Biomarker Changes during 20 Years Preceding Alzheimer's Disease.

BACKGROUND: Biomarker changes that occur in the period between normal cognition and the diagnosis of sporadic Alzheimer's disease have not been extensively investigated in longitudinal studies. METHODS: We conducted a multicenter, nested case-control study of Alzheimer's disease biomarkers in cognitively normal participants who were enrolled in the China Cognition and Aging Study from January 2000 through December 2020. A subgroup of these participants underwent testing of cerebrospinal fluid (CSF), cognitive assessments, and brain imaging at 2-year-to-3-year intervals. A total of 648 participants in whom Alzheimer's disease developed were matched with 648 participants who had normal cognition, and the temporal trajectories of CSF biochemical marker concentrations, cognitive testing, and imaging were analyzed in the two groups. RESULTS: The median follow-up was 19.9 years (interquartile range, 19.5 to 20.2). CSF and imaging biomarkers in the Alzheimer's disease group diverged from those in the cognitively normal group at the following estimated number of years before diagnosis: amyloid-beta (Aß)42, 18 years; the ratio of Aß42 to Aß40, 14 years; phosphorylated tau 181, 11 years; total tau, 10 years; neurofilament light chain, 9 years; hippocampal volume, 8 years; and cognitive decline, 6 years. As cognitive impairment progressed, the changes in CSF biomarker levels in the Alzheimer's disease group initially accelerated and then slowed. CONCLUSIONS: In this study involving Chinese participants during the 20 years preceding clinical diagnosis of sporadic Alzheimer's disease, we observed the time courses of CSF biomarkers, the times before diagnosis at which they diverged from the biomarkers from a matched group of participants who remained cognitively normal, and the temporal order in which the biomarkers became abnormal. (Funded by the Key Project of the National Natural Science Foundation of China and others; ClinicalTrials.gov number, NCT03653156.).

Facile Deficiency Engineering in a Cobalt-Free Perovskite Air Electrode to Achieve Enhanced Performance for Protonic Ceramic Fuel Cells.

As a crucial component responsible for the oxygen reduction reaction (ORR), cobalt-rich perovskite-type cathode materials have been extensively investigated in protonic ceramic fuel cell (PCFC). However, their widespread application at a commercial scale is considerably hindered by the high cost and inadequate stability. In response to these weaknesses, the study presents a novel cobalt-free perovskite oxide, Ba0.95La0.05(Fe0.8Zn0.2)0.95O3-δ (BLFZ0.95), with the triple-conducting (H+|O2-|e-) property as an active and robust air electrode for PCFC. The B-site deficiency state contributes significantly to the optimization of crystal and electronic structure, as well as the increase in oxygen vacancy concentration, thus in turn favoring the catalytic capacity. As a result, the as-obtained BLFZ0.95 electrode demonstrates exceptional electrochemical performance at 700 °C, representing extremely low area-specific resistance of 0.04 Ω cm2 in humid air (3 vol.% H2O), extraordinarily high peak power density of 1114 mW cm-2, and improved resistance against CO2 poisoning. Furthermore, the outstanding long-term durability is achieved without visible deterioration in both symmetrical and single cell modes. This study presents a simple but crucial case for rational design of cobalt-free perovskite cathode materials with appreciable performance via B-site deficiency regulation.

A Single-Atom Fe-N-C Catalyst with Ultrahigh Utilization of Active Sites for Efficient Oxygen Reduction.

Fe-N-C single-atom catalysts (SACs) are emerging as a promising class of electrocatalysts for the oxygen reduction reaction (ORR) to replace Pt-based catalysts. However, due to the limited loading of Fe for SACs and the inaccessibility of internal active sites, only a small portion of the sites near the external surface are able to contribute to the ORR activity. Here, this work reports a metal-organic framework-derived Fe-N-C SAC with a hierarchically porous and concave nanoarchitecture prepared through a facile but effective strategy, which exhibits superior electrocatalytic ORR activity with a half-wave potential of 0.926 V (vs RHE) in alkaline media and 0.8 V (vs RHE) in acidic media while maintaining excellent stability. The superior ORR activity of the as-designed catalyst stems from the unique architecture, where the hierarchically porous architecture contains micropores as Fe SAC anchoring sites, meso-/macro-pores as accessible channels, and concave shell for increasing external surface area. The unique architecture has dramatically enhanced the utilization of previously blocked internal active sites, as confirmed by a high turnover frequency of 3.37 s-1 and operando X-ray absorption spectroscopy analysis with a distinct shift of adsorption edge.

A Nonstoichiometric Niobium Oxide/Graphite Composite for Fast-Charge Lithium-Ion Batteries.

Electrification of transportation has spurred the development of fast-charge energy storage devices. High-power lithium-ion batteries require electrode materials that can store lithium quickly and reversibly. Herein, the design and construction of a Nb2 O5-δ /graphite composite electrode that demonstrates remarkable rate capability and durability are reported. The presence of graphite enables the formation of a dominant Nb12 O29 phase and a minor T-Nb2 O5 phase. The high rate capability is attributed to the enhanced electronic conductivity and lower energy barriers for fast lithium diffusion in both Nb12 O29 and T-Nb2 O5 , as unraveled by density functional theory calculations. The excellent durability or long cycling life is originated from the coherent redox behavior of Nb ions and high reversibility of lithium intercalation/deintercalation, as revealed by operando X-ray absorption spectroscopy analysis. When tested in a half-cell at high cycling rates, the composite electrode delivers a specific capability of 120 mAh g-1 at 80 C and retains over 150 mAh g-1 after 2000 cycles at 30 C, implying that it is a highly promising anode material for fast-charging lithium-ion batteries.

Operando Investigation into Dynamic Evolution of Cathode-Electrolyte Interfaces in a Li-Ion Battery.

While Li-ion battery cathode-electrolyte interfaces (CEIs) have been extensively investigated in recent decades, accurately identifying the chemical nature and tracking the dynamics of the CEIs during electrochemical cycling still remain a grand challenge. Here we report our findings in the investigation into the dynamic evolution of the interface between a LiNi0.33Co0.33Mn0.33O2 (LNMC) cathode and an ethylene carbonate/dimethyl carbonate (EC/DMC)-based electrolyte using surface-enhanced Raman spectroscopy (SERS) performed on a model cell under typical battery operating conditions. In particular, the strong SERS activity provided by a monolayer of Au nanocubes deposited on a model LNMC electrode (additive-free) enables quasi-quantitative assessment of the CEI evolution during cycling, proving information vital to revealing the dynamics of the species adsorbed on the LNMC surface as a function of cell potential. Furthermore, our theoretical calculation, which is based on the interaction between a model interface-bound molecule and a model LNMC surface, agrees with our experimental observation. The carefully designed operando SERS platform has demonstrated high sensitivity, good surface specificity, and excellent compatibility with extensive electrochemical measurements; it is also applicable to fundamental studies of dynamic interfaces in other electrochemical energy storage and conversion systems.

"One-for-All" Strategy in Fast Energy Storage: Production of Pillared MOF Nanorod-Templated Positive/Negative Electrodes for the Application of High-Performance Hybrid Supercapacitor.

Currently, metal-organic frameworks (MOFs) are intensively studied as active materials for electrochemical energy storage applications due to their tunable structure and exceptional porosities. Among them, water stable pillared MOFs with dual ligands have been reported to exhibit high supercapacitor (SC) performance. Herein, the "One-for-All" strategy is applied to synthesize both positive and negative electrodes of a hybrid SC (HSC) from a single pillared MOF. Specifically, Ni-DMOF-TM ([Ni(TMBDC)(DABCO)0.5 ], TMBDC: 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid, DABCO: 1,4-diazabicyclo[2.2.2]-octane) nanorods are directly grown on carbon fiber paper (CFP) (denoted as CFP@TM-nanorods) with the help of triethylamine and function as the positive electrode of HSC under alkaline electrolyte. Meanwhile, calcinated N-doped hierarchical porous carbon nanorods (CFP@TM-NPCs) are produced and utilized as the negative counter-electrode from a one-step heat treatment of CFP@TM-nanorods. After assembling these two electrodes together to make a hybrid device, the TM-nanorods//TM-NPCs exhibit a wide voltage window of 1.5 V with a high sloping discharge plateau between 1-1.2 V, indicating its great potential for practical applications. This as-described "One-for-All" strategy is widely applicable and highly reproducible in producing MOF-based electrode materials for HSC applications, which shortens the gap between experimental synthesis and practical application of MOFs in fast energy storage.

High-Performance Energy Storage and Conversion Materials Derived from a Single Metal-Organic Framework/Graphene Aerogel Composite.

Metal oxides and carbon-based materials are the most promising electrode materials for a wide range of low-cost and highly efficient energy storage and conversion devices. Creating unique nanostructures of metal oxides and carbon materials is imperative to the development of a new generation of electrodes with high energy and power density. Here we report our findings in the development of a novel graphene aerogel assisted method for preparation of metal oxide nanoparticles (NPs) derived from bulk MOFs (Co-based MOF, Co(mIM)2 (mIM = 2-methylimidazole). The presence of cobalt oxide (CoOx) hollow NPs with a uniform size of 35 nm monodispersed in N-doped graphene aerogels (NG-A) was confirmed by microscopic analyses. The evolved structure (denoted as CoOx/NG-A) served as a robust Pt-free electrocatalyst with excellent activity for the oxygen reduction reaction (ORR) in an alkaline electrolyte solution. In addition, when Co was removed, the resulting nitrogen-rich porous carbon-graphene composite electrode (denoted as C/NG-A) displayed exceptional capacitance and rate capability in a supercapacitor. Further, this method is readily applicable to creation of functional metal oxide hollow nanoparticles on the surface of other carbon materials such as graphene and carbon nanotubes, providing a good opportunity to tune their physical or chemical activities.

Unraveling the Nature of Anomalously Fast Energy Storage in T-Nb2O5.

While T-Nb2O5 has been frequently reported to display an exceptionally fast rate of Li-ion storage (similar to a capacitor), the detailed mechanism of the energy storage process is yet to be unraveled. Here we report our findings in probing the nature of the ultrafast Li-ion storage in T-Nb2O5 using both experimental and computational approaches. Experimentally, we used in operando Raman spectroscopy performed on a well-designed model cell to systematically characterize the dynamic evolution of vibrational band groups of T-Nb2O5 upon insertion and extraction of Li ions during repeated cycling. Theoretically, our model shows that Li ions are located at the loosely packed 4g atomic layers and prefer to form bridging coordination with the oxygens in the densely packed 4h atomic layers. The atomic arrangement of T-Nb2O5 determines the unique Li-ion diffusion path topologies, which allow direct Li-ion transport between bridging sites with very low steric hindrance. The proposed model was validated by computational and experimental vibrational analyses. A comprehensive comparison between T-Nb2O5 and other important intercalation-type Li-ion battery materials reveals the key structural features that lead to the exceptionally fast kinetics of T-Nb2O5 and the cruciality of atomic arrangements for designing a new generation of Li-ion conduction and storage materials.

Rationally Designed 3D Fe and N Codoped Graphene with Superior Electrocatalytic Activity toward Oxygen Reduction.

Pyrolyzing Fe- and N-contained precursor together or separately with graphene results in codoped graphene dominated by bonded or separated Fe and N configuration, respectively. While the FeN bonded case greatly enhances activity toward oxygen reduction, the separated one does not. This rationally designed Fe and N codoped 3D graphene exhibits superior electrocatalytic activity than the state-of-the-art Pt/C catalyst.

Facile mechanochemical synthesis of nano SnO2/graphene composite from coarse metallic Sn and graphite oxide: an outstanding anode material for lithium-ion batteries.

A facile method for the large-scale synthesis of SnO2 nanocrystal/graphene composites by using coarse metallic Sn particles and cheap graphite oxide (GO) as raw materials is demonstrated. This method uses simple ball milling to realize a mechanochemical reaction between Sn particles and GO. After the reaction, the initial coarse Sn particles with sizes of 3-30 µm are converted to SnO2 nanocrystals (approximately 4 nm) while GO is reduced to graphene. Composite with different grinding times (1 h 20 min, 2 h 20 min or 8 h 20 min, abbreviated to 1, 2 or 8 h below) and raw material ratios (Sn:GO, 1:2, 1:1, 2:1, w/w) are investigated by X-ray diffraction, X-ray photoelectron spectroscopy, field-emission scanning electron microscopy and transmission electron microscopy. The as-prepared SnO2 /graphene composite with a grinding time of 8 h and raw material ratio of 1:1 forms micrometer-sized architected chips composed of composite sheets, and demonstrates a high tap density of 1.53 g cm(-3). By using such composites as anode material for LIBs, a high specific capacity of 891 mA h g(-1) is achieved even after 50 cycles at 100 mA g(-1).

Organic Nitrate Additive for High-Rate and Large-Capacity Lithium Metal Anode in Carbonate Electrolyte.

Lithium nitrate has been widely used to improve the interfacial stability of Li metal anode in ether electrolyte. However, the low solubility limits its application in carbonate electrolytes for high-voltage Li metal batteries. Herein, nitrated polycaprolactone (PCL-ONO2 ), which is prepared via the acylation of polycaprolactone diol (PCL-diol) followed by the grafting of nitrate group, has been proposed as an electrolyte additive to introduce high-concentration NO3 - into carbonate electrolytes for the first time. The theoretical calculations and X-ray photoelectron spectroscopy depth profiling demonstrate that the PCL-ONO2 additive preferentially reacts with Li metal and in situ constructs a stable dual-layered solid electrolyte interphase film, presenting an inner nitride-rich layer and an outer flexible PCL-based layer on the surface of Li metal anode. As a result, the Li metal anode delivers an impressive long-term cycling performance over 1400 h at an elevated area capacity of 10.0 mAh cm-2 and an ultrahigh current density of 10.0 mA cm-2 in the Li symmetrical cells. Moreover, the PCL-ONO2 additive enables the full cells constructed by coupling high-loading LiFePO4 (20.0 mg cm-2 ) or LiNi0.5 Co0.2 Mn0.3 (16.5 mg cm-2 ) cathode and thin Li metal anode (≈50 µm) to demonstrate greatly improved cycling stability and rate capability.

Competitive Redox Chemistries in Vanadium Niobium Oxide for Ultrafast and Durable Lithium Storage.

Niobium pentoxide (Nb2O5) anodes have gained increasing attentions for high-power lithium-ion batteries owing to the outstanding rate capability and high safety. However, Nb2O5 anode suffers poor cycle stability even after modified and the unrevealed mechanisms have restricted the practical applications. Herein, the over-reduction of Nb5+ has been demonstrated to be the critical reason for the capacity loss for the first time. Besides, an effective competitive redox strategy has been developed to solve the rapid capacity decay of Nb2O5, which can be achieved by the incorporation of vanadium to form a new rutile VNbO4 anode. The highly reversible V3+/V2+ redox couple in VNbO4 can effectively inhibit the over-reduction of Nb5+. Besides, the electron migration from V3+ to Nb5+ can greatly increase the intrinsic electronic conductivity for VNbO4. As a result, VNbO4 anode delivers a high capacity of 206.1 mAh g-1 at 0.1 A g-1, as well as remarkable cycle performance with a retention of 93.4% after 2000 cycles at 1.0 A g-1. In addition, the assembled lithium-ion capacitor demonstrates a high energy density of 44 Wh kg-1 at 5.8 kW kg-1. In summary, our work provides a new insight into the design of ultra-fast and durable anodes.

Catalysis Sans Catalyst Loss: The Origins of Prolonged Stability of Graphene-Metal-Graphene Sandwich Architecture for Oxygen Reduction Reactions.

Over the past decades, the design of active catalysts has been the subject of intense research efforts. However, there has been significantly less deliberate emphasis on rationally designing a catalyst system with a prolonged stability. A major obstacle comes from the ambiguity behind how catalyst degrades. Several degradation mechanisms are proposed in literature,   but with a lack of systematic studies, the causal relations between degradation and those proposed mechanisms remain ambiguous. Here, a systematic study of a catalyst system comprising of small particles and single atoms of Pt sandwiched between graphene layers, GR/Pt/GR, is studied to  unravel the degradation mechanism of the studied electrocatalyst for oxygen reduction reaction(ORR). Catalyst suffers from atomic dissolution under ORR harsh acidic and oxidizing operation voltages. Single atoms trapped in point defects within the top graphene layer on their way hopping through toward the surface of GR/Pt/GR architecture. Trapping mechanism renders individual Pt atoms as single atom catalyst sites catalyzing ORR for thousands of cycles before washed away in the electrolyte. The GR/Pt/GR catalysts also compare favorably to state-of-the-art commercial Pt/C catalysts and demonstrates a rational design of a hybrid nanoarchitecture with a prolonged stability for thousands of operation cycles.

Activating the oxygen electrocatalytic activity of layer-structured Ca0.5CoO2 nanofibers by iron doping.

The development of low-cost, highly efficient and stable electrocatalysts for the oxygen evolution reaction (OER) is of great significance for many promising energy storage and conversion applications, including metal-air batteries and water splitting technology. Here we report a layer-structured Ca0.5CoO2 nanofibers composed of interconnected ultrathin nanoplates, synthesized using an electrospinning process. The OER activity of Ca0.5CoO2 can be dramatically improved by iron doping, and the overpotential of Ca0.5Co1-xFexO2 (x = 0.25) is only 346 mV at a current density of 10 mA cm-2. The mass activity and intrinsic activity of Ca0.5Co0.75Fe0.25O2 at 1.6 V are, respectively, ∼18.7 and ∼11.4 times higher than those of Ca0.5CoO2. Iron doping modifies the electronic structure of Ca0.5CoO2, resulting in partial oxidation of the surface cobalt and increased amount of highly oxidative species (O22-/O2). Consequently, Ca0.5Co0.75Fe0.25O2 nanofibers with tuned electronic states have shown great potential as cost-effective and efficient electrocatalysts for OER.

Surface restructuring of a perovskite-type air electrode for reversible protonic ceramic electrochemical cells.

Reversible protonic ceramic electrochemical cells (R-PCECs) are ideally suited for efficient energy storage and conversion; however, one of the limiting factors to high performance is the poor stability and insufficient electrocatalytic activity for oxygen reduction and evolution of the air electrode exposed to the high concentration of steam. Here we report our findings in enhancing the electrochemical activity and durability of a perovskite-type air electrode, Ba0.9Co0.7Fe0.2Nb0.1O3-δ (BCFN), via a water-promoted surface restructuring process. Under properly-controlled operating conditions, the BCFN electrode is naturally restructured to an Nb-rich BCFN electrode covered with Nb-deficient BCFN nanoparticles. When used as the air electrode for a fuel-electrode-supported R-PCEC, good performances are demonstrated at 650 °C, achieving a peak power density of 1.70 W cm-2 in the fuel cell mode and a current density of 2.8 A cm-2 at 1.3 V in the electrolysis mode while maintaining reasonable Faradaic efficiencies and promising durability.

Mangrove Root-Inspired Carbon Nanotube Film for Micro-Direct Methanol Fuel Cells.

The functional microporous layer, acting as a mass-transfer control medium with a rational structure and surface morphology as well as high electrical conductivity, significantly affects the performance of micro-direct methanol fuel cells (µDMFCs). Bioinspired by the architecture and multi-functional properties of mangrove roots, this study develops a simple and versatile strategy based on magnetron sputtering and chemical vapor deposition to fabricate a mangrove root-inspired carbon nanotube film (MR-CNTF) as the functional interface in µDMFCs. It has features such as ultralightweight, high porosity, and good electrical conductivity. During the synthesis process, an apex-growth model of CNTF is identified. The results indicate that the MR-CNTF used as a cathodic microporous layer can remarkably facilitate the oxygen transport and water management. Because of its multi-functional structure and excellent material characteristics, the passive µDMFC displays a peak power density of 14.9 mW cm-2 at 68 mA cm-2. This value is 88.6% higher than the highest power density of the one based on a carbon nanotube array (7.9 mW cm-2) and 45% higher than that of the conventional carbon black (10.7 mW cm-2). We believe that this novel material with its multi-functional structure illuminates a promising application for fuel cells and other energy storage and conversion devices.

High-Performance and Highly Safe Solvate Ionic Liquid-Based Gel Polymer Electrolyte by Rapid UV-Curing for Lithium-Ion Batteries.

Utilizing ionic liquids (ILs) with low flammability as the precursor component for a gel polymer electrolyte is a smart strategy out of safety concerns. Solvate ionic liquids (SILs) consist of equimolar lithium bis(trifluoromethylsulfonyl)imide and tetraglyme, alleviating the main problems of high viscosity and low Li+ conductivity of conventional ILs. In this study, within a very short time of 30 s, a SIL turns immobile using efficient and controllable UV-curing with an ethoxylated trimethylolpropane triacrylate (ETPTA) network, forming a homogeneous SIL-based gel polymer electrolyte (SGPE) with enhanced thermal stability (216 °C), robust mechanical strength (compression modulus: 1.701 MPa), and high ionic conductivity (0.63 mS cm-1 at room temperature). A Li|SGPE|LiFePO4 cell demonstrates high charge/discharge reversibility and cycling stability with a capacity retention rate of 99.7% after 750 cycles and an average Coulombic efficiency of 99.7%, owing to its excellent electrochemical compatibility with Li-metal. A close-contact electrode/electrolyte interface is formed by in situ curing of the electrolyte on the electrode surface, which enables the pouch full cell to work stably under the conditions of cutting/bending. In view of the excellent mechanical, thermal, and electrochemical performances of SGPE, it is believed to be a promising gel polymer electrolyte for constructing high-safety lithium-ion batteries (LIBs).

Facile Room-Temperature Synthesis of a Highly Active and Robust Single-Crystal Pt Multipod Catalyst for Oxygen Reduction Reaction.

Economical production of highly active and robust Pt catalysts on a large scale is vital to the broad commercialization of polymer electrolyte membrane fuel cells. Here, we report a low-cost, one-pot process for large-scale synthesis of single-crystal Pt multipods with abundant high-index facets, in an aqueous solution without any template or surfactant. A composite consisting of the Pt multipods (40 wt %) and carbon displays a specific activity of 0.242 mA/cm2 and a mass activity of 0.109 A/mg at 0.9 V (versus a reversible hydrogen electrode) for oxygen reduction reaction, corresponding to ∼124% and ∼100% enhancement compared with those of the state-of-the-art commercial Pt/C catalyst (0.108 mA/cm2 and 0.054 A/mg). The single-crystal Pt multipods also show excellent stability when tested for 4500 cycles in a potential range of 0.6-1.1 V and another 2000 cycles in 0-1.2 V. More importantly, the superior performance of the Pt multipods/C catalyst is also demonstrated in a membrane electrode assembly (MEA), achieving a power density of 774 mW/cm2 (1.29 A/cm2) at 0.6 V and a peak power density of ∼1 W/cm2, representing 34% and 20% enhancement compared with those of a MEA based on the state-of-the-art commercial Pt/C catalyst (576 and 834 mW/cm2).

Evaluation of the Volumetric Activity of the Air Electrode in a Zinc-Air Battery Using a Nitrogen and Sulfur Co-doped Metal-free Electrocatalyst.

While numerous oxygen electrocatalysts have been reported to enhance zinc-air battery (ZAB) performance, highly efficient electrocatalysts for the oxygen electrocatalysis need to be developed for broader commercialization of ZABs. Furthermore, areal (instead of volumetric) power density has been used to benchmark the performance of ZABs, often causing ambiguities or confusions. Here, we propose a methodology for evaluating the performance of a ZAB using the volumetric (rather than the areal) power density by taking into consideration the air electrode thickness. A nitrogen and sulfur co-doped metal-free oxygen reduction electrocatalyst (N-S-PC) is used as a model catalyst for this new metric. The electrocatalyst exhibited a half-wave potential of 0.88 V, which is similar to that of the Pt/C electrocatalyst (0.89 V) due to the effects of co-doping and a highly mesoporous structure. In addition, the use of volumetric activity allows fair comparison among different types of air electrodes. The N-S-PC-loaded air electrode demonstrated a higher peak power density (5 W cm-3) than the carbon felt or paper electrode in the ZAB test under the same testing conditions.