A highly stable and flexible zeolite electrolyte solid-state Li-air battery.

Solid-state lithium (Li)-air batteries are recognized as a next-generation solution for energy storage to address the safety and electrochemical stability issues that are encountered in liquid battery systems1-4. However, conventional solid electrolytes are unsuitable for use in solid-state Li-air systems owing to their instability towards lithium metal and/or air, as well as the difficulty in constructing low-resistance interfaces5. Here we present an integrated solid-state Li-air battery that contains an ultrathin, high-ion-conductive lithium-ion-exchanged zeolite X (LiX) membrane as the sole solid electrolyte. This electrolyte is integrated with cast lithium as the anode and carbon nanotubes as the cathode using an in situ assembly strategy. Owing to the intrinsic chemical stability of the zeolite, degeneration of the electrolyte from the effects of lithium or air is effectively suppressed. The battery has a capacity of 12,020 milliamp hours per gram of carbon nanotubes, and has a cycle life of 149 cycles at a current density of 500 milliamps per gram and at a capacity of 1,000 milliamp hours per gram. This cycle life is greater than those of batteries based on lithium aluminium germanium phosphate (12 cycles) and organic electrolytes (102 cycles) under the same conditions. The electrochemical performance, flexibility and stability of zeolite-based Li-air batteries confer practical applicability that could extend to other energy-storage systems, such as Li-ion, Na-air and Na-ion batteries.

Porous Copper-Loaded Zeolites for High-Efficiency Capture of Iodine from Spent Fuel Reprocessing Off-Gas.

Capturing volatile radionuclide iodine produced in the nuclear industry is a crucial environmental issue. In previous studies, the principal efficient adsorbent for iodine capture was silver-containing zeolite. As silver-containing zeolites are expensive, alternate copper-loaded porous zeolites, including CuCl loaded NaY reduced by H2 (denoted as H2CuY) and CO (denoted as COCuY), were studied for iodine adsorption at moderate temperatures. The current work also discusses the influence of copper valency on iodine adsorption. Due to the copper sites and nanosized pore structure, H2CuY and COCuY showed high iodine adsorption capacities of 450 and 219 mg/g, respectively. The iodine adsorption capacity of H2CuY was higher than that of silver-loaded zeolites. Moreover, H2CuY and COCuY adsorbed volatile iodine through a chemical mechanism involving the copper sites of different valencies, and the Cu0 was more effective in adsorbing iodine than Cu+. These copper-loaded zeolites with strong chemical interactions with iodine and high iodine adsorption capacities provided the possibility for iodine adsorption application in the nuclear industry.

Molecular Insight into Bubble Nucleation on the Surface with Wettability Transition at Controlled Temperatures.

A surface with a smart wettability transition has recently been proposed to enhance the boiling heat transfer in either macro- or microscale systems. This work explores the mechanisms of bubble nucleation on surfaces with wettability transitions at controlled temperatures by molecular simulations. The results of the interaction energy at the interface and potential energy distribution of water molecules show that the nanostructure promotes nucleation over the copper surface and causes lower absolute potential energy to provide fixed nucleation sites for the initial generation of the bubble nucleus and shortens the incipient nucleation time, as compared to the mixed-wettability or hydrophilic nanostructure surface. An investigation on more nanostructured surfaces shows that a surface (F) with a wettability transition temperature of 620.0 K has the shortest average incipient nucleation time at 1672 ps with a wall temperature of 634.3 K. The surface with tunable wettability has also a high interfacial thermal conductance at low superheats, but it may not promote the critical heat flux at high superheats. The heat-transfer performance of the smart surface is better than the plate, the hydrophobic nanostructure, and the mixed-wettability surfaces, while it is lower than the hydrophilic nanostructure surface. This proposes a new method and provides insight for promoting bubble nucleation on a surface with temperature-dependent wettability.

Electron Beam Irradiation-Induced Formation of Defect-Rich Zeolites under Ambient Condition within Minutes.

Zeolites are a well-known family of microporous aluminosilicate crystals with a wide range of applications. Their industrial synthetic method under hydrothermal condition requires elevated temperature and long crystallization time and is therefore quite energy-consuming. Herein, we utilize high-energy electron beam irradiation generated by an industrial accelerator as a distinct type of energy source to activate the formation reaction of Na-A zeolite. The initial efforts afford an attractive reaction process that can be achieved under ambient conditions and completed within minutes with almost quantitative yield, leading to notable energy saving of one order of magnitude compared to the hydrothermal reaction. More importantly, electron beam irradiation simultaneously exhibits an etching effect during the formation of zeolite generating a series of crystal defects and additional pore windows that can be controlled by irradiation dose. These observations give rise to significantly enhanced surface area and heavy metal removal capabilities in comparison with Na-A zeolite synthesized hydrothermally. Finally, we show that this method can be applied to many other types of zeolites.

A Layered Cationic Aluminum Oxyhydroxide as a Highly Efficient and Selective Trap for Heavy Metal Oxyanions.

Cationic framework materials, especially pure inorganic cationic frameworks that can efficiently and selectively capture harmful heavy metal oxyanions from aqueous solution are highly desired yet scarcely reported. Herein, we report the discovery of a 2D cationic aluminum oxyhydroxide, JU-111, which sets a new benchmark for heavy metal oxyanion sorbents, especially for CrVI . Its structure was solved based on 3D electron diffraction tomography data. JU-111 shows fast sorption kinetics (ca. 20 min), high capture capacity (105.4 mg g-1 ), and broad working pH range (3-10) toward CrVI oxyanions. Unlike layered double hydroxides (LDHs), which are poorly selective in the presence of CO3 2- , JU-111 retains excellent selectivity for CrVI even under a large excess of CO3 2- . These superior features coupled with the ultra-low cost and environmentally benign nature make JU-111 a promising candidate for toxic metal oxyanion remediation as well as other potential applications.

Association of cumulative resting heart rate exposure with rapid renal function decline: a prospective cohort study with 27,564 older adults.

OBJECTIVE: To evaluate the prospective association between cumulative resting heart rate (cumRHR) and rapid renal function decline (RRFD) in a cohort of individuals aged 60 and older. METHODS: In the Tianjin Chronic Kidney Disease Cohort Study, the individuals who underwent three consecutive physical examinations between 2014 and 2017, with estimated glomerular filtration rate (eGFR) greater than 60 mL/min per 1.73 m2 and aged 60 years or older were enrolled. A total of 27,564 patients were prospectively followed up from January 1, 2017 to December 31, 2020. The 3-year cumRHR was calculated. The primary outcome was RRFD, defined as an annualized decline in eGFR of 5 mL/min per 1.73 m2 or greater. Logistic and restricted spline regression models and subgroup analysis were used to investigate the association of cumRHR with RRFD after adjusting for all confounders. RESULTS: During a median follow-up of 3.2 years, a total of 4,347 (15.77%) subjects developed RRFD. In fully-adjusted models, compared with the lowest quartile of cumRHR, the odds ratio (OR) for the highest was 1.44 (1.28-1.61), P < 0.001. Furthermore, each 1-standard deviation (27.97 beats/min per year) increment in cumRHR was associated with a 17% (P < 0.001) increased risk of RRFD, with a linear positive correlation (P for non-linear = 0.803). Participants with a 3-year cumRHR ≥ 207 (beats/min) * year (equivalent to ≥ 69 beats/min per year in 3 years) were found to be at a higher risk of RRFD. CONCLUSIONS: The cumRHR is significantly associated with a higher risk of RRFD among older adults. These results might provide an effective goal for managing and delaying the decline of renal function in the older adults.

Two-Dimensional Cationic Aluminoborate as a New Paradigm for Highly Selective and Efficient Cr(VI) Capture from Aqueous Solution.

Water pollutants existing in their oxyanion forms have high solubility and environmental mobility. To capture these anionic pollutants, cost-effective inorganic materials with cationic frameworks and outstanding removal performance are ideal adsorbents. Herein, we report that two-dimensional (2D) cationic aluminoborate BAC(10) sets a new paradigm for highly selective and efficient capture of Cr(VI) and other oxyanions from aqueous solution. The structure of Cr(VI)-exchanged BAC(10) sample (Cr(VI)@BAC(10), H0.22·Al2BO4.3·(HCrO4)0.22·2.64H2O) has been successfully solved by continuous rotation electron diffraction. The crystallographic data show that the 2D cationic layer of BAC(10) is built by AlO6 octahedra, BO4 tetrahedra, and BO3 triangles. Partial chromate ions exchanged with Cl- ions are located within the interlayer region, which are chemically bonded to the aluminoborate layer. BAC(10) shows faster adsorption kinetics compared to the commercial anion exchange resin (AER) and layered double hydroxides (LDHs), a higher maximum adsorption capacity of 139.1 mg/g than that of AER (62.77 mg/g), LDHs (81.43 mg/g), and a vast majority of cationic MOFs, and a much broader working pH range (2-10.5) than LDHs. Moreover, BAC(10) also shows excellent Cr(VI) oxyanion removal performance for a solution with a low concentration (1-10 mg/L), and the residual concentration can be reduced to below 0.05 mg/L of the WHO drinking water criterion. These superior properties indicate that BAC(10) is a promising material for remediation of Cr(VI) and other harmful oxyanions from wastewater.

Does Economic Policy Uncertainty Matter for Healthcare Expenditure in China? A Spatial Econometric Analysis.

A growing body of research has documented the determinants of healthcare expenditure, but no known empirical research has focused on investigating the spatial effects between economic policy uncertainty (EPU) and healthcare expenditure. This study aims to explore the spatial effects of EPU on healthcare expenditure using the panel data of 29 regions in China from 2007 to 2017. Our findings show that healthcare expenditure in China has the characteristics of spatial clustering and spatial spillover effects. Our study also shows that EPU has positive spatial spillover effects on healthcare expenditure in China; that is, EPU affects not only local healthcare expenditure but also that in other geographically close or economically connected regions. Our study further indicates that the spatial spillover effects of EPU on healthcare expenditure only exist in the eastern area. The findings of this research provide some key implications for policymakers in emerging markets.

The inorganic cation-tailored "trapdoor" effect of silicoaluminophosphate zeolite for highly selective CO2 separation.

Functional nanoporous materials are widely explored for CO2 separation, in particular, small-pore aluminosilicate zeolites having a "trapdoor" effect. Such an effect allows the specific adsorbate to push away the sited cations inside the window followed by exclusive admission to the zeolite pores, which is more advantageous for highly selective CO2 separation. Herein, we demonstrated that the protonated organic structure-directing agent in the small-pore silicoaluminophosphate (SAPO) RHO zeolite can be directly exchanged with Na+, K+, or Cs+ and that the Na+ form of SAPO-RHO exhibited unprecedented separation for CO2/CH4, superior to all of the nanoporous materials reported to date. Rietveld refinement revealed that Na+ is sited in the center of the single eight-membered ring (s8r), while K+ and Cs+ are sited in the center of the double 8-rings (d8rs). Theoretical calculations showed that the interaction between Na+ and the s8r in SAPO-RHO was stronger than that in aluminosilicate RHO, giving an enhanced "trapdoor" effect and record high selectivity for CO2 with the separation factor of 2196 for CO2/CH4 (0.02/0.98 bar). The separation factor of Na-SAPO-RHO for CO2/N2 was 196, which was the top level among zeolitic materials. This work opens a new avenue for gas separation by using diverse silicoaluminophosphate zeolites in terms of the cation-tailored "trapdoor" effect.

Fabricating Mechanically Robust Binder-Free Structured Zeolites by 3D Printing Coupled with Zeolite Soldering: A Superior Configuration for CO2 Capture.

3D-printing technology is a promising approach for rapidly and precisely manufacturing zeolite adsorbents with desirable configurations. However, the trade-off among mechanical stability, adsorption capacity, and diffusion kinetics remains an elusive challenge for the practical application of 3D-printed zeolites. Herein, a facile "3D printing and zeolite soldering" strategy is developed to construct mechanically robust binder-free zeolite monoliths (ZM-BF) with hierarchical structures, which can act as a superior configuration for CO2 capture. Halloysite nanotubes are employed as printing ink additives, which serve as both reinforcing materials and precursor materials for integrating ZM-BF by ultrastrong interfacial "zeolite-bonds" subjected to hydrothermal treatment. ZM-BF exhibits outstanding mechanical properties with robust compressive strength up to 5.24 MPa, higher than most of the reported structured zeolites with binders. The equilibrium CO2 uptake of ZM-BF reaches up to 5.58 mmol g-1 (298 K, 1 bar), which is the highest among all reported 3D-printed CO2 adsorbents. Strikingly, the dynamic adsorption breakthrough tests demonstrate the superiority of ZM-BF over commercial benchmark zeolites for flue gas purification and natural gas and biogas upgrading. This work introduces a facile strategy for designing and fabricating high-performance hierarchically structured zeolite adsorbents and even catalysts for practical applications.

Three-Dimensional-Printed Core-Shell Structured MFI-Type Zeolite Monoliths for Volatile Organic Compound Capture under Humid Conditions.

Crystalline aluminosilicate zeolites with high sorption capacity and low production cost have been recognized as a promising adsorbent for volatile organic compound (VOC) capture. However, the ubiquitous water vapor in the VOC streams may compete with VOCs during the practical separation process because of the hydrophilic property of aluminosilicate zeolites. Herein, a self-supporting core-shell structured MFI-type zeolite monolith was fabricated by 3D-printing aluminosilicate ZSM-5 zeolites as the core, followed by coating silicalite-1 zeolites as a hydrophobic shell via post-hydrothermal crystallization. Natural sepiolite nanofibers (SNFs) were employed as printing ink additives for reinforcing the mechanical stability of 3D-printed ZSM-5 monoliths. Colloidal silica was also introduced into the printing inks, affording continuous growth of silicalite-1 layers (with a thickness of ∼200 nm) over ZSM-5 crystals. Such core-shell structured MFI-type zeolite monoliths exhibited superior dynamic adsorption performance for toluene at 298 K under humid conditions (relative humidity: 50%), with a saturated adsorption capacity of 44.3 mg/g. This work provides a facile strategy for designing self-supporting zeolite monoliths with core-shell architectures for adsorption/separation and other advanced applications.