Latest ArticlesCo3O4 has been widely explored in electrocatalytic 5-hydroxymethyl-furfural (HMF) oxidation. However, the poor intrinsic ability has seriously limited its electrochemical ability. Heteroatom-doping is an efficient method to enhance the electrocatalytic ability of catalyst by regulating electronic structure. Herein, we have modulated the electronic structure of Co3O4 by high valance Mo6+-doping. With the introduction of Mo6+, the content of Co2+ was increased and metal-oxygen bond was strength. Electrochemical results suggested that the electrocatalytic ability of Co3O4 towards HMF oxidation has been dramatically improved and reaction kinetics has been fasten. Theoretical calculations demonstrated that the surrounding cobalt sites after Mo6+-doping with assembled electron has a strong adsorption ability towards HMF molecule leading to more favourable oxidation of HMF. Post characterizations demonstrated pristine Co3O4 structure was kept after electrolysis cycles and CoOOH active species were formed. This work provides a valuable reference for developing efficient heteroatom-doped electrocatalysts for HMF oxidation.
Herein, a bidirectional polarization strategy is proposed for hosting efficient and durable lithium-sulfur battery (Li-S) electrochemistry. By co-doping electronegative N and electropositive B in graphene matrix (BNrGO), the bidirectional electron redistribution enables a higher polysulfide affinity over its mono-doped counterparts, contributing to strong sulfur immobilization and fast conversion kinetics. As a result, BNrGO as the cathode host matrix realizes excellent cycling stability over 1000 cycles with a minimum capacity fading of 0.027% per cycle, and superb rate capability up to 10 C. Meanwhile, decent areal capacity (6.46 mAh/cm2) and cyclability (300 cycles) are also achievable under high sulfur loading and limited electrolyte. This work provides instructive insights into the interaction between doping engineering and sulfur electrochemistry for pursuing superior Li-S batteries.
Superior bifunctional electrocatalysts with ultra-high stability and excellent efficiency are crucial to boost the oxygen evolution reaction (OER) and the hydrogen evolution reduction (HER) in the overall water splitting (OWS) for the sustainable production of clean fuels. Herein, comprehensive density functional theory (DFT) computations were performed to explore the potential of several single transition metal (TM) atoms anchored on various S-doped black phosphorenes (TM/Snx-BP) for bifunctional OWS electrocatalysis. The results revealed that these candidates display good stability, excellent electrical conductivity, and diverse spin moments. Furthermore, the Rh/S12-BP catalyst was identified as an eligible bifunctional catalyst for OWS process due to the low overpotentials for OER (0.43 V) and HER (0.02 V), in which Rh and its adjacent P atoms were identified as the active sites. Based on the computed Gibbs free energies of OH*, O*, OOH* and H*, the corresponding volcano plots for OER and HER were established. Interestingly, the spin moments and the charge distribution of the active sites determine the catalytic trends of OER and HER. Our findings not only propose a promising bifunctional catalyst for OWS, but also widen the potential application of BP in electrocatalysis.
Cycloaddition of CO2 and epoxide into cyclic carbonate is one of the most efficient ways for CO2 conversion with 100% atom-utilization. Metal–organic frameworks are a kind of potential heterogeneous catalysts, however, high temperature, high pressure, and high-purity CO2 are still required for the reaction. Here, we report two new Zn(Ⅱ) imidazolate frameworks incoporating MoO42– or WO42– units, which can catalyse cycloaddition of CO2 and epichlorohydrin at room temperature and atomospheric pressure, giving 95% yield after 24 h in pure CO2 and 98% yield after 48 h in simulated flue gas (15% CO2 + 85% N2), respectively. For comparison, the analogic Zn(Ⅱ) imidazolate framework MAF-6 without non-3d metal oxide units showed 71% and 33% yields under the same conditions, respectively. The insightful modulation mechanisms of the MoO42– unit in optimizing the electronic structure of Zn(Ⅱ) centre, facilitating the rate-determined ring opening process, and minimizing the reaction activation energy, were revealed by X-ray photoelectron spectroscopy, temperature programmed desorption and computational calculations.
Mesoporous carbon supported with transition metals nanoparticles performs desired activities for oxygen reduction reaction (ORR) and clean energy conversion devices such as Zn–air batteries. In this work, we synthesized N-doped mesoporous carbon loaded with cobalt nanoparticles (CoMCN) through self-assembly method. There are sufficient mesopores on the carbon substrate which stem from the pore-forming agent. These mesopores can provide enough accessible active sites and profitable charge/mass transport for ORR. The high content of pyridinic and graphitic N is beneficial for promoting O2 adsorption and reduction. The smaller value of ID/IG indicates the higher degree of graphitization of CoMCN, providing better electronic conductivity. The half-wave potential of CoMCN is 0.865 V in basic solution, which is 24 mV more positive than that of the commercial Pt/C (0.841 V). In addition, CoMCN performs excellent methanol tolerance and stability under both basic and acidic conditions. The Zn–air battery assembled with CoMCN performs the larger power density and open-circuit voltage than the commercial Pt/C-based battery, indicating the potential application in energy conversion systems. This work provides thoughtful ideas for fabricating transition metal nanoparticles based porous carbon for electrocatalysis and metal–air batteries.
Hierarchical NiO nanosheets@nanorods have been rationally designed and constructed for efficient urea electrooxidation in an alkaline solution. The critical synthetic strategy, engaging the one-step anion-competitive reaction, precisely integrates two nickel-based materials into a heterostructure with Ni(OH)2 nanosheets and NiC2O4 nanorods. Benefiting from the hierarchically porous structure and high specific surface area, the NiO NNs can improve the escape efficiency of gas in electrochemical reactions and maintain sustainability. Furthermore, this distinctive structure can expose highly dispersed active sites for enhancing urea molecules' adsorption, surface-dependent redox reactions, and electrical conductivities. As a result, these hierarchical NiO nanosheets@nanorods exhibit superior activity with a low overpotential of 156 mV at 10 mA/cm2, and a slight Tafel slope of 40.7 mV/dec, and high stability with almost no decay of 12,000 s for urea electrooxidation. This work promotes the application of well-designed hierarchical structure in electrooxidizing urea and provides a possibility for highly efficient electrolysis of alkaline urea wastewater.
Lithium batteries have been widely used in all over the world for its high energy density, long-term cycle stability. While the resources of lithium metal and transition metal are limited, which restrict their applications in the grid energy storage. Dual ion sodium batteries (DISBs) possess higher energy density, especially owning high power density for its higher operating voltage (> 4.5 V). Nevertheless, the poor oxidation tolerance of carbonate electrolyte and the co-intercalation of solvents accompanied with anions are main obstacles to make the DISBs commercialization. Herein, a physical barrier (artificial SEI film) is pre-constructed in the Na||graphite batteries to solve these thorny problems. With the CSMG (covered SEI on modified graphite), batteries deliver higher capacity 40 mAh/g even under the current density of 300 mA/g and the capacity retention maintains very well after 100 cycles at a high operating voltage. Moreover, the function mechanism was revealed by in-situ XRD, demonstrating that the pre-constructed SEI can effectively suppress the irreversible phase transition and exfoliation of graphite, resulting from the co-intercalation of anions. Additionally, the work voltage windows of carbonate electrolyte are significantly broadened by establishing electrode/electrolyte interphase. This method opens up an avenue for the practical application of DISBs on the grid energy storage and other fields.
Non-centrosymmetric chalcogenides are attracting considerable attention as highly promising infrared nonlinear optical (IR-NLO) candidates, but it is challenging to simultaneously achieve sufficient second-harmonic-generation coefficient (deff > 0.5 × AgGaS2) and large energy gap (Eg > 3.5 eV). In this work, a novel ternary chalcogenide, Cs5Ga9S16 with an ultra-wide Eg of 4.05 eV, has been successfully obtained. This sulfide belongs to the monoclinic space group Pn (No. 7) with a novel 3D anionic [Ga9S16]5– framework that is formed by super-polyhedral [Ga9S23] units through corner-sharing S atoms. Such a unique crystal structure displays desirable characteristics which indicate a promising IR-NLO candidate: favourable phase-matching feature, sufficient deff (0.7 × AgGaS2), ultrahigh laser-induced damage threshold (31.6 × AgGaS2) and broad transparent region (0.27−14.96 µm). In addition, systematic theoretical studies and structural analysis suggest that the desirable IR-NLO performances can be attributed to the super-polyhedral building blocks. This finding may provide useful insight into the understanding and designing other high-performance IR-NLO candidates with super-polyhedral-built structures.
With the quick development of sustainable energy sources, aqueous zinc-ion batteries (AZIBs) have become a highly potential energy storage technology. It is a crucial step to construct desired electrode materials for improving the total performance of AZIBs. In recent years, considerable efforts have focused on the modification of vanadium-based cathode materials. In this review, we summarized defect engineering strategies of vanadium-based cathodes, including oxygen defects, cation vacancies and heterogeneous doping. Then, we discussed the effect of various defects on the electrochemical performance of electrode materials. Finally, we proposed the future challenges and development directions of V-based cathode materials.
Free-standing electrodes are promising candidates for flexible rechargeable batteries, toward the application of flexible energy storage devices, due to their merits of additive-free, lightweight, and high energy density. Herein, we report a free-standing SnNb2O6@CSN flexible film with SnNb2O6 encapsulated in 3D carbon skeleton nanofibers by electrospinning and carbonization processes as flexible anode for sodium-ion batteries (SIBs). The 3D carbon skeleton nanofibers serve as ion/electron transport pathway to improve the electrochemical reaction kinetics and meanwhile alleviate the volume changes of SnNb2O6 during charge-discharge processes. The as-constructed half-cell (SnNb2O6@CSN‖Na) exhibits excellent cycling stability of 99.2 mAh/g at 0.5 A/g after 950 cycles (coulombic efficiency of ~100%) and a high rate performance of 108.6 mAh/g at 10 A/g. In addition, the pouch cell can light up the LEDs at different bending angles (0°, 90°, 180°). This research shows a promising anode material for flexible energy storage electronics.
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