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Manganese(II) halides have been a new generation of optoelectronic materials due to their fascinating luminescent properties, however, lacking specific solvent-responsive analogues with high quantum efficiency. Herein, we prepared three single crystals, [Pr(MIm)2][MnBr4] ([Pr(MIm)2]2+= 1,3-di(methylimidazolium)-propane, Compound 1), [Pr(EIm)2][MnBr4] ([Pr(EIm)2]2+= 1,3-di(ethylimidazolium)-propane, Compound 2), and [Bu(MIm)2][MnBr4] ([Bu(MIm)2]2+= 1,4-di(methylimidazolium)-butane, Compound 3), where different Bola-type cations were chosen as organic components to separate [MnBr4]2–tetrahedrons. All three compounds emitted bright green light with excellent quantum yields of 95.3, 80.0, and 96.2%, benefiting from the large Mn···Mn distance. More interestingly, Compound 3showed a highly selective response to methanol in a series of tested organic solvents, with a rapid and reversible change in emission color from green to red. The single crystal of [Bu(MIm)2][MnBr4]·CH3OH with red emission proved that the luminescence switching was attributed to the adsorption of CH3OH molecules into the lattice space in the form of the O–H···Br hydrogen bonds. To our knowledge, for tetrahedrally coordinated Mn(II) species, the reversible emission color switching between green and red triggered by a solvent without the change of coordination number is achieved for the first time, providing promising applications for the specific detection of methanol.

Identification of catalytic active sites is pivotal in the design of highly effective heterogeneous metal catalysts, especially for structure-sensitive reactions. Downsizing the dimension of the metal species on the catalyst increases the dispersion, which is maximized when the metal exists as single atoms, namely, single-atom catalysts (SACs). SACs have been reported to be efficient for various catalytic reactions. We show here that the Pt SACs, although with the highest metal atom utilization efficiency, are totally inactive in the cyclohexane (C6H12) dehydrogenation reaction, an important reaction that could enable efficient hydrogen transportation. Instead, catalysts enriched with fully exposed few-atom Pt ensembles, with a Pt–Pt coordination number of around 2, achieve the optimal catalytic performance. The superior performance of a fully exposed few-atom ensemble catalyst is attributed to its high d-band center, multiple neighboring metal sites, and weak binding of the product.

Objectives: Examine the impacts of age, diabetes, gender, and access type on vascular access (VA) associated costs among Chinese hemodialysis (HD) patients.Methods: We retrospectively included patients whose first permanent VA was created at the West China Hospital. Clinical characteristics, maturation, intervention, utilization, and exchange of every VA, as well as VA-related infection were collected. The study period for each patient was from HD initiation to the last follow-up. VA-related costs, including those for placement and intervention procedures, were calculated according to the standards set in 2019 for Chinese tertiary hospitals. Mann-WhitneyU and Chi-square tests were conducted for comparisons between groups.Results: A total of 358 Chinese HD patients experienced functionally 143 arteriovenous fistula (AVF), 22 arteriovenous graft (AVG), and 439 tunneled cuffed central venous catheter (tcCVC) during a median study period of 26 (IQR 13–44) months, of which 42.5% used more than one permanent VA. The median annual VA-related cost in the groups of age >75 years and ⩽75 years, diabetes and non-diabetes, male and female, was $525 and $397 (p= 0.016), $459 and $462 (p= 0.64), $476 and $445 (p= 0.94), respectively. The median monthly costs for AVF ($18), AVG ($289), and tcCVC ($37) were significantly different.Conclusion: HD patients aged >75 years had significantly higher annual VA-related costs. However, the annual VA-related costs did not differ across the diabetes groups or the gender groups. AVF was the most cost-effective permanent VA type in China, partly due to the inexpensive materials used compared to AVG or tcCVC.

The water–gas shift (WGS) reaction is an industrially important source of pure hydrogen (H2) at the expense of carbon monoxide and water1,2. This reaction is of interest for fuel-cell applications, but requires WGS catalysts that are durable and highly active at low temperatures3. Here we demonstrate that the structure (Pt1–Ptn)/a-MoC, where isolated platinum atoms (Pt1) and subnanometre platinum clusters (Ptn) are stabilized on a-molybdenum carbide (a-MoC), catalyses the WGS reaction even at 313 kelvin, with a hydrogen-production pathway involving direct carbon monoxide dissociation identified. We find that it is critical to crowd the a-MoC surface with Pt1and Ptnspecies, which prevents oxidation of the support that would cause catalyst deactivation, as seen with gold/a-MoC (ref. 4), and gives our system high stability and a high metal-normalized turnover number of 4,300,000 moles of hydrogen per mole of platinum. We anticipate that the strategy demonstrated here will be pivotal for the design of highly active and stable catalysts for effective activation of important molecules such as water and carbon monoxide for energy production.

We report the syntheses of highly dispersed CoNi bimetallic catalysts on the surface of α-MoC based on the strong metal support interaction (SMSI) effect. The interaction between the nearly atomically dispersed Co and Ni atoms was observed for the first time by the real-space chemical mapping at the atomic level. Combined with the ability of α-MoC to split water at low temperatures, the as-synthesized CoNi/α-MoC catalysts exhibited robust and synergistic performance for the hydrogen production from hydrolysis of ammonia borane. The metal-normalized activity of the bimetallic 1.5Co1.5Ni/α-MoC catalyst reached 321.1 molH2·mol–1CoNi·min–1at 298 K, which surpasses all the noble metal-free catalysts ever reported and is four times higher than that of the commercial Pt/C catalyst.

In the field of heterogeneous catalysis, transition metal carbides (TMCs) have attracted growing and extensive attention as a group of important catalytic materials for a variety of energy-related reactions. Due to the incorporation of carbon atoms at the interstitial sites, TMCs possess much higher density of states near the Fermi level, endowing the material with noble-metal-like electron configuration and catalytic behaviors. Crystal structure, site occupancies, surface termination, and metal/carbon defects in the bulk phase or at the surface are the structural factors that influence the behavior of the TMCs in catalytic reactions.

Direct selective oxidation of light alkanes, such as ethane, into value-added chemical products under mild reaction conditions remains a challenge in both industry and academia. Herein, the iridium cluster and atomically dispersed iridium catalysts have been successfully fabricated using nanodiamond as support. The obtained iridium cluster catalyst shows remarkable performance for selective oxidation of ethane under oxygen at 100 °C, with an initial activity as high as 7.5 mol/mol/h and a selectivity to acetic acid higher than 70% after five in situ recycles. The presence of CO in the reaction feed is pivotal for the excellent reaction performance. On the basis of X-ray photoelectron spectroscopy (XPS) analysis, the critical role of CO was revealed, which is to maintain the metallic state of reactive Ir species during the oxidation cycles.

High temperature physical vapor transport (HTPVT) was employed to grow polycrystalline SiC ceramics with high density and purity, induced by nano SiC particles as seeds. The obtained SiC ceramics were identified as 6H-SiC with a mainly preferred orientation along the (0 0 0 6) plane, and an obvious refinement of grain size was demonstrated for the SiC seeds. Mean grain sizes of the obtained SiC ceramics were 112 μm and 314 μm, by using the SiC seeds with the mean particle size of 50 nm and 500 nm, respectively, which were obviously smaller than that of the seed-free sample (960 μm). The samples obtained with the seeds also demonstrated enhanced flexural strength and hardness, attributing to the reduced mean grain size. Furthermore, SiC ceramics without seeds via HTPVT exhibited a high thermal conductivity of 242 W·(m·K)−1 at room temperature due to the highly preferred orientation. While the degree of preferred orientation of seed-induced samples was lower, the thermal conductivity of SiC ceramics induced by seeding still maintained at least 200 W·(m·K)−1 at room temperature, this level was much higher than most other methods. Therefore, seed-induced method appears to be an effective way to control structures and behavior of SiC ceramics through HTPVT. [ABSTRACT FROM AUTHOR]

ZnO semiconductor oxides are versatile functional materials that are used in photoelectronics, catalysis, sensing, etc. The Zn+–O–surface electronic states of semiconductor oxides were formed on the ZnO surface by Zn 4s and O 2p orbital coupling with the diboron compound’s B 2p orbitals. The formation of spin-coupled surface states was based on the spin–orbit interaction on the interface, which has not been reported before. This shows that the semiconductor oxide’s spin surface states can be modulated by regulating surface orbital energy. The Zn+–O–surface electronic states were confirmed by electron spin resonance results, which may help in expanding the fundamental research on spintronics modulation and quantum transport.

Lead halide perovskites are emerging as promising candidates for high-efficiency light-emitting diode (LED) applications because of their tunable band gaps and high quantum yield (QY). However, it remains a challenge to obtain stable red emitting materials with high QY. Herein, we report a facile and convenient hot-injection strategy to synthesize Mn-doped two-dimensional (2D) perovskite nanosheets. The emission peak can be tuned from 597 to 658 nm by manipulating the crystal field strength. In particular, a QY as high as 97% for 2D perovskite is achieved. The as-prepared perovskite also possesses excellent stability, whose emission property can be maintained for almost one year. A monochrome LED is further fabricated by employing the as-prepared perovskite as phosphor, which also shows high long-term stability. We believe that these highly efficient and stable perovskites will open up new opportunities in LED applications.

The hydrogenation activity of noble metal, especially platinum (Pt), catalysts can be easily inhibited by the presence of a trace amount of carbon monoxide (CO) in the reaction feeds. Developing CO-resistant hydrogenation catalysts with both high activity and selectivity is of great economic interest for industry as it allows the use of cheap crude hydrogen and avoids costly product separation. Here we show that atomically dispersed Pt over α-molybdenum carbide (α-MoC) constitutes a highly CO-resistant catalyst for the chemoselective hydrogenation of nitrobenzene derivatives. The Pt1/α-MoC catalyst shows promising activity in the presence of 5,000 ppm CO, and has a strong chemospecificity towards the hydrogenation of nitro groups. With the assistance of water, high hydrogenation activity can also be achieved using CO and water as a hydrogen source, without sacrificing selectivity and stability. The weakened CO binding over the electron-deficient Pt single atom and a new reaction pathway for nitro group hydrogenation confer high CO resistivity and chemoselectivity on the catalyst.

Blue-emitting perovskite nanocrystals (NCs) are known to exhibit low photoluminescence (PL) quantum yield (QY) compared to green- and red-emitting counterparts, which is due to the presence of localized trap states on the surface. Here, we demonstrate a new method to synthesize high-efficiency blue-emitting perovskite NCs by anion exchange of 0D and 3D perovskite NCs. The remarkable enhancement of the PL QY is caused by surface reconstruction and subsequent suppression of nonradiative recombination centers of 3D perovskite NCs during the anion exchange. Remarkably, these high-efficiency NCs have two appealing applications. First, they can be applied in backlight display, where the GaN light-emitting diode is usually used as the blue emission source. We found that the as-prepared NCs were facile to tune their emission peaks and possessed narrow linewidths. As a downconverter, the NCs realize an ultrapure blue light for backlight display. Second, benefiting from the existence of 0D perovskite, anticounterfeiting inks can also be achieved based on these blue-emitting perovskite NCs. The encoding/reading strategy relies on the conversion of 0D perovskites. These findings provide new opportunities for blue-emitting perovskite NCs and broaden their application.

Selective activation of chemical bonds in multifunctional oxygenates on solid catalysts is a crucial challenge for sustainable biomass upgrading. Molybdenum carbides and nitrides preferentially activate C═O and C–OH bonds over C═C and C–C bonds in liquid-phase hydrogenation of bioderived furfural, leading to highly selective formations of furfuryl alcohol (FA) and its subsequent hydrogenolysis product (2-methyl furan (2-MF)). We demonstrate that pure-phase α-MoC is more active than β-Mo2C and γ-Mo2N for catalyzing furfural hydrogenation, and the hydrogenation selectivity on these catalysts can be conveniently manipulated by alcohol solvents without significant changes in reaction rates (e.g., > 90% yields of FA in methanol solvent and of 2-MF in 2-butanol solvent at 423 K). Combined experimental and theoretical assessments of these solvent effects unveil that it is the hydrogen donating ability of the solvents that governs the hydrogenation rate of the reactants, while strong dissociative adsorption of the alcohol solvent on Mo-based catalysts results in surface decoration which controls the reaction selectivity via enforcing steric hindrance on the formation of relevant transient states. Such solvent-induced surface modification of Mo-based catalysts provides a compelling strategy for highly selective hydrodeoxygenation processes of biomass feedstocks.

We reported here a strategy to use a defective nanodiamond-graphene (ND@G) to prepare an atomically dispersed metal catalyst, i.e., in the current case atomically dispersed palladium catalyst which is used for selective hydrogenation of acetylene in the presence of abundant ethylene. The catalyst exhibits remarkable performance for the selective conversion of acetylene to ethylene: high conversion (100%), ethylene selectivity (90%), and good stability. The unique structure of the catalyst (i.e., atomically dispersion of Pd atoms on graphene through Pd–C bond anchoring) blocks the formation of unselective subsurface hydrogen species and ensures the facile desorption of ethylene against the overhydrogenation to undesired ethane, which is the key for the outstanding selectivity of the catalyst.

Abstract

Synthesis of atomically dispersed catalysts with high metal loading and thermal stability is challenging but particularly valuable for industrial application in heterogeneous catalysis. Here, we report a facile synthesis of a thermally stable atomically dispersed Ir/α-MoC catalyst with metal loading as high as 4 wt%, an unusually high value for carbide supported metal catalysts. The strong interaction between Ir and the α-MoC substrate enables high dispersion of Ir on the α-MoC surface, and modulates the electronic structure of the supported Ir species. Using quinoline hydrogenation as a model reaction, we demonstrate that this atomically dispersed Ir/α-MoC catalyst exhibits remarkable reactivity, selectivity and stability, for which the presence of high-density isolated Ir atoms is the key to achieving high metal-normalized activity and mass-specific activity. We also show that the water-promoted quinoline hydrogenation mechanism is preferred over the Ir/α-MoC, and contributes to high selectivity towards 1,2,3,4-tetrahydroquinoline. The present work demonstrates a new strategy in constructing a high-loading atomically dispersed catalyst for the hydrogenation reaction.Atomically dispersed Ir/α-MoC catalyst with high metal loading exhibits remarkable activity, selectivity and stability for quinoline hydrogenation reaction through water-promoted hydrogenation mechanism.

Developing room-temperature phosphorescence (RTP) materials with color-tunability performance in an aqueous environment is crucial for application in optoelectronic areas to a higher stage, such as multicolor display, visual detection of external stimulus, and high-level information anticounterfeiting, but still faces a formidable challenge. Herein, we propose an efficient design strategy to develop excitation wavelength-responsive RTP supramolecular co-assembly systems of a simple benzoic acid derivative and Laponite (Lap) clay nanoplates in aqueous solution, displaying an ultralong lifetime (0.632 s) and a high phosphorescence quantum efficiency (18.04%) simultaneously. Experimental and theoretical research studies suggest that this distinctive feature is due to the generation of more and efficient intersystem crossing pathways benefiting from the coexistence of isolated and J-aggregation states via controlling the doping of the benzoic acid derivative and the inhibition of phosphorescence quenching by water because of the synergistic effects of robust hydrogen-bonding interactions between Lapand the benzoic acid derivative, J-aggregations of the benzoic acid derivative, and good oxygen tolerance of the Lapclay. By virtue of their excellent RTP performances in aqueous solution, the visual colorimetric detection of Ag+in a water environment was achieved for the first time, and visible and high-level information encryption was accomplished as well.

Covalent organic frameworks (COFs) have great application potentials in photocatalytic water treatment. By using p-phenylenediamine with different numbers and locations of heterocyclic nitrogen atoms as a precursor, five types of COFs with different nitrogen positions were synthesized. We found that Cr(VI) photoreduction,Escherichia coliinactivation, and paracetamol degradation by COFs were heterocyclic nitrogen location-dependent. Particularly, the photocatalytic performance for all three tested pollutants by five types of COFs followed the order of the best performance for COF-PDZ with two ortho position heterocyclic N atoms, medium for COF-PMD with two meta position heterocyclic N atoms, and COF-PZ with two para position heterocyclic N atoms, and COF-PD with a single heterocyclic N atom, the worst performance for COF-1 without a heterocyclic N atom. Compared to the other COFs, COF-PDZ contained improved quantum efficiency and thus enhanced generation of electrons. The lower energy barriers and larger energy gaps of COF-PDZ contributed to its improved quantum efficiencies. The stronger affinity to Cr(VI) with lower adsorption energy of COF-PDZ also contributed to its excellent Cr(VI) reduction performance. By transferring into a more stable keto form, COF-PDZ showed great stability through five regeneration and reuse cycles. Overall, this study provided an insight into the synthesis of high-performance structure-dependent COF-based photocatalysts.

Pure dense silicon carbide (SiC) ceramics were obtained via the high-temperature physical vapor transport (HTPVT) method using graphite paper as the growth substrate. The phase composition, the evolution of microstructure, the thermal diffusivity and thermal conductivity at RT to 200∘C were investigated. The obtained samples had a relative density of higher than 98.7% and a large grain size of 1mm, the samples also had a room-temperature thermal conductivity of 242W⋅(m⋅K)−1and with the temperature increased to 200∘C, the thermal conductivity still maintained at 160W⋅(m⋅K)−1.