Search

Abstract Metal‐organic frameworks (MOFs), a special sort of three‐dimensional crystalline porous lattices composed of organic multi‐site connectors and metal nodes, are characterized by unique porosity and high specific surface area, which have attracted a wide range of interest as electrode materials for the electrochemical energy storage devices in recent years. In this contribution, we outline the current research progress on the construction of pristine MOFs, MOF composites, and MOF derivatives and their applications as electrode materials in supercapacitors (SCs) and lithium‐ion batteries (LIBs). Specifically, we discuss the shortcomings of MOFs‐based electrode materials for SCs and LIBs. The innovative work on performance improvements by combining MOFs with other conductive materials and derivating MOFs into metal sulfides, metal oxides, metal phosphides, and porous carbon is also presented in detail. Finally, our perspectives on the challenges in the future for a grasp of the potential mechanisms are tentatively provided. This review will inspire more developments and applications of MOFs‐based electrode materials for electrochemical energy storage.

Urea–formaldehyde (UF) resin is the most widely used adhesive resin. However, it is necessary to improve its flame-retardant performance to expand its applications. In this study, exploiting electrostatic interactions, anionic phytic acid and cationic chitosan were combined to form a bio-based intumescent flame-retardant, denoted phytic acid–chitosan polyelectrolyte (PCS). The molecular structure of the urea–formaldehyde resin was optimized by crosslinking with melamine and plasticizing with polyvinyl alcohol-124. Thus, by combining PCS with the urea–formaldehyde resin and with ammonium polyphosphate and ammonium chloride as composite curing agents, flame-retardant urea–formaldehyde resins (FRUFs) were prepared. Compared to traditional UF resin, FRUF showed excellent flame retardancy and not only reached the UL-94 V-0 level, but the limit of oxygen index was also as high as 36%. Compared to those of UF, the total heat release and peak heat release rate of FRUF decreased by 86.44% and 81.13%, respectively. The high flame retardancy of FRUF originates from the combination of oxygen and heat isolation by the dense carbon layer, quenching of phosphorus free radicals, and dilution of oxygen by a non-flammable gas. In addition, the mechanical properties of the FRUF remained good, even after modification. The findings of this study provide a reference for the flame-retardant application of FRUF for applications in multiple fields.

To broaden the applications of wood, it is necessary to prepare flame-retardant coatings that can protect wood substrates during combustion. In this study, a bio-based, intumescent, flame-retardant phytic acid–melamine polyelectrolyte (PM) was prepared using phosphorus-rich biomass phytic acid and nitrogen-rich melamine as raw materials through an ion crosslinking reaction. Subsequently, a series of bio-based, flame-retardant wood coatings were prepared by optimizing the structure of urea–formaldehyde resin with the addition of melamine, sodium lignosulfonate, and PM as a flame-retardant curing agent. Woods coated with PM-containing coatings displayed significantly improved flame-retardant performances in comparison to uncoated woods. For PM-cured woods, the measured values of total heat release and total smoke production were 91.51% and 57.80% lower, respectively, compared with those of uncoated wood. Furthermore, the fire growth index decreased by 97.32%, indicating a lower fire hazard. This increase in flame retardancy and smoke suppression performance is due to the dense expanded carbon layer formed during the combustion of the coating, which isolates oxygen and heat. In addition, the mechanical properties of the flame-retardant coatings cured with PM are similar to those cured with a commercial curing agent, NH4Cl. In addition, the prepared flame-retardant coating can also stain the wood. This study proves the excellent flame-retarding and curing effect of ammonium phytate in urea–formaldehyde resin coatings and provides a new approach for the application of bio-based flame retardants in wood coatings.

Abstract The leakage of organic phase change materials (OPCMs) at temperatures above their melting point severely limits their large‐scale application. The introduction of porous supports has been identified as an efficient leakage‐proofing method. In this study, a novel carbonized Cu‐coated melamine foam (MF)/reduced graphene oxide (rGO) framework (MF/rGO/Cu‐C) is constructed as a support for fabricating stabilized multifunctional OPCMs. MF serves as the supporting material, while rGO and Cu act as functional reinforcements. As a thermal energy storage material, polyethylene glycol (PEG) is encapsulated into MF/rGO/Cu‐C through a vacuum‐assisted impregnation method to obtain PEG@MF/rGO/Cu‐C composite with excellent comprehensive performance. PEG@MF/rGO/Cu‐C exhibits high phase change enthalpies of 148.3 J g−1 (melting) and 143.9 J g−1 (crystallization), corresponding to a high energy storage capability of 92.7%. Simultaneously, MF/rGO/Cu‐C endues the composite with an enhanced thermal conductivity of 0.4621 W m−1 K−1, which increases by 463% compared to that of PEG@MF. Furthermore, PEG@MF/rGO/Cu‐C displays great light‐to‐thermal and electric‐to‐thermal conversion capabilities, thermal cycle stability, light‐to‐thermal cycle stability, and shape stability, showing promising application prospects in different aspects.

Due to the strong oxidizing properties of H2O2, excessive discharge of H2O2 will cause great harm to the environment. Moreover, H2O2 is also an energetic material used as fuel, with specific attention given to its safety. Therefore, it is of great importance to explore and prepare good sensitive materials for the detection of H2O2 with a low detection limit and high selectivity. In this work, a kind of hydrogen peroxide electrochemical sensor has been fabricated. That is, polypyrrole (PPy) has been electropolymerized on the glass carbon electrode (GCE), and then Ag and Cu nanoparticles are modified together on the surface of polypyrrole by electrodeposition. SEM analysis shows that Cu and Ag nanoparticles are uniformly deposited on the surface of PPy. Electrochemical characterization results display that the sensor has a good response to H2O2 with two linear intervals. The first linear range is 0.1–1 mM (R2 = 0.9978, S = 265.06 μA/ (mM × cm2)), and the detection limit is 0.027 μM (S/N = 3). The second linear range is 1–35 mM (R2 = 0.9969, 445.78 μA/ (mM × cm2)), corresponding to 0.063 μM of detection limit (S/N = 3). The sensor reveals good reproducibility (σ = 2.104), repeatability (σ = 2.027), anti-interference, and stability. The recoveries of the electrode are 99.84–103.00% (for 0.1–1 mM of linear range) and 98.65–104.80% (for 1–35 mM linear range). Furthermore, the costs of the hydrogen peroxide electrochemical sensor proposed in this work are reduced largely by using non-precious metals without degradation of the sensing performance of H2O2. This study provides a facile way to develop nanocomposite electrochemical sensors.

The precise liquidus projection of the V-Ti-Fe system are crucial for designing high-performance hydrogen permeation alloys, but there are still many controversies in the research of this system. To this end, this article first uses the CALPHAD (CALculation of PHAse Diagrams) method to reconstruct the alloy phase diagram and compares and analyses existing experimental data, confirming that the newly constructed phase diagram in this article has good reliability and accuracy. Second, this obtained phase diagram was applied to the subsequent development process of hydrogen permeation alloys, and the (Ti65Fe35)100−xVx (x = 0, 2.5, 5, 10, 15, 25) alloys with dual-phase {bcc-(V, Ti) + TiFe} structure were successfully explored. In particular, the alloys with x values equal to 2.5 at.% and 5 at.% exhibit relatively high hydrogen permeability. Third, to further increase the H2 flux permeation through the alloys, a 500-mm-long tubular (Ti65Fe35)95V5 membrane for hydrogen permeation was prepared for the first time. Hydrogen permeation testing showed that this membrane had a very high H2 flux (4.06 mL min−1), which is ca. 6.7 times greater than the plate-like counterpart (0.61 mL min−1) under the same test conditions. This work not only indicates the reliability of the obtained V-Ti-Fe phase diagram in developing new hydrogen permeation alloys, but also demonstrates that preparing tubular membranes is one of the most important means of improving H2 flux.

At present, the V-Ti-Co phase diagram is not established, which seriously hinders the subsequent development of this potential hydrogen permeation alloy system. To this end, this article constructed the first phase diagram of the V-Ti-Co system by using the CALculation of PHAse Diagrams (CALPHAD) approach as well as relevant validation experiments. On this basis, hydrogen-permeable VxTi50Co50−x (x = 17.5, 20.5, …, 32.5) alloys were designed, and their microstructure characteristics and hydrogen transport behaviour were further studied by XRD, SEM, EDS, and so on. It was found that six ternary invariant reactions are located in the liquidus projection, and the phase diagram is divided into eight phase regions by their connecting lines. Among them, some alloys in the TiCo phase region were proven to be promising candidate materials for hydrogen permeation. Typically, VxTi50Co50−x (x = 17.5–23.5) alloys, which consist of the primary TiCo and the eutectic {bcc-(V, Ti) and TiCo} structure, show a high hydrogen permeability without hydrogen embrittlement. In particular, V23.5Ti50Co26.5 exhibit the highest permeability of 4.05 × 10−8 mol H2 m−1s−1Pa−0.5, which is the highest value known heretofore in the V-Ti-Co system. The high permeability of these alloys is due in large part to the simultaneous increment of hydrogen solubility and diffusivity, and is closely related to the composition of hydrogen permeable alloys, especially the Ti content in the (V, Ti) phase. The permeability of this alloy system is much higher than those of Nb-TiCo and/or Nb-TiNi alloys.

As traditional energy structures transition to new sources, hydrogen is receiving significant research attention owing to its potential as a clean energy source. The most significant problem with electrochemical hydrogen evolution is the need for highly efficient catalysts to drive the overpotential required to generate hydrogen gas by electrolyzing water. Experiments have shown that the addition of appropriate materials can reduce the energy required for hydrogen production by electrolysis of water and enable it to play a greater catalytic role in these evolution reactions. Therefore, more complex material compositions are required to obtain these high-performance materials. This study investigates the preparation of hydrogen production catalysts for cathodes. First, rod-like NiMoO4/NiMo is grown on NF (Nickel Foam) using a hydrothermal method. This is used as a core framework, and it provides a higher specific surface area and electron transfer channels. Next, spherical NiS is generated on the NF/NiMo4/NiMo, thus ultimately achieving efficient electrochemical hydrogen evolution. The NF/NiMo4/NiMo@NiS material exhibits a remarkably low overpotential of only 36 mV for the hydrogen evolution reaction (HER) at a current density of 10 mA·cm−2 in a potassium hydroxide solution, indicating its potential use in energy-related applications for HER processes.

Abstract Used as high‐performance electrodes, both structural and compositional alterations of carbon materials play very important roles in energy conversion/storage devices. Especially in supercapacitors, hierarchical pores and heteroatom doping in carbon materials are indispensable. Here the rambutan‐like hierarchically porous carbon microspheres (PCMs) have been constructed via a hydrothermal treatment, followed by carbonization/activation. The hierarchically porous microstructure is composed of three‐dimensional porous carbon networks, which give rise to a large surface area. Moreover, N and O functional groups are introduced in the as‐prepared samples, which could generate the extra pseudocapacitance. Benefitting from the interconnected hierarchical and open structure, PCM exhibits outstanding capacitive performance, for example, superior specific capacitance and rate capability (397 and 288 F g−1 at 0.5 and 20 A g−1, respectively), as well as long cycling stability (about 95% capacitance retention after 10,000 cycles). These encouraging results may pave an efficient way to fabricate advanced supercapacitors in the future.

In this study, MXene-derived/NiCoFe-LDH heterostructures with three-dimensional interconnected porous network microstructures were prepared, leveraging the excellent electrical conductivity and growth platform provided by the MXene material. The remarkable specific capacitance of metal oxides was fully exploited. The composite exhibited high specific capacitance and excellent stability, with a specific capacitance of 1305 F g−1 at 1 A g−1 and a capacitance of 85.7% of the initial performance after 6000 charge/discharge tests at 10 A g−1. A two-electrode assembly was constructed using activated carbon as the negative electrode material corresponding to 49.5 Wh kg−1 at 800 W kg−1, indicating that the electrodes could achieve rapid charge/discharge. The findings of this study indicate that the composite material comprising LDH/MXene has significant potential for supercapacitor applications.

Metal organic frameworks (MOFs) are a kind of porous coordination polymer supported by organic ligands with metal ions as connection points. They have a controlled structure and porosity and a significant specific surface area, and can be used as functional linkers or sacrificial templates. However, long diffusion pathways, low conductivity, low cycling stability, and the presence of few exposed active sites limit the direct application of MOFs in energy storage applications. The targeted design of MOFs has the potential to overcome these limitations. This study proposes a facile method to grow and immobilize MOFs on layered double hydroxides through an in situ design. The proposed method imparts not only enhanced conductivity and cycling stability, but also provides additional active sites with excellent specific capacitance properties due to the interconnectivity of MOF nanoparticles and layered double hydroxide (LDH) nanosheets. Due to this favorable heterojunction hook, the NiMo-LDH@NiCo-MOF composite exhibits a large specific capacitance of 1536 F·g−1 at 1 A·g−1. In addition, the assembled NiMo-LDH@NiCo-MOF//AC asymmetric supercapacitor can achieve a high-energy density value of 60.2 Wh·kg−1 at a power density of 797 W·kg−1, indicating promising applications.

Biological templates have unique structures, which are promising as a carbon source for electrode materials in energy storage devices. Yeast, a type of single-celled fungus widely available in nature possesses a unique elliptical structure and could be an ideal candidate for excellent performance supercapacitor electrode materials. In this work, we used a self-template technique to synthesize hollow carbon spheres using yeast cells as the carbon source (YC). NiCo2S4 nanosheets were further grown on the YC surface by hydrothermal synthesis. The functional groups on the YC facilitate the adsorption of the metal ions, which enables strong anchoring of the NiCo2S4 nanosheets. The YC/NiCo2S4 composite exhibits great electrochemical performance, showing a specific capacitance of 747 F g−1 at 1 A g−1. Furthermore, a device composed of an YC/NiCo2S4 positive electrode and an activated carbon negative electrode shows a maximum energy density of 43.7 Wh kg−1 at 400 W kg−1. Considering the low environmental impact of preparing the yeast-derived material and the outstanding performance of YC/NiCo2S4, the composite is a promising candidate for use in energy storage devices.

In this work, three additives BiOX (BiOI, BiOBr, and BiOF) for Al-H2O reaction have been synthesized using chemical methods. SEM analysis shows that the structure of BiOF is nanoparticles, while BiOBr and BiOI have flower-like structures composed of nanosheets. Then, Al-BiOI, Al-BiOBr, and Al-BiOF composites have been prepared using the ball milling method. The effect of halogen ions on the performance of hydrogen generation from Al hydrolysis has been explored. The results indicate that the conversion yields of Al-BiOBr, Al-BiOI, and Al-BiOF for hydrogen generation are 96.3%, 95.3%, and 8.9%, respectively. In particular, the maximum hydrogen generation rate (MHGR) of Al-BiOI is as high as 3451.8 mL g−1 min−1, eight times higher than that of Al-BiOBr. Furthermore, the influence rule of BiOX (X = F, Cl, Br, and I) on Al-H2O reaction has been studied using density functional theory. The results illustrate that HI can be more easily adsorbed on the Al surface as compared with HF, HCl, and HBr. Meanwhile, the bond length between halogen ions and the Al atom increased in the order of F−, Cl−, Br−, and I−. Therefore, the dissociation of I− from the Al surface becomes easier and will expose more active sites to enhance the reaction activity of Al. In summary, the BiOI has the most favorable performance to Al-H2O reaction.

Supercapacitors, as a new type of green electrical energy storage device, are a potential solution to environmental problems created by economic development and the excessive use of fossil energy resources. In this work, nitrogen/oxygen (N/O)-doped porous carbon materials for high-performance supercapacitors are fabricated by calcining and activating an organic crosslinked polymer prepared using polyethylene glycol, hydroxypropyl methylcellulose, and 4,4-diphenylmethane diisocyanate. The porous carbon exhibits a large specific surface area (1589 m2·g−1) and high electrochemical performance, thanks to the network structure and rich N/O content in the organic crosslinked polymer. The optimized porous carbon material (COCLP-4.5), obtained by adjusting the raw material ratio of the organic crosslinked polymer, exhibits a high specific capacitance (522 F·g−1 at 0.5 A·g−1), good rate capability (319 F·g−1 at 20 A·g−1), and outstanding stability (83% retention after 5000 cycles) in a three-electrode system. Furthermore, an energy density of 18.04 Wh·kg−1 is obtained at a power density of 200.0 W·kg−1 in a two-electrode system. This study demonstrates that organic crosslinked polymer-derived porous carbon electrode materials have good energy storage potential.

Abstract Electrochemical capacitors (ECs) are a vital class of electrical energy storage (EES) devices that display the capacity of rapid charging and provide high power density. In the current era, interest in using ionic liquids (ILs) in high‐performance EES devices has grown exponentially, as this novel versatile electrolyte media is associated with high thermal stability, excellent ionic conductivity, and the capability to withstand high voltages without undergoing decomposition. ILs are therefore potentially useful materials for improving the energy/power performances of ECs without compromising on safety, cyclic stability, and power density. The current review article underscores the importance of ILs as sustainable and high‐performance electrolytes for electrochemical capacitors.

In this study, the substitution of Mg with Zr in La0.7Mg0.3(Ni0.85Co0.15)3.5 was carried out with the purpose of improving the electrochemical performances. The structural and hydrogen storage properties in both gas-solid reaction and the electrochemical system were systematically studied on La0.7(Mg0.3−xZrx)(Ni0.85Co0.15)3.5 (x = 0.05, 0.1, 0.2, 0.3) alloys. Each tested alloy is composed of LaNi3 phase, LaNi5 phase and ZrNi3 phase with different phase abundances. The electrochemical studies indicated that all Zr-substituted anodes possessed a much higher cycling capacity retention than pristine La0.7Mg0.3(Ni0.85Co0.15)3.5. However, the maximum discharge capacity was reduced with the increase of Zr content. The potential-step tests showed that the diffusion of hydrogen atoms inside the anodes was decelerated after the introduction of Zr.

In order to improve the dehydrogenation properties of the Li-B-N-H system, a flower-like NiO was successfully synthesized using the hydrothermal method. The effect of the NiO on the dehydrogenation properties of the LiBH4-2LiNH2 system was studied. The results showed that the dehydrogenation properties of the LiBH4-2LiMH2 system were significantly enhanced by doping with NiO. The composite doped with 5 wt. % NiO exhibited optimal hydrogen storage properties. It released about 10.5 wt. % hydrogen below 300 °C, and the onset dehydrogenation temperature was only 90 °C, 110 °C lower than that of LiBH4-2LiNH2. The isothermal dehydrogenation experiment indicated that the LiBH4-2LiNH2-5 wt. % NiO composite released 8.8 wt. % hydrogen within 15 min at 150 °C. Structural analysis revealed that the as-prepared NiO was reduced to metallic Ni, which worked as an active catalytic species in the remainder of the dehydrogenation process. The Mass Spectrometer (MS) analyses showed that the doped NiO inhibited the content of NH3 released in the process of the dehydrogenation of LiBH4-2LiNH2-NiO.

In this study, the effects of the solvent used to prepare Co–B alloy on its catalytic properties were investigated. The solvent effects on the morphology, composition, and specific surface area of the alloy particles were also examined. The morphology of the alloy particles was found to be dependent on the solvent. The particles were granular in water, methanol, and acetone, although the particle diameters differed, whereas they were nanoflake-like in acetonitrile. Acetonitrile produced the largest surface area of the alloy particles, but the lowest catalytic activity for the hydrolysis of NaBH4 owing to the ready oxidation of the particles in air. The Co–B in acetone exhibited the highest catalytic activity, represented by a hydrogen generation rate of 5733 mL·min−1·g−1 during the hydrolysis of 1.5 wt % NaBH4 at 298 K. This hydrogen generation rate is more than twice that produced by the Co–B in water.

Doping with additives in a Li-Mg-N-H system has been regarded as one of the most effective methods of improving hydrogen storage properties. In this paper, we prepared Li3AlH6 and evaluated its effect on the dehydrogenation properties of 2LiNH2-MgH2. Our studies show that doping with Li3AlH6 could effectively lower the dehydrogenation temperatures and increase the hydrogen content of 2LiNH2-MgH2. For example, 2LiNH2-MgH2-0.1Li3AlH6 can desorb 6.43 wt % of hydrogen upon heating to 300 °C, with the onset dehydrogenation temperature at 78 °C. Isothermal dehydrogenation testing indicated that 2LiNH2-MgH2-0.1Li3AlH6 had superior dehydrogenation kinetics at low temperature. Moreover, the release of byproduct NH3 was successfully suppressed. Measurement of the thermal diffusivity suggests that the enhanced dehydrogenation properties may be ascribed to the fact that doping with Li3AlH6 could improve the heat transfer for solid–solid reaction.

The Co-B amorphous alloys were prepared via a chemical reduction method by sodium borohydride, using three different cobalt salts (CoCl2·6H2O, CoSO4·7H2O, and Co(NO3)2·6H2O) as sources of cobalt. As anode materials in alkaline rechargeable batteries, the Co-B alloy prepared from CoCl2·6H2O has a maximum specific discharge capacity of 844.6 mAh/g, and 306.4 mAh/g is retained even after 100 cycles at a discharge current of 100 mA/g. When Co(NO3)2·6H2O is used as a raw material, the formation of Co3(BO3)2 worsens the electrochemical properties of the sample, i.e., a maximum capacity of only 367.0 mAh/g.

In this study, polypyrrole (PPy) nanofibers were used to synthesize a super-activated carbon material. A highly-dispersed Co-Ni-B catalyst was supported on PPy nanofiber-derived activated carbon (PAC) by chemical reduction. The Co-Ni-B/PAC hybrid catalyst exhibited excellent catalytic performance for the decomposition of ammonia borane (AB) in an aqueous alkaline solution at room temperature. The size of the metal particles, morphology of Co-Ni-B/PAC, and catalytic activity of the supported catalyst were investigated. Ni-B, Co-B, and Co-Ni-B catalysts were also synthesized in the absence of PAC under similar conditions for comparison. The maximum hydrogen generation rate (1451.2 mL−1·min−1·g−1 at 25 °C) was obtained with Co-Ni-B/PAC. Kinetic studies indicated that the hydrolysis reaction of AB was first order with respect to Co-Ni-B/PAC, and the activation energy was 30.2 kJ·mol−1. Even after ten recycling experiments, the catalyst showed good stability owing to the synergistic effect of Co-Ni-B and PAC.

BackgroundCyanobacteria account for 20-30% of Earth's primary photosynthetic productivity and convert solar energy into biomass-stored chemical energy at the rate of approximately 450 TW [1]. These single-cell microorganisms are resilient predecessors of all higher oxygenic phototrophs and can be found in self-sustaining, nitrogen-fixing communities the world over, from Antarctic glaciers to the Sahara desert [2].Methodology/principal findingsHere we show that diverse genera of cyanobacteria including biofilm-forming and pelagic strains have a conserved light-dependent electrogenic activity, i.e. the ability to transfer electrons to their surroundings in response to illumination. Naturally-growing biofilm-forming photosynthetic consortia also displayed light-dependent electrogenic activity, demonstrating that this phenomenon is not limited to individual cultures. Treatment with site-specific inhibitors revealed the electrons originate at the photosynthetic electron transfer chain (P-ETC). Moreover, electrogenic activity was observed upon illumination only with blue or red but not green light confirming that P-ETC is the source of electrons. The yield of electrons harvested by extracellular electron acceptor to photons available for photosynthesis ranged from 0.05% to 0.3%, although the efficiency of electron harvesting likely varies depending on terminal electron acceptor.Conclusions/significanceThe current study illustrates that cyanobacterial electrogenic activity is an important microbiological conduit of solar energy into the biosphere. The mechanism responsible for electrogenic activity in cyanobacteria appears to be fundamentally different from the one exploited in previously discovered electrogenic bacteria, such as Geobacter, where electrons are derived from oxidation of organic compounds and transported via a respiratory electron transfer chain (R-ETC) [3], [4]. The electrogenic pathway of cyanobacteria might be exploited to develop light-sensitive devices or future technologies that convert solar energy into limited amounts of electricity in a self-sustainable, CO(2)-free manner.