Controllable Crystallization of Two-Dimensional Bi Nanocrystals with Morphology-Boosted CO2 Electroreduction in Wide pH Environments.

Two-dimensional low-melting-point (LMP) metal nanocrystals are attracting increasing attention with broad and irreplaceable applications due to their unique surface and topological structures. However, the chemical synthesis, especially the fine control over the nucleation (reduction) and growth (crystallization), of such LMP metal nanocrystals remains elusive as limited by the challenges of low standard redox potential, low melting point, poor crystalline symmetry, etc. Here, a controllable reduction-melting-crystallization (RMC) protocol to synthesize free-standing and surfactant-free bismuth nanocrystals with tunable dimensions, morphologies, and surface structures is presented. Especially, ultrathin bismuth nanosheets with flat or jagged surfaces/edges can be prepared with high selectivity. The jagged bismuth nanosheets, with abundant surface steps and defects, exhibit boosted electrocatalytic CO2 reduction performances in acidic, neutral, and alkaline aqueous solutions, achieving the maximum selectivity of near unity at the current density of 210 mA cm-2 for formate evolution under ambient conditions. This work creates the RMC pathway for the synthesis of free-standing two-dimensional LMP metal nanomaterials and may find broader applicability in more interdisciplinary applications.

Construction of Interlayer Conjugated Links in 2D Covalent Organic Frameworks via Topological Polymerization.

Two-dimensional covalent organic frameworks (2D COFs) are well-defined polymeric sheets that usually stack in an eclipsed mode via van der Waals forces. Extensive efforts have been made to manipulate interlayer interactions, yet there still lack a way to construct conjugated connections between adjacent layers, which is important for (opto)electronic-related applications. Herein, we report an interlayer topological polymerization strategy to transform the well-organized diacetylene columnar arrays in three different 2D COFs (TAPFY-COF, TAPB-COF, and TAPP-COF) into conjugated enyne chains upon heating in the solid state. The resultant COFs (COF-P) with retained high crystallinity possess broadened absorption bands and narrowed band gaps. The newly formed conjugated chains provide extra charge carrier pathways through direct π-electron delocalization. As a proof-of-concept, after topological polymerization, the conductivity of the TAPFY-COF film achieves 2.8 × 10-4 S/cm without doping, and the photothermal, photoacoustic, and oxygen reduction catalytic performance of TAPP-COF is significantly improved.

Metal-Organic Framework Membranes Encapsulating Gold Nanoparticles for Direct Plasmonic Photocatalytic Nitrogen Fixation.

Photocatalytic nitrogen fixation reaction can harvest the solar energy to convert the abundant but inert N2 into NH3. Here, utilizing metal-organic framework (MOF) membranes as the ideal assembly of nanoreactors to disperse and confine gold nanoparticles (AuNPs), we realize the direct plasmonic photocatalytic nitrogen fixation under ambient conditions. Upon visible irradiation, the hot electrons generated on the AuNPs can be directly injected into the N2 molecules adsorbed on Au surfaces. Such N2 molecules can be additionally activated by the strong but evanescently localized surface plasmon resonance field, resulting in a supralinear intensity dependence of the ammonia evolution rate with much higher apparent quantum efficiency and lower apparent activation energy under stronger irradiation. Moreover, the gas-permeable Au@MOF membranes, consisting of numerous interconnected nanoreactors, can ensure the dispersity and stability of AuNPs, further facilitate the mass transfer of N2 molecules and (hydrated) protons, and boost the plasmonic photocatalytic reactions at the designed gas-membrane-solution interface. As a result, an ammonia evolution rate of 18.9 mmol gAu-1 h-1 was achieved under visible light (>400 nm, 100 mW cm-2) with an apparent quantum efficiency of 1.54% at 520 nm.

The Emerging of Aqueous Zinc-Based Dual Electrolytic Batteries.

As high performance and safety alternatives to the batteries with organic electrolytes, aqueous zinc-based batteries are still far from satisfactory in practical use because of the limitation of the intercalation reaction mechanism and the strict requirements for the cathodes. Very recently, zinc-based dual electrolytic batteries (DEBs), where the cathode and anode are both based on reversible electrolytic reactions, are emerging. It features with electrode-free configuration, thus avoiding the preliminary active materials or electrode fabrication procedures. Meanwhile, the new battery chemistry typically possesses a high specific capacity, output voltage, faster reaction rates, and long cycling life. Herein, the advances of the development of various zinc-based DEBs, including Zn-MnO2 , Zn-Br2 , and Zn-I2 DEBs, are systematically summarized. This review will focus on the working mechanisms of these batteries and how the decoupling catholyte and anolyte affect their output voltages. The perspectives of the opportunities and challenges are also suggested in the aspects of protecting zinc anode, enhancing volumetric energy density, suppressing fast self-discharge, and developing multifunctional integrated zinc-based DEBs.

Urban growth drives trait composition of urban spontaneous plant communities in a mountainous city in China.

Urban ecosystems feature intense anthropogenic activities and environmental stressors that filter species with varying life-history traits. The traits therefore provide an essential aspect to understanding how species respond to urban environments. We conducted this study in Chongqing, a mountainous city in southwestern China, and tested the hypothesis that the velocity of urban growth can alter functional compositions of urban plant communities through selection on species' taxonomic distributions and functional traits. We found that for most traits, their values spanned a wide range across the 70 spontaneous species in this study, and seed size and leaf element composition played a key role in contributing to the functional differentiation among species. At the same time, urban growth intensity was negatively correlated with leaf N concentration, the N:P ratio, and specific leaf area (SLA), and positively correlated with the leaf C:N ratio. This suggests that species in urban centers are associated with an acquisitive nutrient-use strategy and may gain strong competitive strategies to be favored by greater selective pressure in those long-term urban centers. Lastly, we show that urbanization as a strong filter tends to reduce the chance of species with unique traits for the spontaneous plant communities. Our study offers insights into mechanisms through which spontaneous plant communities are filtered by urbanization with a special focus on the ecological consequences of the velocity of urban growth.

Decarboxylation-Induced Defects in MOF-Derived Single Cobalt Atom@Carbon Electrocatalysts for Efficient Oxygen Reduction.

Developing transition metal single-atom catalysts (SACs) for oxygen reduction reaction (ORR) is of great importance. Zeolitic imidazolate frameworks (ZIFs) as a subgroup of metal-organic frameworks (MOFs) are distinguished as SAC precursors, due to their large porosity and N content. However, the activity of the formed metal sites is limited. Herein, we report a decarboxylation-induced defects strategy to improve their intrinsic activity via increasing the defect density. Carboxylate/amide mixed-linker MOF (DMOF) was chosen to produce defective Co SACs (Co@DMOF) by gas-transport of Co species to DMOF upon heating. Comparing with ZIF-8 derived SAC (Co@ZIF-8-900), Co@DMOF-900 with more defects yet one fifth Co content and similar specific double-layer capacitance show better ORR activity and eight times higher turnover frequency (2.015 e s-1 site-1 ). Quantum calculation confirms the defects can weaken the adsorption free energy of OOH on Co sites and further boost the ORR process.

Metal-Triazolate-Framework-Derived FeN4 Cl1 Single-Atom Catalysts with Hierarchical Porosity for the Oxygen Reduction Reaction.

The construction of single-atom catalysts (SACs) with high single atom densities, favorable electronic structures and fast mass transfer is highly desired. We have utilized metal-triazolate (MET) frameworks, a subclass of metal-organic frameworks (MOFs) with high N content, as precursors since they can enhance the density and regulate the electronic structure of single-atom sites, as well as generate abundant mesopores simultaneously. Fe single atoms dispersed in a hierarchically porous N-doped carbon matrix with high metal content (2.78 wt %) and a FeN4 Cl1 configuration (FeN4 Cl1 /NC), as well as mesopores with a pore:volume ratio of 0.92, were obtained via the pyrolysis of a Zn/Fe-bimetallic MET modified with 4,5-dichloroimidazole. FeN4 Cl1 /NC exhibits excellent oxygen reduction reaction (ORR) activity in both alkaline and acidic electrolytes. Density functional theory calculations confirm that Cl can optimize the adsorption free energy of Fe sites to *OH, thereby promoting the ORR process. The catalyst demonstrates great potential in zinc-air batteries. This strategy selects, designs, and adjusts MOFs as precursors for high-performance SACs.

Metal organic framework MIL-53(Fe) as an efficient artificial oxidase for colorimetric detection of cellular biothiols.

Biothiols play critical roles in many biological processes and their aberrant is related to a variety of syndromes. A simple and reliable colorimetric method is developed in this work for biothiols detection based on an oxidase mimic, a metal organic framework (MOF) MIL-53(Fe), and a peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB). In this design, MIL-53(Fe) is utilized to catalyze the conversion of TMB to a blue colored 3,3',5,5'-tetramethylbenzidine diimine, which can be read on a spectrophotometer at 652 nm. The oxidation-induced blue color generation can be efficiently inhibited by biothiols, thus a colorimetric analytical method is proposed for biothiols detection based on the above system. Under optimal conditions, a linear relationship in a range from 1 to 100 µM and a limit of detection (LOD) at 120 nM are achieved with Cys as a model target. The developed platform is further applied to evaluate cellular biothiols in normal (RWPE-1) and cancer (LNCap) cell lines, revealing that the overall biothiols level in LNCap is much higher than that in RWPE-1. This work renders a powerful tool for identifying cancer cells in a simple manner for biomedical diagnosis associated with biothiols.

Efficient direct repairing of lithium- and manganese-rich cathodes by concentrated solar radiation.

Lithium- and manganese-rich layered oxide cathode materials have attracted extensive interest because of their high energy density. However, the rapid capacity fading and serve voltage decay over cycling make the waste management and recycling of key components indispensable. Herein, we report a facile concentrated solar radiation strategy for the direct recycling of Lithium- and manganese-rich cathodes, which enables the recovery of capacity and effectively improves its electrochemical stability. The phase change from layered to spinel on the particle surface and metastable state structure of cycled material provides the precondition for photocatalytic reaction and thermal reconstruction during concentrated solar radiation processing. The inducement of partial inverse spinel phase is identified after concentrated solar radiation treatment, which strongly enhances the redox activity of transition metal cations and oxygen anion, and reversibility of lattice structure. This study sheds new light on the reparation of spent cathode materials and designing high-performance compositions to mitigate structural degradation.

Phase Change Nanocapsules Enabling Dual-Mode Thermal Management for Fast-Charging Lithium-Ion Batteries.

The fast-charging performance of conventional lithium-ion batteries (LIBs) is determined by the working temperature. LIBs may fail to work under harsh conditions, especially in the low-temperature range of the local environment or in the high-temperature circumstances resulting from the release of substantial Joule heating in the short term. Constructing a thermal engineering framework for thermal regulation and maintaining the battery running at an appropriate temperature range are feasible strategies for developing temperature-tolerant, fast-charging LIBs. In this work, we prepare phase change nanocapsules as a thermal regulating layer on the cell surface. The polyurea shells of the nanocapsules are decorated with polyaniline, where the molecular vibration of polyaniline is enhanced under solar irradiation, enabling light-to-heat conversion that achieves an effective temperature increment at low temperatures. Based on the large latent heat storage capability of the n-octadecane core in the nanocapsules, the thermal regulating layer is sufficient to modulate strong heat release when operating LIBs at a high current rate, which efficiently prevents strong side reactions at high temperatures or even the occurrence of thermal runaway. This work highlights the promise of optimizing the operating temperature with a thermal regulator to ensure the safety and performance stability of fast-charging LIBs.

Multiple H-Bonding Cross-Linked Supramolecular Solid-Solid Phase Change Materials for Thermal Energy Storage and Management.

Solid-solid phase change materials (SSPCMs) are considered among the most promising candidates for thermal energy storage and management. However, the application of SSPCMs is consistently hindered by the canonical trade-off between high TES capacity and mechanical robustness. In addition, they suffer from poor recyclability due to chemical cross-linking. Herein, a straightforward but effective strategy for fabricating supramolecular SSPCMs with high latent heat and mechanical strength is proposed. The supramolecular polymer employs multiple H-bonding interactions as robust physical cross-links. This enables SSPCM with a high enthalpy of phase transition (142.5 J g-1 ), strong mechanical strength (36.9 MPa), and sound shape stability (maintaining shape integrity at 120 °C) even with a high content of phase change component (97 wt%). When SSPCM is utilized to regulate the operating temperature of lithium-ion batteries, it significantly diminishes the battery working temperature by 23 °C at a discharge rate of 3 C. The robust thermal management capability enabled through solid-solid phase change provides practical opportunities for applications in fast discharging and high-power batteries. Overall, this study presents a feasible strategy for designing linear SSPCMs with high latent heat and exceptional mechanical strength for thermal management.

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To explore the effects of different electron acceptors on soil methane emission and responses of soil microorganisms to different light conditions, a strict anaerobic 20-day incubation experiment was conducted with eight treatments: darkness + Fe3+ (DF); darkness + NO3- (DN); darkness +SO42- (DS); darkness + distilled water (DCK); light + Fe3+ (LF); light + NO3- (LN); light +SO42- (LS); light + distilled water (LCK). The changes of methane concentration in the anaerobic incubation flask and the variation of the abundance of bacteria, archaea, fungi and six soil functional genes were analyzed. Results showed that soil methane emission under NO3-, SO42- addition and control (CK) was significantly lower under light conditions than dark, except the Fe3+ treatment. DN, DCK and LF treatments had the highest abundance of bacteria, fungi and archaea genes, respectively. The gene abundance of methanogenic mcrA, sulfate-reducing bacteria Dsr, and carbon-fixing CbbL were significantly up-regulated in the LF, while that of methanotrophs pmoA, iron-reducing bacteria Geo, and denitrifying bacteria nosZ were significantly up-regulated in the LN, DCK and LCK, respectively. Results of Pearson correlation and RDA analysis showed that CH4 emission was significantly positively correlated with CO2 concentration, pH, ammonium-nitrogen, and total N contents, and negatively correlated with N2O concentration, Eh, nitrate, and total C contents. Under dark condition, methane emission was positively correlated with archaea and pmoA genes abundance, and negatively correlated with other genes abundance. Under light condition, methane emission was negatively correlated with the abundance of soil microbe and functional genes. In general, methane emission under light condition was significantly lower than that under dark condition (except for the Fe3+ treatment). These results showed that it was helpful to reduce methane emission under light condition, but the increase or decrease of methane emission was closely related to the type of electron acceptors and the functional responses of soil micro-organisms.

Fast constructing polarity-switchable zinc-bromine microbatteries with high areal energy density.

Microbatteries (MBs) are promising candidates to provide power for various miniaturized electronic devices, yet they generally suffer from complicated fabrication procedures and low areal energy density. Besides, all cathodes of current MBs are solid state, and the trade-off between areal capacity and reaction kinetics restricts their wide applications. Here, we propose a dual-plating strategy to facilely prepare zinc-bromine MBs (Zn-Br2 MBs) with a liquid cathode to achieve both high areal energy density and fast kinetics simultaneously. The Zn-Br2 MBs deliver a record high areal energy density of 3.6 mWh cm-2, almost an order of magnitude higher than available planar MBs. Meanwhile, they show a polarity-switchable feature to tolerate confusion of cathode and anode. This strategy could also be extended to other battery systems, such as Zn-I2 and Zn-MnO2 MBs. This work not only proposes an effective construction method for MBs but also enriches categories of microscale energy storage devices.

Enabling fast-charging selenium-based aqueous batteries via conversion reaction with copper ions.

Selenium (Se) is an appealing alternative cathode material for secondary battery systems that recently attracted research interests in the electrochemical energy storage field due to its high theoretical specific capacity and good electronic conductivity. However, despite the relevant capacity contents reported in the literature, Se-based cathodes generally show poor rate capability behavior. To circumvent this issue, we propose a series of selenium@carbon (Se@C) composite positive electrode active materials capable of delivering a four-electron redox reaction when placed in contact with an aqueous copper-ion electrolyte solution (i.e., 0.5 M CuSO4) and copper or zinc foils as negative electrodes. The lab-scale Zn | |Se@C cell delivers a discharge voltage of about 1.2 V at 0.5 A g-1 and an initial discharge capacity of 1263 mAh gSe-1. Interestingly, when a specific charging current of 6 A g-1 is applied, the Zn | |Se@C cell delivers a stable discharge capacity of around 900 mAh gSe-1 independently from the discharge rate. Via physicochemical characterizations and first-principle calculations, we demonstrate that battery performance is strongly associated with the reversible structural changes occurring at the Se-based cathode.

Hybrid Poly(AMPS-CS)-Au Microneedle Arrays to Enrich Metabolites from Skin for Early Disease Diagnosis.

Recently, some metabolites in skin interstitial fluid (SIF) have become emerging re×sources for early disease diagnosis. However, their low level in SIF and difficulty to sampling are the biggest obstacle to further potential application. Here, a swellable microneedle array patch (MNAP) with high mechanical strength is presented, and the rapid enrichment of positively charged metabolites is achieved. The MNAP is fabricated by poly (chondroitin sulfate-acrylamido-2-methylpropane sulfonic acid)-gold nanoparticles (GNPs) composites via a micro-molding. The negatively charged copolymer hydrogel not only enrich positively charged metabolites, but also provide swellable capacity. The in situ synthesis of GNPs in the process of copolymerization make the GNPs cross-link to the hydrogel, which further enhance the MNAP mechanical strength and enrichment efficiency for positively charged metabolites. By using the MNAP, around 5 mg SIF in 10 min from the high fat/cholecalciferol/methimazole-induced atherogenesis rat is extracted and 23 metabolites including 13 quaternary ammonium cationic compounds can be detected and quantified by using a LC-QTOF-MS. Dysregulated L-carnitine and choline metabolism are discovered a week earlier in the SIF than in the serum, achieving early diagnosis of the metabolism syndrome disease. This MNAP also helps users complete home sampling for early disease diagnosis and monitoring.

A Cascade Battery: Coupling Two Sequential Electrochemical Reactions in a Single Battery.

Currently, rechargeable electrochemical batteries generally operate on one reversible electrochemical reaction during discharging and charging cycles. Here, a cascade battery that couples two sequential electrochemical reactions in a single battery is proposed. Such a concept is demonstrated in an aqueous Zn-S hybrid battery, where solid sulfur serves as the cathode in the first discharge step and the generated Cu2 S catalyzes Cu2+ reduce to Cu/Cu2 O to provide the second discharge step. The cascade battery shows many merits compared to traditional batteries. First, it integrates two batteries internally, eliminating the use of additional inactive connecting materials required for external integration. Second, it can more fully utilize the inactive reaction chamber of the battery than traditional batteries. Third, cascade battery can bypass the challenges of thick solid electrode to access high areal capacity. An ultrahigh areal capacity of 48 mAh cm-2 is achieved even at a low solid cathode loading (9.6 mg cm-2 ). The cascade battery design breaks the stereotype of conventional battery configuration, providing a paradigm for constructing two-in-one batteries.

Modulating the electrocatalytic CO2 reduction performances of bismuth nanoparticles with carbon substrates with controlled degrees of oxidation.

The catalytic performances of metal nanoparticles can be widely tuned and promoted by the metal-support interactions. Here, we report that the morphologies and electrocatalytic CO2 reduction reaction (CO2RR) properties of bismuth nanoparticles (BiNPs) can be rationally modulated by their interactions with carbon black (CB) supports by controlling the degree of surface oxidation. Appropriately oxidized CB supports can provide sufficient oxygen-containing groups for anchoring BiNPs with tunable sizes and surface areas, desirable key intermediate adsorption abilities, appropriate surface wettability, and adequate electron transfer abilities. As a result, the optimized Bi/CB catalysts exhibited a promoted CO2RR performance with a Faradaic efficiency of 94% and a current density of 16.7 mA cm-2 for HCOO- at -0.9 V versus a reversible hydrogen electrode. Our results demonstrate the significance of regulating the interactions between supports and metal nanoparticles for both synthesis of the catalyst and electrolysis applications, which may find broader applicability in more electrocatalyst designs.

Dendritic cells reprogrammed by CEA messenger RNA loaded multi-functional silica nanospheres for imaging-guided cancer immunotherapy.

The application and understanding of dendritic cell (DC) based immune cancer therapy are largely hindered by insufficient or improper presentation of antigens and the inability to track the homing of reprogrammed DCs to draining lymph nodes in real-time. To tackle these challenges, multi-functional and hierarchically structured silica nanospheres are rationally designed and fabricated, which encapsulate quantum dots to permit near infrared deep tissue imaging and are loaded with carcinoembryonic antigen messenger RNA (CEAmRNA) to enable stable and abundant antigen expression in DCs. After being injected into animals and inducing an antigen-specific immune response, the homing process of reprogrammed labelled DCs from peripheral tissues to draining lymph nodes can be simultaneously and precisely tracked. Significant inhibition of tumor growth is achieved via strong antigen-specific immune responses including induced DC maturation, enhanced T cell proliferation and cytotoxic T lymphocyte (CTL)-mediated responses. Both in vitro and in vivo experiments demonstrate the high effectiveness of this new strategy of imaging-guided cancer immunotherapy by using reprogrammed DCs as immunotherapeutic and tracking agents.

Nitrogen-Doped Carbon as a Host for Tellurium for High-Rate Li-Te and Na-Te Batteries.

A nitrogen-doped hierarchical porous carbon sponge, used as a matrix for tellurium accommodation, was designed and prepared in this work. The porosity of the matrix played an important role in enhancing the electrochemical performance of Li/Na-Te batteries. Specifically, the mesopores could accommodate active materials whereas the macropores provided sufficient space for partial Te accommodation and volume expansion in discharge. In addition, N heteroatoms in carbon species could enhance the electrical conductivity and widen its application in lithium/sodium storage. The monolithic and flaky architecture of the nitrogen-doped hierarchical porous carbon sponge/tellurium composite offered a highly conductive network for fast electron transportation. As a result, the nitrogen-doped hierarchical porous carbon sponge/tellurium composite achieved a superior rate performance for Li-Te and Na-Te batteries.

Manipulating irreversible phase transition of NaCrO2 towards an effective sodium compensation additive for superior sodium-ion full cells.

During the first charge process of full cells, a solid electrolyte interphase (SEI) film is formed when the active ion from the cathode is consumed, resulting in irreversible capacity loss. This phenomenon has shown to be more serious in sodium-ion full cells than in lithium-ion full cells. Although many strategies have been employed to alleviate the loss of sodium ions, such as presodiation and construction of an artificial solid electrolyte interface, they are both cumbersome and time-consuming. For the first time, NaCrO2 was used as an effective self-sacrificing sodium compensation additive in sodium-ion full cells due to the irreversible phase transition of NaCrO2 in a high voltage region can deliver an irreversible capacity of up to 230 mAh g-1. Based on this design, sodium-ion full cells coupled with hard carbon as the anode exhibited higher capacity, less polarization, greater energy density, and superior cycle stability than those of a pristine electrode. This is mainly attributed to the removal of sodium ions from NaCrO2, which compensates for the loss of sodium ions consumed during the formation of the SEI film on the anode surface during the first charge process. Overall, this work opens up a new avenue for exploring sodium compensation strategy and contributing to practical application of sodium-ion full cells.