-NH2 , Pt@UiO-66-NH2 exhibits remarkable activity and selectivity, in comparison to Pt/carbon, Pt@UiO-66, and Pd@UiO-66-NH2 . Pt@UiO-66-NH2 also outperforms Pt nanoparticles supported on the external surface of the same MOF (Pt/UiO-66-NH2 ). To our knowledge, this work demonstrates the first examples of one-pot synthesis of nitrones using recyclable multifunctional heterogeneous catalysts.

We demonstrate that dynamic nuclear polarization (DNP)-enhanced 1H-X heteronuclear correlation (HETCOR) measurements of hydrogen-rich surface species are better accomplished by using proton-free solvents. This approach notably prevents HETCOR spectra from being obfuscated by the solvent-derived signals otherwise present in DNP measurements. Additionally, in the hydrogen-rich materials studied here, which included functionalized mesoporous silica nanoparticles and metal organic frameworks, the use of proton-free solvents afforded higher sensitivity gains than the commonly used solvents containing protons. We also explored the possibility of using a solvent-free sample formulation and the feasibility of indirect detection in DNP-enhanced HETCOR experiments.

Circulation patterns associated with cold events over East Asia during the winter months of 1948–2014 are classified into four regimes by applying a k-means clustering method based on the area-weighted pattern correlation. The earliest precursor signals for two regimes are anticyclonic anomalies, which evolve into Ural and central Siberian blocking-like circulation patterns. The earliest precursor signals for the other two regimes are cyclonic anomalies, both of which evolve to amplify the East Asian trough (EAT). Both the blocking-like circulation patterns and amplified EAT favor the initialization of cold events. On average, the blocking-related regimes tend to last longer. The lead time of the earliest precursor signal for the central Siberian blocking-related regime is only 4 days, while those for the other regimes range from 16 to 18 days. The North Atlantic Oscillation plays essential roles both in triggering the precursor for the Ural blocking-related regime and in amplifying the precursors for all regimes. All regimes preferentially occur during the positive phase of the Eurasian teleconnection pattern and the negative phase of the El Nino–Southern Oscillation. For three regimes, surface cooling is primarily due to reduced downward infrared radiation and enhanced cold advection. For the remaining regime, which is associated with the southernmost cooling center, sensible and latent heat release and horizontal cold advection dominate the East Asian cooling.