Encapsulating metal organic framework into hollow mesoporous carbon sphere as efficient oxygen bifunctional electrocatalyst

Applying metal organic frameworks (MOFs) in electrochemical systems is a currently emerging field owing to the rich metal nodes and highly specific surface area of MOFs. However, the problems for MOFs that need to be solved urgently are poor electrical conductivity and low ion transport. Here we present a facile in situ growth method for the rational synthesis of MOFs@hollow mesoporous carbon spheres (HMCS) yolk–shell-structured hybrid material for the first time. The size of the encapsulated Zeolitic Imidazolate Framework-67 (ZIF-67) is well controlled to 100 nm due to the spatial confinement effect of HMCS, and the electrical conductivity of ZIF-67 is also increased significantly. The ZIF@HMCS-25% hybrid material obtained exhibits a highly efficient oxygen reduction reaction activity with 0.823 V (vs. reversible hydrogen electrode) half-wave potential and an even higher kinetic current density (J_K = 13.8 mA cm⁻²) than commercial Pt/C. ZIF@HMCS-25% also displays excellent oxygen evolution reaction performance and the overpotential of ZIF@HMCS-25% at 10 mA cm⁻² is 407 mV. In addition, ZIF@HMCS-25% is further employed as an air electrode for a rechargeable Zn–air battery, exhibiting a high power density (120.2 mW cm⁻² at 171.4 mA cm⁻²) and long-term charge/discharge stability (80 h at 5 mA cm⁻²). This MOFs@HMCS yolk–shell design provides a versatile method for the application of MOFs as electrocatalysts directly.     

Graphdiyne-based metal atomic catalysts for synthesizing ammonia

Development of novel catalysts for nitrogen reduction at ambient pressures and temperatures with ultrahigh ammonia (NH₃) yield and selectivity is challenging. In this work, an atomic catalyst with separated Pd atoms on graphdiyne (Pd-GDY) was synthesized, which shows fascinating electrocatalytic properties for nitrogen reduction. The catalyst has the highest average NH₃ yield of 4.45 ± 0.30 mg_NH3 mg_Pd⁻¹ h⁻¹, almost tens of orders larger than for previously reported catalysts, and 100% reaction selectivity in neutral media. Pd-GDY exhibits almost no decreases in NH₃ yield and Faradaic efficiency. Density functional theory calculations show that the reaction pathway prefers to perform at the (Pd, C1, C2) active area because of the strongly coupled (Pd, C1, C2), which elevates the selectivity via enhanced electron transfer. By adjusting the p–d coupling accurately, reduction of self-activated nitrogen is promoted by anchoring atom selection, and side effects are minimized.     

A highly efficient atomically thin curved PdIr bimetallene electrocatalyst

The multi-metallene with an ultrahigh surface area has great potential in precise tuning of surface heterogeneous d-electronic correlation by surface strain effect for the distinctive surface electronic structure, which is a brand new class of promising 2D electrocatalyst for sustainable energy device application. However, achieving such an atomically thin multi-metallene still presents a great challenge. Herein, we present a new synthetic method for an atomic-level palladium-iridium (PdIr) bimetallene with an average thickness of only ∼1.0 nm for achieving superior catalysis in the hydrogen evolution reaction (HER) and the formic acid oxidation reaction (FAOR). The curved PdIr bimetallene presents a top-ranked high electrochemical active area of 127.5 ± 10.8 m² g_Pd+Ir⁻¹ in the reported noble alloy materials, and exhibits a very low overpotential, ultrahigh activity and improved stability for HER and FAOR. DFT calculation reveals that the PdIr bimetallene herein has a unique lattice tangential strain, which can induce surface distortion while concurrently creating a variety of concave-convex featured micro-active regions formed by variously coordinated Pd sites agglomeration. Such a strong strain effect correlates the abnormal on-site active 4d¹⁰-t_2g-orbital Coulomb correlation potential and directly elevates orbital-electronegativity exposure within these active regions, resulting in a preeminent barrier-free energetic path for significant enhancement of FAOR and HER catalytic performance.     

A highly alkaline-stable metal oxide@metal–organic framework composite for high-performance electrochemical energy storage

Most metal–organic frameworks (MOFs) hardly maintain their physical and chemical properties after exposure to alkaline aqueous solutions, thus precluding their use as potential electrode materials for electrochemical energy storage devices. Here, we present the design and synthesis of a highly alkaline-stable metal oxide@MOF composite, Co₃O₄ nanocube@Co-MOF (Co₃O₄@Co-MOF), via a controllable and facile one-pot hydrothermal method under highly alkaline conditions. The obtained composite possesses exceptional alkaline stability, retaining its original structure in 3.0 M KOH for at least 15 days. Benefitting from the exceptional alkaline stability, unique structure, and larger surface area, the Co₃O₄@Co-MOF composite shows a specific capacitance as high as 1020 F g⁻¹ at 0.5 A  g⁻¹ and a high cycling stability with only 3.3% decay after 5000 cycles at 5 A g⁻¹. The as-constructed solid-state flexible device exhibits a maximum energy density of 21.6 mWh cm⁻³.     

Integration of bio-inspired lanthanide-transition metal cluster and P-doped carbon nitride for efficient photocatalytic overall water splitting

Photosynthesis in nature uses the Mn₄CaO₅ cluster as the oxygen-evolving center to catalyze the water oxidation efficiently in photosystem II. Herein, we demonstrate bio-inspired heterometallic LnCo₃ (Ln = Nd, Eu and Ce) clusters, which can be viewed as synthetic analogs of the CaMn₄O₅ cluster. Anchoring LnCo₃ on phosphorus-doped graphitic carbon nitrides (PCN) shows efficient overall water splitting without any sacrificial reagents. The NdCo₃/PCN-c photocatalyst exhibits excellent water splitting activity and a quantum efficiency of 2.0% at 350 nm. Ultrafast transient absorption spectroscopy revealed the transfer of a photoexcited electron and hole into the PCN and LnCo₃ for hydrogen and oxygen evolution reactions, respectively. A density functional theory (DFT) calculation showed the cooperative water activation on lanthanide and O−O bond formation on transition metal for water oxidation. This work not only prepares a synthetic model of a bio-inspired oxygen-evolving center but also provides an effective strategy to realize light-driven overall water splitting.     

Ultra-thin metal-organic framework nanoribbons

Structure engineering of metal-organic frameworks (MOFs) at the nanometer scale is attracting increasing interest due to their unique properties and new functions that normally cannot be achieved in bulk MOF crystals. Here, we report the preparation of ultra-thin MOF nanoribbons (NRBs) by using metal-hydroxide nanostructures as the precursors. Importantly, this general method can be used to synthesize various kinds of ultra-thin MOF NRBs, such as MBDC (M = Co, Ni; BDC = 1,4-benzenedicarboxylate), NiCoBDC, CoTCPP (TCPP = tetrakis(4-carboxyphenyl)porphyrin) and MIL-53(Al) NRBs. As a proof-of-concept application, the as-prepared ultra-thin CoBDC NRBs have been successfully used as a fluorescent sensing platform for DNA detection, which exhibited excellent sensitivity and selectivity. The present strategy might open an avenue to prepare MOF nanomaterials with new structures and unique properties for various promising applications.     

Influence of Altered Hormonal Status on Platelet 5-HT and MAO-B Activity in Cigarette Smokers

The present study was designed to understand the cigarette smoking-induced alterations in hormones and the resulting changes in platelet serotonin (5-hydroxytryptamine, 5-HT) and monoamine oxidase (MAO-B) activity in chronic smokers. Human male volunteers aged 35 ± 8 years, were divided into two groups, namely controls and smokers (12 ± 2 cigarettes per day for 7–10 years). Results showed that cigarette smoking significantly (p < 0.05) elevated plasma triiodothyronine (T₃), cortisol and testosterone levels with significant (p < 0.05) reduction in plasma tryptophan and thyroxin (T₄). Moreover, smokers showed reduced platelet 5-HT levels and MAO-B activity. In smokers, plasma cortisol was negatively correlated with tryptophan (r = −0.386), platelet MAO-B (r = −0.264), and 5-HT (r = −0.671), and positively correlated with testosterone (r = 0.428). However, testosterone was negatively correlated with platelet MAO-B (r = −0.315), and 5-HT (r = −.419) in smokers. Further, smokers plasma T₃ levels were negatively correlated with platelet MAO-B (r = −0.398), and 5-HT (r = −0.541), whereas T₄ levels were positively correlated with platelet MAO-B (r = 0.369), and 5-HT (r = 0.454). In conclusion, our study showed that altered testosterone and cortisol levels may aggravate behavior, mood disturbances and symptoms of depression by decreasing platelet 5-HT and MAO-B activity in smokers.     

Enabling Mg metal anodes rechargeable in conventional electrolytes by fast ionic transport interphase

Rechargeable magnesium batteries have received extensive attention as the Mg anodes possess twice the volumetric capacity of their lithium counterparts and are dendrite-free. However, Mg anodes suffer from surface passivation film in most glyme-based conventional electrolytes, leading to irreversible plating/stripping behavior of Mg. Here we report a facile and safe method to obtain a modified Mg metal anode with a Sn-based artificial layer via ion-exchange and alloying reactions. In the artificial coating layer, Mg₂Sn alloy composites offer a channel for fast ion transport and insulating MgCl₂/SnCl₂ bestows the necessary potential gradient to prevent deposition on the surface. Significant improved ion conductivity of the solid electrolyte interfaces and decreased overpotential of Mg symmetric cells in Mg(TFSI)₂/DME electrolyte are obtained. The coated Mg anodes can sustain a stable plating/stripping process over 4000 cycles at a high current density of 6 mA cm⁻². This finding provides an avenue to facilitate fast ion diffusion kinetics of Mg metal anodes in conventional electrolytes.     

Robust prediction of hourly PM2.5 from meteorological data using LightGBM

Retrieving historical fine particulate matter (PM_2.5) data is key for evaluating the long-term impacts of PM_2.5 on the environment, human health and climate change. Satellite-based aerosol optical depth has been used to estimate PM_2.5, but estimations have largely been undermined by massive missing values, low sampling frequency and weak predictive capability. Here, using a novel feature engineering approach to incorporate spatial effects from meteorological data, we developed a robust LightGBM model that predicts PM_2.5 at an unprecedented predictive capacity on hourly (R² = 0.75), daily (R² = 0.84), monthly (R² = 0.88) and annual (R² = 0.87) timescales. By taking advantage of spatial features, our model can also construct hourly gridded networks of PM_2.5. This capability would be further enhanced if meteorological observations from regional stations were incorporated. Our results show that this model has great potential in reconstructing historical PM_2.5 datasets and real-time gridded networks at high spatial-temporal resolutions. The resulting datasets can be assimilated into models to produce long-term re-analysis that incorporates interactions between aerosols and physical processes.     

Serum Testosterone, 17β-Estradiol and PSA Levels in Subjects with Prostate Disorders

Prostate carcinoma is the most frequently diagnosed malignancy and the second leading cause of death as a result of cancer in men in the US and other parts of the world. There are conflicting reports on the serum levels of testosterone and 17β-estradiol (E₂) in benign prostatic hyperplasia (BPH) and prostate cancer. This study was designed to evaluate the serum concentrations of these hormones in patients with these disorders. Serum levels of prostate specific antigen (PSA), total testosterone and estradiol were determined in 228 subjects comprising of 116 subjects with BPH, 62 subjects with prostate cancer (CaP) and 50 age-matched apparently healthy controls, using ELISA methods. PSA levels were significantly elevated (p < 0.05) in BPH subjects than controls, while there was no significant difference (p > 0.05) in testosterone and estradiol levels of these subjects. PSA and estradiol levels were significantly higher (p < 0.05) in CaP subjects than in controls, while there was no observed significant difference (p > 0.05) in testosterone levels. CaP subjects had significantly raised PSA, testosterone, and estradiol levels than BPH subjects. The mean molar ratio of testosterone: E₂ was lowest among CaP patients (134:1) and highest among controls (166:1). Significant positive correlation between PSA and 17β-estradiol was observed in prostate disorders (BPH and CaP patients: r = 0.347; p = 0.000). Significant negative correlations between testosterone and PSA were also observed among BPH patients (r = −0.221, p = 0.049) and control subjects (r = −0.490, p = 0.000). No significant correlation existed between testosterone and PSA in CaP patients (r = 0.051, p = 0.693). Correlations between age and estradiol in both BPH and CaP were not significant (p > 0.05). This study has shown that, there was a significant increase in serum estradiol in CaP subjects, while the testosterone levels in both BPH and CaP subjects were not different from those of controls.     

Silylamido supported dinitrogen heterobimetallic complexes: syntheses and their catalytic ability

Molybdenum dinitrogen complexes supported by monodentate arylsilylamido ligand, [Ar(Me₃Si)N]₃MoN₂Mg(THF)₂[N(SiMe₃)Ar] (5) and [Ar(Me₃Si)N]₃MoN₂SiMe₃ (6) (Ar = 3,5-Me₂C₆H₃) were synthesized and structurally characterized, and proved to be effective catalysts for the disproportionation of cyclohexadienes and isomerization of terminal alkenes. The ¹H NMR spectrum suggested that the bridging nitrogen ligand remains intact during the catalytic reaction, indicating possible catalytic ability of the Mo-N=N motif.     

Ultra-small hollow ternary alloy nanoparticles for efficient hydrogen evolution reaction

Hollow nanoparticles with large specific surface area and high atom utilization are promising catalysts for the hydrogen evolution reaction (HER). We describe herein the design and synthesis of a series of ultra-small hollow ternary alloy nanostructures using a simple one-pot strategy. The same technique was demonstrated for hollow PtNiCu nanoparticles, hollow PtCoCu nanoparticles and hollow CuNiCo nanoparticles. During synthesis, the displacement reaction and oxidative etching played important roles in the formation of hollow structures. Moreover, our hollow PtNiCu and PtCoCu nanoparticles were single crystalline, with an average diameter of 5 nm. Impressively, ultra-small hollow PtNiCu nanoparticles, containing only 10% Pt, exhibited greater electrocatalytic HER activity and stability than a commercial Pt/C catalyst. The overpotential of hollow PtNiCu nanoparticles at 10 mA cm⁻² was 28 mV versus reversible hydrogen electrode (RHE). The mass activity was 4.54 A mg_Pt⁻¹ at −70 mV versus RHE, which is 5.62-fold greater than that of a commercial Pt/C system (0.81 A mg_Pt⁻¹). Through analyses of bonding and antibonding orbital filling, density functional theory calculations demonstrated that the bonding strength of different metals to the hydrogen intermediate (H^*) was in the order of Pt > Co > Ni > Cu. The excellent HER performance of our hollow PtNiCu nanoparticles derives from moderately synergistic interactions between the three metals and H^*. This work demonstrates a new strategy for the design of low-cost and high-activity HER catalysts.     

Potential-tuned selective electrosynthesis of azoxy-, azo- and amino-aromatics over a CoP nanosheet cathode

Azoxy-, azo- and amino-aromatics are among the most widely used building blocks in materials science pharmaceuticals and synthetic chemistry, but their controllable and green synthesis has not yet been well established. Herein, a facile potential-tuned electrosynthesis of azoxy-, azo- and amino-aromatics via aqueous selective reduction of nitroarene feedstocks over a CoP nanosheet cathode is developed. A series of azoxy-, azo- and amino-compounds with excellent selectivity, good functional group tolerance and high yields are produced by applying different bias input. The synthetically significant and challenging asymmetric azoxy-aromatics can be controllably synthesized in moderate to good yields. The use of water as the hydrogen source makes this strategy remarkably fascinating and promising. In addition, deuterated aromatic amines with a high deuterium content can be readily obtained by using D₂O. By pairing with anodic oxidation of aliphatic amines to nitriles, synthetically useful building blocks can be simultaneously produced in a CoP||Ni₂P two-electrode electrolyzer. Only 1.25 V is required to achieve a current density of 20 mA cm⁻², which is much lower than that of overall water splitting (1.70 V). The paired oxidation and reduction reactions can also be driven using a 1.5 V battery to synthesize nitrile and azoxybenzene with good yields and selectivity, further emphasizing the flexibility and controllability of our method. This work paves the way for a promising approach to the green synthesis of valuable chemicals through potential-controlled electrosynthesis.     

Rational design of high-quality 2D/3D perovskite heterostructure crystals for record-performance polarization-sensitive photodetection

Polarization-sensitive photodetection is central to optics applications and has been successfully demonstrated in photodetectors of two-dimensional (2D) materials, such as layered hybrid perovskites; however, achieving high polarization sensitivity in such a photodetector remains extremely challenging. Here, for the first time, we demonstrate a high-performance polarization-sensitive photodetector using single-crystalline 2D/3D perovskite heterostructure, namely, (4-AMP)(MA)₂Pb₃Br₁₀/MAPbBr₃ (MA = methylammonium; 4-AMP = 4-(aminomethyl)piperidinium), which exhibits ultrahigh polarization sensitivity up to 17.6 under self-driven mode. To our knowledge, such a high polarization selectivity has surpassed all of the reported perovskite-based devices, and is comparable to, or even better than, the traditional inorganic heterostructure-based photodetectors. Further studies reveal that the built-in electric field formed at the junction can spatially separate the photogenerated electrons and holes, reducing their recombination rate and thus enhancing the performance for polarization-sensitive photodetection. This work provides a new source of polarization-sensitive materials and insights into designing novel optoelectronic devices.     

Plasmonic evolution of atomically size-selected Au clusters by electron energy loss spectrum

The plasmonic response of gold clusters with atom number (N) = 100–70 000 was investigated using scanning transmission electron microscopy-electron energy loss spectroscopy. For decreasing N, the bulk plasmon remains unchanged above N = 887 but then disappears, while the surface plasmon firstly redshifts from 2.4 to 2.3 eV above N = 887 before blueshifting towards 2.6 eV down to N = 300, and finally splitting into three fine features. The surface plasmon''s excitation ratio is found to follow N^0.669, which is essentially R². An atomically precise evolution picture of plasmon physics is thus demonstrated according to three regimes: classical plasmon (N = 887–70 000), quantum confinement corrected plasmon (N = 300–887) and molecule related plasmon (N < 300).     

(NH4)3B11PO19F3: a deep-UV nonlinear optical crystal with unique [B5PO10F]∞ layers

Deep-ultraviolet (DUV) nonlinear optical (NLO) crystals that can extend the output range of coherent light below 200 nm are pivotal materials for solid-state lasers. To date, KBe₂BO₃F₂ (KBBF) is the only usable crystal that can generate DUV coherent light by direct second harmonic generation (SHG), but the layered growth habit and toxic ingredients limit its application. Herein, we report a new fluoroborophosphate, (NH₄)₃B₁₁PO₁₉F₃ (ABPF), containing four different functional units: [BO₃], [BO₄], [BO₃F] and [PO₄]. ABPF exhibits a KBBF-like structure while eliminating the limitations of KBBF crystal. The unique [B₅PO₁₀F]_∞ layers enhance ABPF’s performance; for example, it has a large SHG response (1.2 × KDP) and a sufficient birefringence (0.088 at 1064 nm) that enables the shortest phase-matching wavelength to reach the DUV region. Meanwhile, the introduction of strong B-O-P covalent bonds decreases the layered growth habit. These findings will enrich the structural chemistry of fluoroborophosphate and contribute to the discovery of more excellent DUV NLO crystals.     

Prevalence of Vitamin D Deficiency in a Pediatric Hospital of Eastern India

Vitamin D deficiency is highly prevalent in Indian children of northern, western and southern states. Serum 25 hydroxy cholecalferol (ng/ml) was analyzed in 310 children and adolescents of pediatric hospital of Kolkata, India. Serum calcium (mg/dl), phosphorous (mg/dl) and alkaline phosphatase (IU/L) data was obtained. Median 25(OH)D was 19 ng/ml. 19.2 % of population had serum 25(OH)D < 10 ng/ml (severe deficiency), 52.9 % had <20 ng/ml (deficiency), 24.5 % had 20–29 ng/ml (insufficiency) and 22.6 % had >30 ng/ml (optimum). Deficiency was highest in adolescents (86.1 %), followed by school children (61.0 %), lowest in pre-school children (41.6 %). 25(OH)D concentrations was lowest in winters (P = 0.002) and spring (P = 0.03) compared to summer. There was no correlation with calcium (P = 0.99), phosphorous (P = 0.23) and ALP (P = 0.63). There is high prevalence of vitamin D deficiency in children and adolescents of eastern India. Prevalence was lower in younger subjects. 25(OH)D did not correlate with bone mineral markers.     

Dual-ligand and hard-soft-acid-base strategies to optimize metal-organic framework nanocrystals for stable electrochemical cycling performance

Most metal-organic frameworks (MOFs) hardly maintain their physical and chemical properties after exposure to acidic, neutral, or alkaline aqueous solutions, resulting in insufficient stability, therefore limiting their applications. Thus, the design and synthesis of stable size/morphology-controlled MOF nanocrystals is critical but challenging. In this study, dual-ligand and hard-soft-acid-base strategies were used to fabricate a variety of 3D pillared-layer [Ni(thiophene-2,5-dicarboxylate)(4,4^′-bipyridine)]_n MOF nanocrystals (1D nanofibers, 2D nanosheets and 3D aggregates) with controllable morphology by varying the concentration of 4,4^′-bipyridine and thus controlling the crystal growth direction. Owing to the shorter ion diffusion length, enhanced electron/ion transfer and strong interactions between thiophene-2,5-dicarboxylate and 4,4^′-bipyridine, the 2D nanosheets showed much larger specific capacitance than 1D nanofibers and 3D aggregates. A single device with an output voltage as high as 3.0 V and exceptional cycling performance (95% of retention after 5000 cycles at 3 mA cm^–2) was realized by configuring two aqueous asymmetric supercapacitive devices in series. The excellent cycling property and charge–discharge mechanism are consistent with the hard-soft-acid-base theory.     

The role of China's terrestrial carbon sequestration 2010–2060 in offsetting energy-related CO2 emissions

Energy consumption dominates annual CO₂ emissions in China. It is essential to significantly reduce CO₂ emissions from energy consumption to reach national carbon neutrality by 2060, while the role of terrestrial carbon sequestration in offsetting energy-related CO₂ emissions cannot be underestimated. Natural climate solutions (NCS), including improvements in terrestrial carbon sequestration, represent readily deployable options to offset anthropogenic greenhouse gas emissions. However, the extent to which China''s terrestrial carbon sequestration in the future, especially when target-oriented managements (TOMs) are implemented, can help to mitigate energy-related CO₂ emissions is far from certain. By synthesizing available findings and using several parameter-sparse empirical models that have been calibrated and/or fitted against contemporary measurements, we assessed China''s terrestrial carbon sequestration over 2010–2060 and its contribution to offsetting national energy-related CO₂ emissions. We show that terrestrial C sequestration in China will increase from 0.375 ± 0.056 (mean ± standard deviation) Pg C yr⁻¹ in the 2010s to 0.458 ± 0.100 Pg C yr⁻¹ under RCP2.6 and 0.493 ± 0.108 Pg C yr⁻¹ under the RCP4.5 scenario in the 2050s, when TOMs are implemented. The majority of carbon sequestration comes from forest, accounting for 67.8–71.4% of the total amount. China''s terrestrial ecosystems can offset 12.2–15.0% and 13.4–17.8% of energy-related peak CO₂ emissions in 2030 and 2060, respectively. The implementation of TOMs contributes 11.9% of the overall terrestrial carbon sequestration in the 2020s and 23.7% in the 2050s. The most likely strategy to maximize future NCS effectiveness is a full implementation of all applicable cost-effective NCS pathways in China. Our findings highlight the role of terrestrial carbon sequestration in offsetting energy-related CO₂ emissions and put forward future needs in the context of carbon neutrality.