[Effects of Exogenous Plant Hormone Spraying on the Phytoremediation by Bidens pilosa L. in Cadmium-contaminated Soil].

To explore the effect of exogenous plant hormone spraying on the absorption of heavy metals by hyperaccumulated plants, Bidens pilosa L. was selected as the tested plant owing to the large biomass, short growth cycle, and high accumulation efficiency. Here, the effect of foliar spraying 6-benzylaminopurine (6-BA), salicylic acid (SA), and 24-epi-brassinosteroid (24-EBR) on the remediation of cadmium (Cd)-contaminated soil by B. pilosa L. was examined. The results showed:① the efficiency of the remediation in Cd-contaminated soil by B. pilosa L. was effectively enhanced after the spraying of all three kinds of exogenous plant hormones with appropriate concentrations. The spraying of the three exogenous plant hormones could promote the cadmium concentration in the leaves of B. pilosa L. to increase by 4.21%, 31.79%, and 14.89%; promote the translocation factor (TF) to increase by 9.67%, 18.83%, and 17.85%; promote the phytoextraction rates (PR) to increase by 15.36%, 32.33%, and 64.38%, respectively. ② The growth of B. pilosa L. was significantly promoted after the spraying of the three kinds of exogenous plant hormones with appropriate concentrations. The spraying of the three exogenous plant hormones could promote plant growth under cadmium stress, and the dry weight of the plant root, stem, and leaf was increased by 37.53%, 74.50%, and 104.02%, respectively. ③ The photosynthesis of B. pilosa L. was significantly enhanced after the spraying of the three kinds of exogenous plant hormones with appropriate concentrations. The chlorophyll concentration of the plant was significantly increased after foliar spraying with plant hormones, and the concentration of chlorophyll a was increased by 79.31%, 92.27%, and 51.12%; the photochemical quenching coefficient (qP) was increased by 11.32%, 89.16%, and 78.43%; and the non-photochemical quenching coefficient (NPQ) was increased by 51.71%, 241.12%, and 27.85%, respectively, after foliar spraying with appropriate concentrations of 6-BA, SA, and 24-EBR. ④ The antioxidant capacity of B. pilosa L. was significantly strengthened after the spraying of the three kinds of exogenous plant hormones with appropriate concentrations. The malondialdehyde (MDA) concentration of the plant was reduced by 62.41%, 68.67%, and 46.76% after the application of 6-BA, SA, and 24-EBR, respectively. Meanwhile, superoxide dismutase (SOD) was increased by 68.33%, 10.28%, and 6.17%, and catalase (CAT) was increased by 31.43%, 37.87%, and 37.31%, respectively. Generally, the spraying of exogenous 6-BA, SA, and 24-EBR with the appropriate concentration under Cd stress could significantly increase the biomass of B. pilosa L. and promote the accumulation of heavy metals in the plant, improve the photosynthetic ability of the plant, reduce the oxidative damage of the plant under heavy metal stress, enhance the antioxidant capacity, and improve the absorption and tolerance of plants to Cd. It also could promote the transfer of Cd from roots to shoots, improve the phytoextraction rates of Cd from the plant, and effectively strengthen the phytoremediation efficiency. Among them, 30 mg·L-1 SA foliar spraying had the best effect.

Decoupling Electrochromism and Energy Storage for Flexible Quasi-Solid-State Aqueous Electrochromic Batteries with High Energy Density.

Currently, reported aqueous electrochromic batteries (ECBs) show only limited capacity with insufficient energy density and power density. Such a limitation is naturally imposed by the rationale that the cathode of ECBs stores charge by an ion intercalation/deintercalation mechanism, where the inherent inhibition of ion diffusion and structural collapse of cathode materials through repetitive charge/discharge cycles lead to low areal capacity and unsatisfactory electrochemical performance with short lifetime. Herein, we decouple the dual functions of electrochromism and energy storage in conventional cathodes of ECBs by introducing a polyaniline/triiodide composite cathode that is in situ formed by direct electrolysis of an iodide-based quasi-solid-state aqueous electrolyte during charging. When paired with a zinc metal anode, the composite cathode can synergistically utilize the electrochromic property of polyaniline, the high-efficiency energy storage of the Zn-I2 system, as well as the effective anchorage of polyiodide by polyaniline to suppress the shuttle effect of triiodide. By selecting 1-butyl-3-methylimidazolium ion (BMI+) as the cation, a liquid-solid cathode/quasi-solid-state electrolyte interface can be achieved to facilitate the interfacial charge transfer, rendering quasi-solid-state aqueous electrochromic batteries with a high areal capacity of 1363 µAh cm-2, energy density of 1650 µWh cm-2, and power density of 5186 µW cm-2.

Ultrafast Synthesis of Metal-Layered Hydroxides in a Dozen Seconds for High-Performance Aqueous Zn (Micro-) Battery.

Efficient synthesis of transition metal hydroxides on conductive substrate is essential for enhancing their merits in industrialization of energy storage field. However, most of the synthetic routes at present mainly rely on traditional bottom-up method, which involves tedious steps, time-consuming treatments, or additional alkaline media, and is unfavorable for high-efficiency production. Herein, we present a facile, ultrafast and general avenue to synthesize transition metal hydroxides on carbon substrate within 13 s by Joule-heating method. With high reaction kinetics caused by the instantaneous high temperature, seven kinds of transition metal-layered hydroxides (TM-LDHs) are formed on carbon cloth. Therein, the fastest synthesis rate reaches ~ 0.46 cm2 s-1. Density functional theory calculations further demonstrate the nucleation energy barriers and potential mechanism for the formation of metal-based hydroxides on carbon substrates. This efficient approach avoids the use of extra agents, multiple steps, and long production time and endows the LDHs@carbon cloth with outstanding flexibility and machinability, showing practical advantages in both common and micro-zinc ion-based energy storage devices. To prove its utility, as a cathode in rechargeable aqueous alkaline Zn (micro-) battery, the NiCo LDH@carbon cloth exhibits a high energy density, superior to most transition metal LDH materials reported so far.

Co3O4-MoSe2@C nanocomposite as a multi-functional catalyst for electrochemical water splitting and lithium-oxygen battery.

Co3O4-MoSe2@C nanocomposite has been prepared by a convenient method via combining hydrothermally synthesized MoSe2@C and Co3O4. When catalyzing the hydrogen evolution reaction and oxygen evolution reaction, the catalyst features low overpotentials of 144 mV and 360 mV (both at 10 mA cm-2current density), respectively. It can also serve as the cathode in the lithium-oxygen battery and the device shows a low charging-discharging overpotential of 1.50 V with a stable performance of over 200 cycles at current density of 1000 mA g-1, shedding light on the design and synthesis of novel multifunctional electrocatalysts for energy conversions.

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.

A Flexible Aqueous Zinc-Iodine Microbattery with Unprecedented Energy Density.

Currently, reported aqueous microbatteries (MBs) only show unsatisfactory electrochemical performance (≤120 mWh cm-3 volumetric energy density and <1000 µWh cm-2 areal energy density) and it remains challenging to develop durable aqueous MBs that can simultaneously offer both high volumetric and areal energy density. Herein, an in situ electrodeposition strategy is adopted to construct a flexible aqueous zinc-iodine MB (ZIDMB). Notably, the fabrication process well avoids the use of common additives (such as binders, conductive agents, and toxic solvent) and also bypasses subsequent time-consuming procedures such as grinding, coating, drying, etc., thus greatly simplifying the manufacture of the ZIDMB. Meanwhile, owing to the suppression of the shuttle effect of triiodide ions and the high ionic conductivity of the polyelectrolyte, the ZIDMB can simultaneously deliver record-high volumetric and areal energy densities of 1647.3 mWh cm-3 and 2339.1 µWh cm-2 , thus achieving values at least 13.5- and 2.3-fold better than those of best available aqueous MBs, respectively. This work affords an innovative strategy to construct an ideal micro-power-source for future miniaturized and integrated electronics.

In Situ Formation of Surface-Induced Oxygen Vacancies in Co9S8/CoO/NC as a Bifunctional Electrocatalyst for Improved Oxygen and Hydrogen Evolution Reactions.

Creating oxygen vacancies and introducing heterostructures are two widely used strategies in Co-based oxides for their efficient electrocatalytic performance, yet both strategies have rarely been used together to design a bifunctional electrocatalyst for an efficient overall water splitting. Herein, we propose a facile strategy to synthesize oxygen-defect-rich Co9S8/CoO hetero-nanoparticles with a nitrogen-doped carbon shell (ODR-Co9S8/CoO/NC) through the in situ conversion of heterojunction along with surface-induced oxygen vacancies, simply via annealing the precursor Co3S4/Co(OH)2/ZIF-67. The as-prepared ODR-Co9S8/CoO/NC shows excellent bifunctional catalytic activities, featuring a low overpotential of 217 mV at 10 mA cm-2 in the oxygen evolution reaction (OER) and 160 mV at 10 mA cm-2 in the hydrogen evolution reaction (HER). This performance excellency is attributed to unique heterostructure and oxygen defects in Co9S8/CoO nanoparticles, the current work is expected to offer new insights to the design of cost-effective, noble-metal-free electrocatalysts.

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.

Efficient and Stable Large-Area Perovskite Solar Cells with Inorganic Perovskite/Carbon Quantum Dot-Graded Heterojunction.

This work reports on a compositionally graded heterojunction for photovoltaic application by cooperating fluorine-doped carbon quantum dots (FCQDs in short) into the CsPbI2.5Br0.5 inorganic perovskite layer. Using this CsPbI2.5Br0.5/FCQDs graded heterojunction in conjunction with low-temperature-processed carbon electrode, a power conversion efficiency of 13.53% for 1 cm2 all-inorganic perovskite solar cell can be achieved at AM 1.5G solar irradiation. To the best of our knowledge, this is one of the highest efficiency reported for carbon electrode based all-inorganic perovskite solar cells so far, and the first report of 1 cm2 carbon counter electrode based inorganic perovskite solar cell with PCE exceeding 13%. Moreover, the inorganic perovskite/carbon quantum dot graded heterojunction photovoltaics maintained over 90% of their initial efficiency after thermal aging at 85° for 1056 hours. This conception of constructing inorganic perovskite/FCQDs graded heterojunction offers a feasible pathway to develop efficient and stable photovoltaics for scale-up and practical applications.

Laser-Assisted Fabrication of Microphotocapacitors with High Energy Density and Output Voltage.

Self-powered devices have great potential in daily applications ranging from portable electronics to wearable body sensors, yet their working lifetime and performance are normally limited by the low energy density of the power unit as well as additional resistive losses induced by connections between electronic and power moieties. Herein, we report an effective programmable laser-assisted fabrication of facilely integrated microphotocapacitors (integrated devices of solar cells and microsupercapacitors, mPCs) exhibiting high output voltage and energy density (32.3 µWh cm-2). An mPC pack (8 mPCs in series within a size of 3 × 3 cm2) delivers an excellent Voc of 7.3 V, and an output voltage of 90 V can be obtained with an array of 14 mPC packs when tested outdoors under solar illumination (63 mW cm-2), setting a new benchmark for integrated self-charging power packs. These devices have also shown good stability (stable operation over 2000 cycles, 2.1 × 104 s) and performance under low- or intermittent-intensity light illuminations, highlighting their abilities to work indoors or under cloudy weather.

Polyaniline/reduced graphene oxide foams as metal-free cathodes for stable lithium-oxygen batteries.

Lithium-oxygen batteries (LOBs) are considered as next-generation energy storage devices owing to their high-energy densities, yet they generally suffer from low actual specific capacity and poor cycle performance. To solve these issues, a range of electrocatalysts have been introduced in the cathode to reduce the overpotential during charge/discharge cycles and minimize unwanted side reactions. Due to relative high costs and limited reserves of noble metals and their compounds, it is important to develop low-cost and efficient metal-free electrocatalysts. Here, we report a simple method to prepare three-dimensional porous polyaniline (PANI)/reduced graphene oxide foams (PPGFs) with different PANI contents via a two-step self-assembly process. When these foams are tested as the cathode in LOBs, the device using the PPGF with 50% PANI content exhibits a discharge capacity up to 36 010 mAh g-1 and an excellent cycling stability (260 cycles at 1000 mAh g-1 and 500 cycles at 500 mAh g-1), provid ing new insights into the design of next-generation metal-free cathodes for LOBs.

Retarding Ostwald Ripening to Directly Cast 3D Porous Graphene Oxide Bulks at Open Ambient Conditions.

Graphene aerogels (GAs) with attractive properties have shown tremendous potentials in energy- and environment-related applications. Unfortunately, current assembly methods for GAs such as sol-gel and freeze-casting processes must be conducted in enclosed spaces with unconventional conditions, thus being literally inoperative for in situ and continuous productions. Herein, a direct slurry-casting method at open ambient conditions is established to arbitrarily prepare three-dimensional (3D) porous graphene oxide (GO) bulks without macroscopic dimension limits on a wide range of solid surfaces by retarding Ostwald ripening of 3D liquid GO foams when being dried in air. A subsequent fast thermal reduction (FTR) of GO foams leads to the formation of graphene aerogels (denoted as FTR-GAs) with hierarchical closed-cellular graphene structures. The FTR-GAs show outstanding high-temperature thermal insulation (70% decrease for 400 °C), as well as superelasticity (>1000 compression-recovery cycles at 50% strain), ultralow density (10-28 mg cm-3), large specific surface area (BET, 206.8 m2 g-1), and high conductivity (ca. 100 S m-1). This work provides a viable method to achieve in situ preparations of high-performance GAs as multifunctional structural materials in aircrafts, high-speed trains, or even buildings for the targets of energy efficiency, comfort, and safety.

Graphene-Based Fibers: Recent Advances in Preparation and Application.

Graphene-based fibers (GBFs) are macroscopic 1D assemblies formed by using microscopic 2D graphene sheets as building blocks. Their unique structure exhibits the same merits as graphene such as low weight, high specific surface area, excellent mechanical/electrical properties, and ease of functionalization. Furthermore, the fibrous nature of GBFs is intrinsically compatible with existing textile technologies, making them suitable for applications in flexible and wearable electronics. Recently, novel synthetic methods have endowed GBFs with new structures and functions, further improving their mechanical and electrical properties. These improvements have rapidly bridged the gaps between laboratory demonstrations and real-life applications in fiber-shaped batteries, supercapacitors, and electrochemical sensors. Recent advances in the fabrication, optimization, and application of GBFs are systematically reviewed and a perspective on their future development is given.

Compact Assembly and Programmable Integration of Supercapacitors.

Microsized supercapacitors (mSCs) with small volume, rapid charge-discharge rate, and ultralong cyclic lifetime are urgently needed to meet the demand of miniaturized portable electronic devices. A versatile self-shrinkage assembling (SSA) strategy to directly construct the compact mSCs (CmSCs) from hydrogels of reduced graphene oxide is reported. A single CmSC is only 0.0023 cm3 in volume, which is significantly smaller than most reported mSCs in fiber/yarn and planar interdigital forms. It exhibits a high capacitance of up to 68.3 F cm-3 and a superior cycling stability with 98% capacitance retention after 25 000 cycles. Most importantly, the SSA technique enables the CmSC as the building block to realize arbitrary, programmable, and multi-dimensional integration for adaptable and complicated power systems. By design on mortise and tenon joint connection, autologous integrated 3D interdigital CmSCs are fabricated in a self-holding-on manner, which thus dramatically reduces the whole device volume to achieve the high-performance capacitive behavior. Consequently, the SSA technique offers a universal and versatile approach for large-scale on-demand integration of mSCs as flexible and transformable power sources.

A 3D-graphene fiber electrode embedded with nitrogen-rich-carbon-coated ZIF-67 for the ultrasensitive detection of adrenaline.

A novel nitrogen-rich-carbon-coated ZIF-67 embedded three-dimensional-graphene (ZIF-67/NC/3DG) fiber was fabricated via a facile one-pot electrodeposition self-assembly method, and used as a prominent electrode for the non-enzymatic detection of adrenaline (Ad). In this design, the prepared ZIF-67 adsorbs Ad through hydrogen bonding and electrostatic interaction, while polypyrrole functions as the precursor of the conductive NC that seamlessly connects ZIF-67 with the 3DG fiber electrode to ameliorate the poor conductivity of the ZIF-67 moiety and thus improve the sensitivity of the ZIF-67/NC/3DG fiber electrode for detecting Ad. The constructed fiber sensor shows a double linear response over the Ad concentration range of 0.06-95 µM with a high sensitivity of 44.6 mA mM-1 cm-2 and 95.0-5900 µM with a good sensitivity of 11.0 mA mM-1 cm-2, giving a low detection limit of 0.02 µM and excellent repeatability. The ZIF-67/NC/3DG fiber electrode was further successfully applied for the determination of Ad in a real sample of human serum, indicating that this fiber electrode is a promising miniaturized sensor for electrochemical analysis.

Efficient Metal-Free Electrocatalysts from N-Doped Carbon Nanomaterials: Mono-Doping and Co-Doping.

N-doped carbon nanomaterials have rapidly grown as the most important metal-free catalysts in a wide range of chemical and electrochemical reactions. This current report summarizes the latest advances in N-doped carbon electrocatalysts prepared by N mono-doping and co-doping with other heteroatoms. The structure-performance relationship of these materials is subsequently rationalized and perspectives on developing more efficient and sustainable electrocatalysts from carbon nanomaterials are also suggested.

Graphitic carbon nitride as polysulfide anchor and barrier for improved lithium-sulfur batteries.

The poor conductivity of sulfur and the shuttle effect of soluble polysulfides have considerably hindered the practical application of lithium-sulfur (Li-S) batteries. Here, we have fabricated a three-dimensional graphitic carbon nitride/reduced graphene oxide (GCN@rGO) network as the sulfur host in Li-S batteries, where the bifunctional GCN strongly binds polysulfides through a chemical interaction and catalyzes the redox reactions of polysulfides. Additionally, GCN coating is also applied to different membranes and when these GCN-coated-membranes (GCMs) are used as separators, they are found to effectively act as the polysulfide barrier to suppress the diffusion of polysulfide intermediates to the Li anode and thus ameliorate the shuttle effect. As a result, the Li-S battery assembled from the GCN@rGO/S cathode and GCM separator exhibited a high initial specific capacity of 1000.6 mAh g-1 at 0.1 C and 87% capacity retention with 0.066% decay per cycle over 200 charge-discharge cycles at 0.5 C.

Electric Power Generation through the Direct Interaction of Pristine Graphene-Oxide with Water Molecules.

Converting ubiquitous environmental energy into electric power holds tremendous social and financial interests. Traditional energy harvesters and converters are limited by the specific materials and complex configuration of devices. Herein, it is presented that electric power can be directly produced from pristine graphene oxide (GO) without any pretreatment or additives once encountering the water vapor, which will generate an open-circuit-voltage of up to 0.4-0.7 V and a short-circuit-current-density of 2-25 µA cm-2 on a single piece of GO film. This phenomenon results from the directional movement of charged hydrogen ions through the GO film. The present work demonstrates and provides an extremely simple method for electric energy generation, which offers more applications of graphene-based materials in green energy converting field.

Enhanced Photocarrier Separation in Hierarchical Graphitic-C3N4-Supported CuInS2 for Noble-Metal-Free Z-Scheme Photocatalytic Water Splitting.

The effective separation of photogenerated electrons and holes in photocatalysts is a prerequisite for efficient photocatalytic water splitting. CuInS2 (CIS) is a widely used light absorber that works properly in photovoltaics but only shows limited performance in solar-driven hydrogen evolution due to its intrinsically severe charge recombination. Here, we prepare hierarchical graphitic C3N4-supported CuInS2 (denoted as GsC) by an in situ growth of CIS directly on exfoliated thin graphitic C3N4 nanosheets (g-C3N4 NS) and demonstrate efficient separation of photoinduced charge carriers in the GsC by forming the Z-scheme system for the first time in CIS-catalyzed water splitting. Under visible light illumination, the GsC features an enhanced hydrogen evolution rate up to 1290 µmol g-1 h-1, which is 3.3 and 6.1 times higher than that of g-C3N4 NS and bare-CIS, respectively, thus setting a new performance benchmark for CIS-based water-splitting photocatalysts.