Vacancy engineering mediated hollow structured ZnO/ZnS S-scheme heterojunction for highly efficient photocatalytic H_(2) production

Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme heterojunction with O and Zn vacancies(VO,Zn-ZnO/ZnS)is rationally constructed via ion-exchange and calcination treatments.In such a photocatalytic system,the hollow structure combined with the introduction of dual vacancies endows the adequate light absorption.Moreover,the O and Zn vacancies serve as the trapping sites for photo-induced electrons and holes,respectively,which are beneficial for promoting the photo-induced carrier separation.Meanwhile,the S-scheme charge transfer mechanism can not only improve the separation and transfer efficiencies of photo-induced carrier but also retain the strong redox capacity.As expected,the optimized VO,Zn-ZnO/ZnS heterojunction exhibits a superior photocatalytic H_(2) production rate of 160.91 mmol g^(-1)h^(-1),approximately 643.6 times and 214.5 times with respect to that obtained on pure ZnO and ZnS,respectively.Simultaneously,the experimental results and density functional theory calculations disclose that the photo-induced carrier transfer pathway follows the S-scheme heterojunction mechanism and the introduction of O and Zn vacancies reduces the surface reaction barrier.This work provides an innovative strategy of vacancy engineering in S-scheme heterojunction for solar-to-fuel energy conversion.

Atomically Dispersed Ruthenium Catalysts with Open Hollow Structure for Lithium-Oxygen Batteries

Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult decomposition of discharge products at present.Here,we have developed N-doped carbon anchored atomically dispersed Ru sites cathode catalyst with open hollow structure(h-RuNC)for Lithium–oxygen battery.On one hand,the abundance of atomically dispersed Ru sites can effectively catalyze the formation and decomposition of discharge products,thereby greatly enhancing the redox kinetics.On the other hand,the open hollow structure not only enhances the mass activity of atomically dispersed Ru sites but also improves the diffusion efficiency of catalytic molecules.Therefore,the excellent activity from atomically dispersed Ru sites and the enhanced diffusion from open hollow structure respectively improve the redox kinetics and cycling stability,ultimately achieving a high-performance lithium–oxygen battery.

MOF-Derived Iron-Cobalt Phosphide Nanoframe as Bifunctional Electrocatalysts for Overall Water Splitting

Transition metal phosphides(TMPs)have emerged as an alternative to precious metals as efficient and low-cost catalysts for water electrolysis.Elemental doping and morphology control are effective approaches to further improve the performance of TMPs.Herein,Fe-doped CoP nanoframes(Fe-CoP NFs)with specific open cage configuration were designed and synthesized.The unique nano-framework structured Fe-CoP material shows overpotentials of only 255 and 122 mV at 10 mA cm^(−2)for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER),respectively,overwhelming most transition metal phosphides.For overall water splitting,the cell voltage is 1.65 V for Fe-CoP NFs at a current density of 10 mA cm^(−2),much superior to what is observed for the classical nanocubic structures.Fe-CoP NFs show no activity degradation up to 100 h which contrasts sharply with the rapidly decaying performance of noble metal catalyst reference.The superior electrocatalytic performance of Fe-CoP NFs due to abundant accessible active sites,reduced kinetic energy barrier,and preferable*O-containing intermediate adsorption is demonstrated through experimental observations and theoretical calculations.Our findings could provide a potential method for the preparation of multifunctional material with hollow structures and offer more hopeful prospects for obtaining efficient earth-abundant catalysts for water splitting.

A novel Ag/ZnO core-shell structure for efficient sterilization synergizing antibiotics and subsequently removing residuals

The massive use of antibiotics has led to the aggravation of bacterial resistance and also brought environmental pollution problems.This poses a great threat to human health.If the dosage of antibiotics is reduced by increasing its bactericidal performance,the emergence of drug resistance is certainly delayed,so that there's not enough time for developing drug resistance during treatment.Therefore,we selected typical representative materials of metal Ag and semiconductor ZnO nano-bactericides to design and synthesize Ag/ZnO hollow core-shell structures(AZ for short).Antibiotics are grafted on the surface of AZ through rational modification to form a composite sterilization system.The research results show that the antibacterial efficiency of the composite system is significantly increased,from the sum(34.7%+22.8%-57.5%)of the antibacterial efficiency of AZ and gentamicin to 80.2%,net synergizes 22.7%,which fully reflects the effect of 1+1>2.Therefore,the dosage of antibiotics can be drastically reduced in this way,which makes both the possibility of bacterial resistance and medical expenses remarkably decrease.Subsequently,residual antibiotics can be degraded under simple illumination using AZ-self as a photocatalyst,which cuts off the path of environmental pollution.In short,such an innovative route has guiding significance for drug resistance.

Revealing interfacial charge redistribution of homologous Ru-RuS_(2) heterostructure toward robust hydrogen oxidation reaction

Precisely tailoring the surface electronic structures of electrocatalysts for optimal hydrogen binding energy and hydroxide binding energy is vital to improve the sluggish kinetics of hydrogen oxidation reac-tion(HOR).Herein,we employ a partial desulfurization strategy to construct a homologous Ru-RuS_(2) heterostructure anchored on hollow mesoporous carbon nanospheres(Ru-RuS_(2)@C).The disparate work functions of the heterostructure contribute to the spontaneous formation of a unique built-in electric field,accelerating charge transfer and boosting conductivity of electrocatalyst.Consequently,Ru-RuS_(2)@C exhibits robust HOR electrocatalytic activity,achieving an exchange current density and mass activity as high as 3.56 mA cm^(-2) and 2.13 mAμg_(Ru)^(-1),respectively.exceeding those of state-of-the-art Pt/C and most contemporary Ru-based HOR electrocatalysts.Surprisingly,Ru-RuS_(2)@C can tolerate 1000 ppm of cO that lacks in Pt/C.Comprehensive analysis reveals that the directional electron transfer across Ru-RuS_(2) heterointerface induces local charge redistribution in interfacial region,which optimizes and balances the adsorption energies of H and OH species,as well as lowers the energy barrier for water formation,thereby promoting theHoR performance.

Apically guiding electron/mass transfer reaction induced by Ag/FeN_(x)Mott-Schottky effect within a hollow star reactor toward high performance zinc-air batteries

The disparity in the transfer of carriers(electrons/mass)during the reaction in zinc-air batteries(ZABs)results in sluggish kinetics of the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),along with elevated overpotentials,thereby imposing additional constraints on its utilization.Therefore,the pre-design and target-development of inexpensive,high-performance,and long-term stable bifunctional catalysts are urgently needed.In this work,an apically guiding dual-functional electrocatalyst(Ag-FeN_(x)-N-C)was prepared,in which a hierarchical porous nitrogen-doped carbon with three-dimensional(3D)hollow star-shaped structure is used as a substrate and high-conductivity Ag nanoparticles are coupled with iron nitride(FeN_(x))nanoparticles.Theoretical calculations indicate that the Mott-Schottky heterojunction as an inherent electric field comes from the two-phase bound of Ag and FeN_(x),of which electron accumulation in the FeN_(x)phase region and electron depletion in the Ag phase region promote orientated-guiding charge migration.The effective modulation of local electronic structures felicitously reforms the d-band electron-group distribution,and intellectually tunes the masstransfer reaction energy barriers for both ORR/OER.Additionally,the hollow star-s haped hierarchical porous structure provides an apical region for fast mass transfer.Experimental results show that the halfwave potential for ORR is 0.914 V,and the overpotential for OER is only 327 mV at 10 mA cm^(-2).A rechargeable ZAB with Ag-FeN_(x)-N-C as the air cathode demonstrates long-term cycling performance exceeding 1500 cycles(500 h),with a power density of 180 mW cm^(-2).Moreover,when employing AgFeN_(x)-N-C as the air cathode,flexible ZABs demonstrate a notable open-circuit voltage of 1.42 V and achieve a maximum power density of 65.6 mW cm^(-2).Ag-FeN_(x)-N-C shows guiding electron/mass transfer route and apical reaction microenvironment for the electrocatalyst architecture in the exploration prospects of ZABs.

Design of ZnSe-CoSe heterostructure decorated in hollow N-doped carbon nanocage with generous adsorption and catalysis sites for the reversibly fast kinetics of polysulfide conversion

Although lithium-sulfur batteries(Li SBs)are regarded as one of the most promising candidates for the next-generation energy storage system,the actual industrial application is hindered by the sluggish solid–liquid phase conversion kinetics,severe shuttle effect,and low sulfur loadings.Herein,a zeolitic imidazolate framework(ZIF)derived heterogeneous ZnSe-CoSe nanoparticles encapsulated in hollow N-doped carbon nanocage(ZnSe-CoSe-HNC)was designed by etching with tannic acid as a multifunctional electrocatalyst to boost the polysulfide conversion kinetics in LiSBs.The hollow structure in ZIF ensures large inner voids for sulfur and buffering volume expansions.Abundant exposed ZnSe-CoSe heterogeneous interfaces serve as bifunctional adsorption-catalytic centers to accelerate the conversion kinetics and alleviate the shuttle effect.Together with the highly conductive framework,the ZnSe-CoSeHNC/S cathode exhibits a high initial reversible capacity of 1305.3 m A h g-1at 0.2 C,high-rate capability,and reliable cycling stability under high sulfur loading and lean electrolyte(maintaining at 745 m A h g-1after 200 cycles with a high sulfur loading of 6.4 mg cm-2and a low electrolyte/sulfur ratio of 6μL mg^(-1)).Theoretical calculations have demonstrated the heterostructures of ZnSe-CoSe offer higher binding energy to lithium polysulfides than that of ZnSe or CoSe,facilitating the electron transfer to lithium polysulfides.This work provides a novel heterostructure with superior catalytic ability and hollow conductive architecture,paving the way for the practical application of functional sulfur electrodes.

Nano-single-crystal-constructed submicron MnCO_(3) hollow spindles enabled by solid precursor transition combined Ostwald ripening in situ on graphene toward exceptional interfacial and capacitive lithium storage

Hollow structuring has been identified as an effective strategy to enhance the cycling stability of electrodes for rechargeable batteries due to the outstanding volume expansion buffering efficiency,which motivates ardent pursuing on the synthetic approaches of hollow materials.Herein,an intriguing route,combining solid precursor transition and Ostwald ripening(SPTOR),is developed to craft nano single-crystal(SC)-constructed MnCO_(3) submicron hollow spindles homogeneously encapsulated in a reduced graphene oxide matrix(MnCO_(3) SMHSs/rGO).It is noteworthy that the H-bonding interaction between Mn_(3)O_(4) nanoparticles(NPs)and oxygen-containing groups on GO promotes uniform anchoring of Mn_(3)O_(4) NPs on GO,mild reductant ascorbic acid triggers the progressive solid-to-solid transition from Mn_(3)O_(4) NPs to MnCO_(3) submicron solid spindles(SMSSs)in situ on GO,and the Ostwald ripening process induces the gradual dissolution of interior polycrystals of MnCO_(3) SMSSs and subsequent recrystallization on surface SCs of MnCO_(3) SMHSs.Remarkably,MnCO_(3) SMHSs/rGO delivers a 500th lithium storage capacity of 2023 mAh g^(-1) at 1000 mAg^(-1),which is 10 times higher than that of MnCO_(3) microspheres/rGO fabricated from a conventional Mn^(2+)salt precursor(202 mAh g^(-1)).The ultrahigh capacity and ultralong lifespan of MnCO_(3) SMHSs/rGO can be primarily attributed to the superior reaction kinetics and reversibility combined with exceptional interfacial and capacitive lithium storage capability,enabled by the fast ion/electron transfer,large specific surface area,and robust electrode pulverization inhibition efficacy.Moreover,fascinating in-depth lithium storage reactions of MnCO_(3) are observed such as the oxidation of Mn^(2+)in MnCO_(3) to Mn^(3+)in charge process after long-term cycles and the further lithiation of Li_(2)CO_(3) in discharge process.As such,the Carbon Energy.SPTOR approach may represent a viable strategy for crafting various hollow functional materials with metastable nanomaterials as precursors.

Heterostructured Mn_(3)O_(4)-MnS Multi-Shelled Hollow Spheres for Enhanced Polysulfide Regulation in Lithium-Sulfur Batteries

Constructing heterojunctions and hollow multi-shelled structures can render materials with fascinating physicochemical properties,and have been regarded as two promising strategies to overcome the severe shuttling and sluggish kinetics of polysulfide in lithium-sulfur(Li-S)batteries.However,a single strategy can only take limited effect.Modulating catalytic hosts with synergistic effects are urgently desired.Herein,Mn_(3)O_(4)-MnS heterogeneous multi-shelled hollow spheres are meticulously designed by controlled sulfuration of Mn2O3 hollow spheres,and then applied as advanced encapsulation hosts for Li-S batteries.Benefiting from the separated spatial confinement by hollow multi-shelled structure,ample exposed active sites and built-in electric field by heterogeneous interface,and synergistic effects between Mn_(3)O_(4)(strong adsorption)and MnS(fast conversion)components,the assembled battery achieves prominent rate capability and decent cyclability(0.016%decay per cycle at 2 C,1000 cycles).More crucially,satisfactory areal capacity reaches up to 7.1 mAh cm^(-2)even with high sulfur loading(8.0 mg cm^(-2))and lean electrolyte(E/S=4.0 pL mg^(-1))conditions.This work will provide inspiration for the rational design of hollow multi-shelled heterostructure for various electrocatalysis applications.

Synergy mechanism of defect engineering in MoS_(2)/FeS_(2)/C heterostructure for high-performance sodium-ion battery

MoS_(2) is a promising anode material in sodium-ion battery technologies for possessing high theoretical capacity.However,the sluggish Na^(+) diffusion kinetics and low electronic conductivity hinder the promises.Herein,a unique MoS_(2)/FeS_(2)/C heterojunction with abundant defects and hollow structure(MFCHHS)was constructed.The synergy of defect engineering in MoS_(2),FeS_(2),and the carbon layer of MFCHHS with a larger specific surface area provides multiple storage sites of Na^(+)corresponding to the surface-controlled process.The MoS_(2)/FeS_(2)/C heterostructure and rich defects in MoS_(2) and carbon layer lower the Na^(+) diffusion energy barrier.Additionally,the construction of MoS_(2)/FeS_(2) heterojunction promotes electron transfer at the interface,accompanying with excellent conductivity of the carbon layer to facilitate reversible electrochemical reactions.The abundant defects and mismatches at the interface of MoS_(2)/FeS_(2) and MoS_(2)/C heterojunctions could relieve lattice stress and volume change sequentially.As a result,the MFCHHS anode exhibits the high capacity of 613.1 mA h g^(-1)at 0.5 A g^(-1) and 306.1 mA h g^(-1) at 20 A g^(-1).The capacity retention of 85.0%after 1400 cycles at 5.0 A g^(-1) is achieved.The density functional theory(DFT)calculation and in situ transmission electron microscope(TEM),Raman,ex-situ X-ray photon spectroscopy(XPS)studies confirm the low volume change during intercalation/deintercalation process and the efficient Na^(+)storage in the layered structure of MoS_(2) and carbon layer,as well as the defects and heterostructures in MFCHHS.We believe this work could provide an inspiration for constructing heterojunction with abundant defects to foster fast electron and Na^(+) diffusion kinetics,resulting in excellent rate capability and cycling stability.

Smart heat isolator with hollow multishelled structures

Safe, green and efficient industrial production has always been the pursuit of the chemical industry. Since thermal energy is the driving force for most of chemical reactions, an ideal reaction tank would have the capacity to automatically regulate heat conduction rate. In detail, this reaction tank should endow an ability that resists the heat loss when the reaction temperature is lower than the target, while accelerating the heat dissipation when the system is overheated. In this case, this smart reactor can not only minimize energy consumption but also reduce safety risks.Hollow structures are known to reduce heat conductivity. Particularly, the hollow structure with multishells can provide more interfaces and thus further inhibit heat transmission, which would be more favorable for heat isolation. Step forward, by coupling HoMSs with temperature-sensitive polymer, a smart heat isolation material has been fabricated in this work. It performs as a good heat isolator at a relatively lower temperature. A heat insulation effect of 6.5℃ can be achieved for the TSPU/3S–TiO_(2)HoMSs with a thickness of 1 mm under the temperature field of 50℃.The thermal conductivity of composite material would be raised under overheating conditions. Furthermore, this composite displays an unusual two-stage phase transformation during heating. Benefiting from the unique multishelled structure, energy is found to be gradually guided into the hollow structure and stored inside. This localized heat accumulation enables the composite to be a potential coating material for intelligent thermal-regulator and site-defined micro-reactor.

Novel Bilayer-Shelled N,O-Doped Hollow Porous Carbon Microspheres as High Performance Anode for Potassium-Ion Hybrid Capacitors

With the advantages of high energy/power density,long cycling life and low cost,dual-carbon potassium ion hybrid capacitors(PIHCs)have great potential in the field of energy storage.Here,a novel bilayer-shelled N,O-doped hollow porous carbon microspheres(NOHPC)anode has been prepared by a self-template method,which is consisted of a dense thin shell and a hollow porous spherical core.Excitingly,the NOHPC anode possesses a high K-storage capacity of 325.9 mA h g^(−1)at 0.1 A g^(−1)and a capacity of 201.1 mAh g^(−1)at 5 A g^(−1)after 6000 cycles.In combination with ex situ characterizations and density functional theory calculations,the high reversible capacity has been demonstrated to be attributed to the co-doping of N/O heteroatoms and porous structure improved K+adsorption and intercalation capabilities,and the stable long-cycling performance originating from the bilayer-shelled hollow porous carbon sphere structure.Meanwhile,the hollow porous activated carbon microspheres(HPAC)cathode with a high specific surface area(1472.65 m^(2)g^(−1))deriving from etching NOHPC with KOH,contributing to a high electrochemical adsorption capacity of 71.2 mAh g^(−1)at 1 A g^(−1).Notably,the NOHPC//HPAC PIHC delivers a high energy density of 90.1 Wh kg^(−1)at a power density of 939.6 W kg^(−1)after 6000 consecutive charge-discharge cycles.

Synthesis and Characterization of Hollow Strontium Carbonate Pompons by Composite Soft Template Method

The hollow strontium carbonate pompons was synthesized for the first time by a controlled reaction precipitation method with sodium dodecyl benzene sulfonate(SDBS)and polyvinyl pyrrolidone(PVP)work together as template.The sampled particles were characterized by scanning electron microscopy(SEM),transmission electron microscopy(TEM),nitrogen adsorption-desorption measurement,X-ray diffraction(XRD),Energy dispersive X-Ray spectroscopy(EDX),Fourier transform infrared spectroscopy(FTIR),Thermogravimetric analysis and differential scanning calorimetry(TGA-DSC),etc.It is shown that the assynthesized hollow strontium carbonate pompons with the size of about 2μm consist of flake-like particles under the optimal reaction conditions.The formation mechanism of hollow strontium carbonate pompons was preliminarily explored.

Hollow sphere of heterojunction(NiCu)S/NC as advanced anode for sodium-ion battery

Metal sulfide is considered as a potential anode for sodium-ion batteries(SIBs),due to the high theoretical capacity,strong thermodynamic stability and low-cost.However,their cycle capacity and rate performance are limited by the excessive expansion rate and low intrinsic conductivity.Herein,heterogeneous hollow sphere NiS-Cu_(9)S_(5)/NC(labeled as(NiCu)S/NC)based on Oswald ripening mechanism was prepared through a simple and feasible methodology.From a structural perspective,the hollow structure provides an expansion buffer and raises the electrochemical active area.In terms of electron/ion during the cycles,Na^(+)storage mechanism is optimized by NiS/Cu_(9)S_(5)heterogeneous interface,which increases the storage sites and shortens the migration path of Na^(+).The formation of built-in electric field strengthens the electron/ion mobility.Based on the first principle calculations,it is further proved the formation of heterogeneous interfaces and the direction of electron flow.As the anode for SIBs,the synthesized(NiCu)S/NC delivers high reverse capacity(559.2 mA h g^(-1)at 0.5 A g^(-1)),outstanding rate performance(185.3 mA h g^(-1)at 15 A g^(-1)),long-durable stability(342.6 mA h g^(-1)at 4 A g^(-1)after 1500cycles,150.0 m A h g^(-1)at 10 A g^(-1)after 20,000 cycles with 0.0025%average attenuation rate).The matching cathode electrode Na_(3)V_(2)(PO_(4))_(3)/C is assembled with(NiCu)S/NC for the full-battery that achieves high energy density(253.7 W h kg^(-1))and reverse capacity(288.7 mA h g^(-1)).The present work provides a distinctive strategy for constructing electrodes with excellent capacity and stability for SIBs.

Electrochemically-induced highly reactive PdO^(*) interface on modulated mesoporous MOF-derived Co_(3)O_(4) support for selective ethanol electro-oxidation

Herein,Pd nanoparticles loaded Co_(3)O_(4)catalysts(Pd@Co_(3)O_(4))are constructed from zeolitic imidazolate framework-67(ZIF-67)for the ethanol oxidation reaction(EOR).It is demonstrated for the first time that the electrochemical conversion of Co_(3)O_(4)support would result in the charge distribution alignment at the Pd/Co_(3)O_(4)interface and induce the formation of highly reactive Pd-O species(PdO^(*)),which can further catalyze the consequent reactions of the intermediates of the ethanol oxidation.The catalyst,Pd@Co_(3)O_(4)-450,obtained under the optimized conditions exhibits excellent EOR performance with a high mass activity of 590 mA mg-1,prominent operational stability,and extraordinary capability for the electro-oxidation of acetaldehyde intermediates.Importantly,the detailed mechanism investigation reveals that Pd@Co_(3)O_(4)-450 could be benefit to the C-C bond cleavage to promote the desirable C1 pathway for the ethanol oxidation reaction.The present strategy based on the metal-support interaction of the catalyst might provide valuable inspiration for the design of high-performing catalysts for the ethanol oxidation reaction.

Constructing BaTiO_(3)/TiO_(2)@polypyrrole composites with hollow multishelled structure for enhanced electromagnetic wave absorbing properties

BaTiO_(3)/TiO_(2)@polypyrrole(PPy)composites with hollow multishelled structure(HoMS)were constructed to enhance the electromagnetic wave absorbing properties of BaTiO_(3)-based absorbing material.BaTiO_(3)/TiO_(2)HoMSs were prepared by hydrothermal crystallization using TiO_(2)Ho MSs as template.Then,FeCl3 was introduced to initiate the oxidative polymerization of pyrrole monomer,forming BaTiO_(3)/TiO_(2)@PPy HoMSs successfully.The electromagnetic wave absorbing properties of BaTiO_(3)/TiO_(2)HoMSs and BaTiO_(3)/TiO_(2)@PPy Ho MSs with different shell number were investigated using a vector network analyzer.The results indicate that BaTiO_(3)/TiO_(2)@PPy HoMSs exhibit improved microwave absorption compared with BaTiO_(3)/TiO_(2)HoMSs.In particular,tripled-shelled BaTiO_(3)/TiO_(2)@PPy HoMS has the most excellent absorbing performance.The best reflection loss can reach up to-21.80 dB at 13.34 GHz with a corresponding absorber thickness of only 1.3 mm,and the qualified absorption bandwidth of tripled-shelled BaTiO_(3)/TiO_(2)@PPy HoMS is up to 4.2 GHz.This work paves a new way for the development of high-performance composite microwave absorbing materials.

Robust S-doped TiO_(2)@N,S-codoped carbon nanotube arrays as free-binder anodes for efficient sodium storage

Titanium dioxide(TiO_2) has been investigated broadly as a stable,safe,and cheap anode material for sodium-ion batteries in recent years.However,the poor electronic conductivity and inherent sluggish sodium ion diffusion hinder its practical applications.Herein,a self-template and in situ vulcanization strategy is developed to synthesize self-supported hybrid nanotube arrays composed of nitrogen/sulfur-codoped carbon coated sulfur-doped TiO_2 nanotubes(S-TiO_2@NS-C) starting from H_2 Ti_2 O_5-H_2 O nanoarrays.The S-TiO_2@NS-C composite with one-dimensional nano-sized subunits integrates several merits.Specifically,sulfur doping strongly improves the Na~+ storage ability of TiO_2@C-N nanotubes by narrowing the bandgap of original TiO_2.Originating from the nanoarrays structures built from hollow nanotubes,carbon layer and sulfur doping,the sluggish Na~+ insertion/extraction kinetics is effectively improved and the volume variation of the electrode material is significantly alleviated.As a result,the S-TiO_2@NS-C nanoarrays present efficient sodium storage properties.The greatly improved sodium storage performances of S-TiO_2@NS-C nanoarrays confirm the importance of rational engineering and synthesis of hollow array architectures with higher complexity.

Nitrogen and sulfur dual-doped high-surface-area hollow carbon nanospheres for efficient CO2 reduction

The electrochemical reduction of CO2(CO2 RR) can substantially contribute to the production of useful chemicals and reduction of global CO2 emissions. Herein, we presented N and S dual-doped high-surface-area carbon materials(SZ-HCN) as CO2 RR catalysts. N and S were doped by one-step pyrolysis of a N-containing polymer and S powder. ZnCl2 was applied as a volatile porogen to prepare porous SZ-HCN. SZ-HCN with a high specific surface area(1510 m2 g–1) exhibited efficient electrocatalytic activity and selectivity for CO2 RR. Electrochemical measurements demonstrated that SZ-HCN showed excellent catalytic performance for CO2-to-CO reduction with a high CO Faradaic efficiency(~93%) at-0.6 V. Furthermore, SZ-HCN offered a stable current density and high CO selectivity over at least 20 h continuous operation, revealing remarkable electrocatalytic durability. The experimental results and density functional theory calculations indicated that N and S dual-doped carbon materials required lower Gibbs free energy to form the COOH* intermediate than that for single-N-doped carbon for CO2-to-CO reduction, thereby enhancing CO2 RR activity.

Cross-Linked Hollow Graphitic Carbon as Low-Cost and High-Performance Anode for Potassium Ion Batteries

Large-scale and low-cost preparation of carbon-based potassium anode with long life and high capacity is one of the footstones for the development of potassium ion batteries(PIBs).Herein,a low-cost carbon-based material,cross-linked hollow graphitic carbon(HGC),is large scale synthesized to apply for PIBs anode.Its hollow structure can afford sufficient space to overcome the damage caused by the volume expansion of graphitic carbon(GC).While the cross-linked structure forms a compact interconnection network that allows electrons to rapid transfer between different GC frameworks.Electrochemical measurements demonstrated that the HGC anode exhibited low charge/discharge plateau(about 0.25 V and 0.1 V)and excellent specific capacity as high as 298 m A h g^(-1)at the current density of 50 m A g^(-1).And more important,after 200 cycles the capacity of HGC anode still shows 269 m A h g^(-1)(the decay rate of per cycle is only 0.048%).Meanwhile,the use of commercial traditional electrolyte(KPF_(6))and cheap raw materials that provide new hope for trying and realizing the large-scale production of PIBs based on carbon anode materials.

Hollow structured Cu@ZrO_(2) derived from Zr-MOF for selective hydrogenation of CO_(2) to methanol

The development of a highly efficient catalyst for CO_(2) activation and selective conversion to methanol is critical to address the issues associated with the high thermal stability of CO_(2) and controllable synthesis of methanol.Cu-based catalysts have been widely studied because of the low cost and excellent performance in mild conditions.However,the improvement of catalytic activity and selectivity remains challenging.Herein,we prepared hollow Cu@ZrO_(2) catalysts through pyrolysis of Cu-loaded Zr-MOF for CO_(2) hydrogenation to methanol.Low-temperature pyrolysis generated highly dispersed Cu nanoparticles with balanced Cu^(0)/Cu^(+)sites,larger amounts of surface basic sites and abundant Cu-ZrO_(2) interface in the hollow structure,contributing to enhanced catalytic capacity for adsorption/activation of CO_(2) and selective hydrogenation to methanol.In situ Fourier Transform Infrared Spectroscopy revealed the methanol formation followed the formate-intermediated pathway.This work would provide a guideline for the design of high-performance catalysts and the understanding of the mechanism and active sites for CO_(2) hydrogenation to methanol.