Germanium-Carbdiyne: A 3D Well-Defined sp-Hybridized Carbon-Based Material with Superhigh Li Storage Property

Carbyne delivers various excellent properties for the existence of the larger number of sp-hybridized carbon atoms.Here,a 3D well-defined porous carbon material germanium-carbdiyne(Ge-CDY)which is comprised of only sp-hybridized carbon atoms bridging by Ge atoms has been developed and investigated.The unique diamond-like structure constructed by linear butadiyne bonds and sp 3-hybridized Ge atoms ensures the stability of Ge-CDY.The large percentage of conjugated alkyne bonds composed of sp-C guarantees the good conductivity and the low band gap,which were further confirmed experimentally and theoretically,endowing Ge-CDY with the potential in electrochemical applications.The well-defined 3D carbon skeleton of Ge-CDY provides abundant uniform nanopores,which is suitable for metal ions storage and diffusion.Further half-cell evaluation also demonstrated Ge-CDY exhibited an excellent performance in lithium storage.All those indicating sp-hybridized carbon-based materials can exhibit great potential to possess excellent properties and be applied in the field of energy,electronic,and so on.

Self-Assembly 3D Porous Crumpled MXene Spheres as Efficient Gas and Pressure Sensing Material for Transient All-MXene Sensors

Environmentally friendly degradable sensors with both hazardous gases and pressure efficient sensing capabilities are highly desired for various promising applications,including environmental pollution monitoring/prevention,wisdom medical,wearable smart devices,and artificial intelligence.However,the transient gas and pressure sensors based on only identical sensing material that concurrently meets the above detection needs have not been reported.Here,we present transient all-MXene NO_(2) and pressure sensors employing three-dimensional porous crumpled MXene spheres prepared by ultrasonic spray pyrolysis technology as the sensing layer,accompanied with water-soluble polyvinyl alcohol substrates embedded with patterned MXene electrodes.The gas sensor achieves a ppb-level of highly selective NO_(2) sensing,with a response of up to 12.11%at 5 ppm NO_(2) and a detection range of 50 ppb-5 ppm,while the pressure sensor has an extremely wide linear pressure detection range of 0.14-22.22 kPa and fast response time of 34 ms.In parallel,all-MXene NO_(2) and pressure sensors can be rapidly degraded in medical H_(2)O_(2) within 6 h.This work provides a new avenue toward environmental monitoring,human physiological signal monitoring,and recyclable transient electronics.

Ge nanoparticles uniformly immobilized on 3D interconnected porous graphene frameworks as anodes for high-performance lithium-ion batteries

Germanium(Ge), an alloy-type anode material for lithium-ion batteries(LIBs), possesses many advantages such as high theoretical capacity and decent electrical conductivity. Nevertheless, its application is restricted by tremendous volume variation and tardy reaction kinetic during discharge/charge process.In this paper, the Ge/3DPG composites with Ge nanoparticles uniformly dispersed in 3D interconnected porous graphene(3DPG) skeleton are successfully prepared using a template-assisted in-situ reduction method. The unique 3D interconnected porous graphene can not only enhance the electronic conductivity and reaction kinetics of the materials, but also provide sufficient buffer space to effectively mitigate the volume expansion during cycling and strengthen the structural integrity. Moreover, the small-sized Ge nanoparticles in close conjunction with the 3D graphene can boost the surface-controlled reaction of the electrode, which contributes to a fast charge–discharge rate capability. The Ge/3DPG composite with optimized Ge/graphene mass ratio delivers high reversible specific capacity(1102 mAh g^(-1) after 100 cycles at 0.2 C), outstanding rate capability(494 mAh g^(-1) at 5 C), and admirable cycling stability(85.3% of capacity retention after 250 cycles at 0.5 C). This work provides a significant inspiration for the design and fabrication of advanced Ge-based anode materials for next-generation highperformance LIBs.

3D hierarchically porous NiO/Graphene hybrid paper anode for long-life and high rate cycling flexible Li-ion batteries

With the rapid emergence of wearable devices, flexible lithium-ion batteries(LIBs) are much more needed than ever. Free-standing graphene-based composite paper electrodes with various active materials have appealed wide applications in flexible LIBs. However, due to the prone-to-restacking feature of graphene layers, a long cycle life at high current densities is rather difficult to be achieved. Herein, a unique threedimensional(3D) hierarchically porous NiO micro-flowers/graphene paper(fNiO/GP) electrode is successfully fabricated. The resulting fNiO/GP electrode shows superior long-term cycling stability at high rates(e.g., storage capacity of 359 mAh/g after 600 cycles at a high current density of 1 A/g). The facile 3D porous structure combines both the advantages of the graphene that is highly conductive and flexible to ensure rapid electrons/ions transfer and buffer the volume expansion of NiO during charge/discharge,and of the micro-sized NiO flowers that induces hierarchical between-layer pores ranging from nanomicro meters to promote the penetration of the electrolyte and prevent the re-stacking of graphene layers. Such structural design will inspire future manufacture of a wide range of active materials/graphene composite electrodes for high performance flexible LIBs.

N,P co-doped 3D porous carbon with self-assembled morphological control via template-free method for potassiumion battery anodes

The larger ionic radius of potassium ions than that of lithium ions significantly limits the accomplishment of rapid diffusion kinetics in graphite electrodes for potassium-ion batteries(PIBs),resulting in comparatively poor rate performance and cycle stability.Herein,we report a high-rate performance and cycling stability amorphous carbon electrode achieved through nitrogen and phosphorous co-doping.The as-prepared N,P co-doped carbon electrodes have distinct 3D structures with large surface areas,hierarchical pore architectures,and increased interlayer spaces resulting from the direct pyrolysis of supramolecular self-assembled aggregates without templates.The obtained electrode N3P1 exhibits a reversible specific capacity of 258 m Ah·g^(-1)at a current density of 0.1A·g^(-1)and a good long-term cycle performance(96.1%capacity retention after 800 cycles at 0.5 A·g^(-1)).Kinetic investigations show that the N3P1 electrode with the welldeveloped porous structure and large number of surface defects exhibits capacitive-driven behavior at all scan rates,which may be attributed by N and P co-doping.Ex-situ transmission electron microscopy analyses in the fully discharged and charged states demonstrate structural stability and reversibility owing to the expanded interlayer space.The suggested synthesis approach is simple and effective for producing heteroatom-doped carbon materials for PIBs and other advanced electrochemical energy storage materials.

Porous Carbon Architecture Assembled by Cross-Linked Carbon Leaves with Implanted Atomic Cobalt for High-Performance Li-S Batteries

The practical application of lithium-sulfur batteries is severely hampered by the poor conductivity,polysulfide shuttle effect and sluggish reaction kinetics of sulfur cathodes.Herein,a hierarchi-cally porous three-dimension(3D)carbon architecture assembled by cross-linked carbon leaves with implanted atomic Co-N4 has been deli-cately developed as an advanced sulfur host through a SiO_(2)-mediated zeolitic imidazolate framework-L(ZIF-L)strategy.The unique 3D architectures not only provide a highly conductive network for fast electron transfer and buffer the volume change upon lithiation-delithi-ation process but also endow rich interface with full exposure of Co-N4 active sites to boost the lithium polysulfides adsorption and conversion.Owing to the accelerated kinetics and suppressed shuttle effect,the as-prepared sulfur cathode exhibits a superior electrochemical perfor-mance with a high reversible specific capacity of 695 mAh g^(−1) at 5 C and a low capacity fading rate of 0.053%per cycle over 500 cycles at 1 C.This work may provide a promising solution for the design of an advanced sulfur-based cathode toward high-performance Li-S batteries.

CoN_(x)C active sites-rich three-dimensional porous carbon nanofibers network derived from bacterial cellulose and bimetal-ZIFs as efficient multifunctional electrocatalyst for rechargeable Zn–air batteries

In this work, a CoNxC active sites-rich three-dimensional porous carbon nanofibers network derived from bacterial cellulose and bimetal-ZIFs is prepared via a nucleation growth strategy and a pyrolysis process.The material displays excellent electrocatalytic activity for the oxygen reduction reaction, reaching a high limiting diffusion current density of -7.8 mA cm^(-2), outperforming metal–organic frameworks derived multifunctional electrocatalysts, and oxygen evolution reaction and hydrogen evolution reaction with low overpotentials of 380 and 107 mV, respectively. When the electrochemical properties are further evaluated, the electrocatalyst as an air cathode for Zn-air batteries exhibits a high cycling stability for63 h as well as a maximum power density of 308 mW cm^(-2), which is better than those for most Zn-air batteries reported to date. In addition, a power density of 152 mW cm^(-2) is provided by the solid-state Zn-air batteries, and the cycling stability is outstanding for 24 h. The remarkable electrocatalytic properties are attributed to the synergistic effect of the 3 D porous carbon nanofibers network and abundant inserted CoNxC active sites, which enable the fast transmission of ions and mass and simultaneously provide a large contact area for the electrode/electrolyte.

Three-dimensional ordered hierarchically porous carbon materials for high performance Li-Se battery

Developing host materials with high specific surface area, good electron conductivity, and fast ion transportation channel is critical for high performance lithium-selenium(Li-Se) batteries. Herein, a series of three dimensional ordered hierarchically porous carbon(3D OHPC) materials with micro/meso/macropores are designed and synthesized for Li-Se battery. The porous structure is tuned by following the concept of the generalized Murray’s law to facilitate the mass diffusion and reduce ion transport resistance.The optimized 3D Se/OHPC cathode exhibits a very high 2 nd discharge capacity of 651 m Ah/g and retains 361 m Ah/g after 200 cycles at 0.2 C. Even at a high current rate of 5 C, the battery still shows a discharge capacity as high as 155 m Ah/g. The improved electrochemical performance is attributed to the synergy effect of the interconnected and well-designed micro, meso and macroporosity while shortened ions diffusion pathways of such Murray materials accelerate its ionic and electronic conductivities leading to the enhanced electrochemical reaction. The diffusivity coefficient in Se/OHPC can reach a very high value of 1.3 × 10^(-11)cm^(2)/s, much higher than those in single pore size carbon hosts. Their effective volume expansion accommodation capability and reduced dissolution of polyselenides ensure the high stability of the battery. This work, for the first time, established the clear relationship between textural properties of cathode materials and their performance and demonstrates that the concept of the generalized Murray’s law can be used as efficient guidance for the rational design and synthesis of advanced hierarchically porous materials and the great potential of 3D OHPC materials as a practical high performance cathode material for Li-Se batteries.

High-Performance and Flexible Co-Planar Integrated Microsystem of Carbon-Based All-Solid-State Micro-Supercapacitor and Real-Time Temperature Sensor

With the rapid development of flexible and portable microelectronics,the extreme demand for miniaturized,mechanically flexible,and integrated microsystems are strongly stimulated.Here,biomass-derived carbons(BDCs)are prepared by KOH activation using Qamgur precursor,exhibiting three-dimensional(3D)hierarchical porous structure.Benefiting from unobstructed 3D hierarchical porous structure,BDCs provide an excellent specific capacitance of 433 F g^(-1)and prominent cyclability without capacitance degradation after 50000 cycles at 50 A g^(-1).Furthermore,BDC-based planar micro-supercapacitors(MSCs)without metal collector,prepared by mask-assisted coating,exhibit outstanding areal-specific capacitance of 84 mF cm^(-2)and areal energy density of 10.6μWh cm^(-2),exceeding most of the previous carbon-based MSCs.Impressively,the MSCs disclose extraordinary flexibility with capacitance retention of almost 100%under extreme bending state.More importantly,a flexible planar integrated system composed of the MSC and temperature sensor is assembled to efficiently monitor the temperature variation,providing a feasible route for flexible MSC-based functional micro-devices.

Flexible and breathable 3D porous SSE/MXene foam towards impact/electromagnetic interference/bacteria multiple protection performance for intelligent wearable devices

As intelligent wearable devices,they will inevitably be subjected to various damages and disturbances from the external environment during daily use.Therefore,it is urgent to develop safeguarding materials with multiple protective properties.Herein,this work developed a flexible and breathable three-dimensional(3D)porous shear stiffening elastomer(SSE)/MXene(M-SSE)foam with impact/electromagnetic interference(EMI)/bacteria multiple protection performance for intelligent wearable devices.The continuous conductive MXene network in the 3D SSE porous structure made M-SSE foam exhibit excellent electromagnetic interference shielding property with a high shielding effectiveness of 34 dB.Attributed to the shear stiffening effect of porous SSE matrix,M-SSE foam possessed unique anti-impact and protection properties.The energy dissipation rate reached up to more than 85%,illustrating M-SSE foam could effectively attenuate the external impact force and absorb the impact energy.Inherited from the excellent photothermal performance of MXene,M-SSE foam achieved a considerable saturated temperature of 98℃ under 0.57 W/cm^(2) laser power.Therefore,M-SSE foam showed extraordinary antimicrobial property for Staphylococcus aureus according to the principle of photothermal sterilization.Finally,for the development of intelligent wearable devices,conductive MSSE foam could be used as an intelligent sensor to monitor various human movements owing to the highly sensitive property.This work greatly expanded the application prospect of multifunctional protective materials in various complex environments and promoted the development of multifunctional smart wearable devices in protection field.

High-performance Ti_(3)C_(2)T_(x)achieved by polyaniline intercalation and gelatinization as a high-energy cathode for zinc-ion capacitor

The actual manufacture of supercapacitors(SCs)is restricted by the inadequate energy density,and the energy density of devices can be properly promoted by assembling zinc-ion capacitors(ZICs)which used capacitive cathode and battery-type anode.Two-dimensional(2D)MXene has brought great focuses in the electrode research on the foundation of large redox-active surface,but the specific capacitance is still affected by the tight stacking of interlaminations.Ti_(3)C_(2)T_(x)@polyaniline(PANI)heterostructures are prepared by uniformly depositing the conductive polymer PANI nanorods as the intercalation agent into the external of Ti_(3)C_(2)T_(x)nanosheets to inhibit stacking.Subsequently,by using graphene oxide(GO)-assisted low-temperature hydrothermal self-assembly manufacture,2D heterostructures are assembled into the three-dimensional(3D)porous crosslinked Ti_(3)C_(2)T_(x)@PANI-reduced graphene oxide(RGO)hydrogels.Attributed to the synergistic work of PANI nanorods,Ti_(3)C_(2)T_(X)nanosheets,and 3D crosslinking frameworks of RGO to match capacitive and battery effects,3D porous hierarchical Ti_(3)C_(2)T_(x)@PANI-RGO heterostructure hydrogels have rich ion transport channels,a large number of active sites,and excellent reaction kinetics.ZIC is assembled by using Ti_(3)C_(2)T_(x)@PANI-RGO heterostructure hydrogels as cathodes and zinc foil as anodes.In this work,Ti_(3)C_(2)T_(x)@PANI-RGO//Zn ZIC exhibits a wide working window(2.0 V),marked specific capacitance(589.89 F·g^(−1)at 0.5 A·g−1),salient energy density(327.71 Wh·kg^(−1)at 513.61 W·kg^(−1)and 192.20 Wh·kg^(−1)at 13,005.87 W·kg^(−1)),and durable cycling stability(97.87%capacitance retention after 10,000 cycles at 10 A·g^(−1)).This study emphasizes the device design of ZICs and the broad prospect of Ti_(3)C_(2)T_(x)-based hydrogels as viable cathodes for ZICs.

Porous 3D carbon-based materials:An emerging platform for efficient hydrogen production

Due to their unique properties and uninterrupted breakthrough in a myriad of clean energy-related applications,carbon-based materials have received great interest.However,the low selectivity and poor conductivity are two primary difficulties of traditional carbon-based materials(zero-dimensional(0D)/one-dimensional(1D)/two-dimensional(2D)),enerating inefficient hydrogen production and impeding the future commercialization of carbon-based materials.To improve hydrogen production,attempts are made to enlarge the surface area of porous three-dimensional(3D)carbon-based materials,achieve uniform interconnected porous channels,and enhance their stability,especially under extreme conditions.In this review,the structural advantages and performance improvements of porous carbon nanotubes(CNTs),g-C_(3)N_(4),covalent organic frameworks(COFs),metal-organic frameworks(MOFs),MXenes,and biomass-derived carbon-based materials are firstly summarized,followed by discussing the mechanisms involved and assessing the performance of the main hydrogen production methods.These include,for example,photo/electrocatalytic hydrogen production,release from methanolysis of sodium borohydride,methane decomposition,and pyrolysis-gasification.The role that the active sites of porous carbon-based materials play in promoting charge transport,and enhancing electrical conductivity and stability,in a hydrogen production process is discussed.The current challenges and future directions are also discussed to provide guidelines for the development of next-generation high-efficiency hydrogen 3D porous carbon-based materials prospected.

Designer uniform Li plating/stripping through lithium–cobalt alloying hierarchical scaffolds for scalable high-performance lithium-metal anodes

Lithium metal anodes are of great interest for advanced high-energy density batteries such as lithiumair, lithium-sulfur and solid-state batteries, due to their low electrode potential and ultra-high theoretical capacity. There are, however, several challenges limiting their practical applications, which include low coulombic efficiency, the uncontrollable growth of dendrites and poor rate capability. Here, a rational design of 3D structured lithium metal anodes comprising of in-situ growth of cobalt-decorated nitrogen-doped carbon nanotubes on continuous carbon nanofibers is demonstrated via electrospinning.The porous and free-standing scaffold can enhance the tolerance to stresses resulting from the intrinsic volume change during Li plating/stripping, delivering a significant boost in both charge/discharge rates and stable cycling performance. A binary Co-Li alloying phase was generated at the initial discharge process, creating more active sites for the Li nucleation and uniform deposition. Characterization and density functional theory calculations show that the conductive and uniformly distributed cobalt-decorated carbon nanotubes with hierarchical structure can effectively reduce the local current density and more easily absorb Li atoms, leading to more uniform Li nucleation during plating. The current work presents an advance on scalable and cost-effective strategies for novel electrode materials with 3D hierarchical microstructures and mechanical flexibility for lithium metal anodes.

Edge sulfurized graphene nanoplatelets via vacuum mechano-chemical reaction for lithium–sulfur batteries

Lithium–sulfur batteries have great potential for high energy applications due to their high capacities,low cost and eco-friendliness. However, the particularly rapid capacity decay owing to the dissolution and diffusion of polysulfide intermediate into the electrolyte still hamper their practical applications.And the reported preparation procedures to sulfur based cathode materials are often complex, and hence are rather difficult to produce at large scale. Here, we report a simple mechano-chemical sulfurization methodology in vacuum environment applying ball-milling method combined both the chemical and physical interaction for the one-pot synthesis of edge-sulfurized grapheme nanoplatelets with 3D porous foam structure as cathode materials. The optimal sample of 70%S–Gn Ps-48 h(ball-milled 48 h) obtains 13.2 wt% sulfur that chemically bonded onto the edge of Gn Ps. And the assembled batteries exhibit high initial discharge capacities of 1089 mAh/g at 0.1 C and 950 mAh/g at 0.5 C, and retain a stable discharge capacity of 776 mAh/g after 250 cycles at 0.5 C with a high Coulombic efficiency of over 98%. The excellent performance is mainly attributed to the mechano-chemical interaction between sulfur and grapheme nanoplatelets. This definitely triggers the currently extensive research in lithium–sulfur battery area.

Circumventing chemo-mechanical failure of Sn foil battery anode by grain refinement and elaborate porosity design

Tin (Sn) metal foil is a promising anode for next-generation high-energy–density lithium-ion batteries (LIBs) due to its high capacity and easy processibility. However, the pristine Sn foil anode suffers nonuniform alloying/dealloying reaction with lithium (Li) and huge volume variation, leading to electrode pulverization and inferior electrochemical performance. Herein, we proposed that reduced grain size and elaborate porosity design of Sn foil can circumvent the nonuniform alloy reaction and buffer the volume change during the lithiation/delithiation cycling. Experimentally, we designed a three-dimensional interconnected porous Sn (3DIP-Sn) foil by a facile chemical alloying/dealloying approach, which showed improved electrochemical performance. The enhanced structure stability of the as-fabricated 3DIP-Sn foil was verified by chemo-mechanical simulations and experimental investigation. As expected, the 3DIP-Sn foil anode revealed a long cycle lifespan of 4400 h at 0.5 mA cm^(−2) and 1 mAh cm^(−2) in Sn||Li half cells. A 3DIP-Sn||LiFePO_(4) full cell with LiFePO_(4) loading of 7.1 mg cm^(−2) exhibited stable cycling for 500 cycles with 80% capacity retention at 70 mA g^(−1). Pairing with high-loading commercial LiNi0.6Co0.2Mn0.2O_(2) (NCM622, 18.4 mg cm^(−2)) cathode, a 3DIP-Sn||NCM622 full cell delivered a high reversible capacity of 3.2 mAh cm^(−2). These results demonstrated the important role of regulating the uniform alloying/dealloying reaction and circumventing the localized strain/stress in improving the electrochemical performance of Sn foil anodes for advanced LIBs.

3D interconnected nanoporous TaN films for photoelectrochemical water splitting: thickness-controlled synthesis and insights into stability

Solar-driven photoelectrochemical(PEC) water splitting is a promising technology for sustainable hydrogen production, which relies on the development of efficient and stable photoanodes for water oxidation reaction. The thickness and microstructure of semiconductor films are generally crucial to their PEC properties. Herein, three-dimensional(3D) interconnected nanoporous Ta3N5 film photoanodes with controlled thickness were successfully fabricated via galvanostatic anodization and NH3 nitridation. The porous Ta3N5 nanoarchitectures(NAs) of 900 nm in thickness showed the highest PEC performance due to the optimal lightharvesting and charge separation. Compared with the holeinduced photocorrosion, the electrochemical oxidation at high anodic potentials resulted in severer performance degradation of Ta3N5. Although the surface oxide layer on deteriorated Ta3N5 photoanodes could be removed by NH3 re-treatment,the PEC performance was only partially recovered. As an alternative, anchoring a dual-layer Co(OH)x/Co OOH co-catalyst shell on the porous Ta3N5 NAs demonstrated substantially enhanced PEC performance and stability. Overall, this work provides reference to controllably fabricate 3D nanoporous Ta3N5-based photoanodes for efficient and stable PEC water splitting via optimizing the light absorption, hole extraction,charge separation and utilization.

Novel 3D grid porous Li_(4)Ti_(5)O_(12) thick electrodes fabricated by 3D printing for high performance lithium-ion batteries

Three-dimensional(3D)grid porous electrodes introduce vertically aligned pores as a convenient path for the transport of lithium-ions(Li-ions),thereby reducing the total transport distance of Li-ions and improving the reaction kinetics.Although there have been other studies focusing on 3D electrodes fabricated by 3D printing,there still exists a gap between electrode design and their electrochemical performance.In this study,we try to bridge this gap through a comprehensive investigation on the effects of various electrode parameters including the electrode porosity,active material particle diameter,electrode electronic conductivity,electrode thickness,line width,and pore size on the electrochemical performance.Both numerical simulations and experimental investigations are conducted to systematically examine these effects.3D grid porous Li_(4)Ti_(5)O_(12)(LTO)thick electrodes are fabricated by low temperature direct writing technology and the electrodes with the thickness of 1085μm and areal mass loading of 39.44 mg·cm^(−2) are obtained.The electrodes display impressive electrochemical performance with the areal capacity of 5.88 mAh·cm^(−2)@1.0 C,areal energy density of 28.95 J·cm^(−2)@1.0 C,and areal power density of 8.04 mW·cm^(−2)@1.0 C.This study can provide design guidelines for obtaining 3D grid porous electrodes with superior electrochemical performance.

Integration of 3D interconnected porous microstructure and high electrochemical property for boron-doped diamond by facile strategy

Three-dimensional(3D)porous boron-doped diamond(BDD)flm is an attractive electrode material but tough to synthesize.Herein,the 3D porous BDD flms were constructed in a facile and template-free way.The BDD/non-diamond carbon(NDC)composite flms were frstly fabricated by hot flament chemical vapor deposition(HFCVD)technique,and then the porous BDD flms with 3D interconnected porous microstructure,different pore size and NDC-free diamond were achieved by selective removal of NDC.It is manifested that higher electrochemical response,large double layer capacitance(17.54 m F/cm^(2))in diamond electrodes,wide electrochemical window of 2.6 V and superior long-term stability were achieved for 3D porous BDD flm.This derives from the synergistic effect of microstructure and phase composition of the porous flms.3D interconnected structure possesses prominent improvement of effective surface area and accessible porous channel,signifcantly enhancing the species adsorption and mass transfer.The3D porous BDD flms,composed of NDC-free diamond,exhibit excellent structural stability and corrosion resistance,which favor the enhancement of long-term stability and water splitting overpotential.The facile fabricating approach and excellent structure/electrochemical character demonstrate the appealing application in many electrochemical felds for 3D porous BDD flms,such as energy storage and conversion,wastewater treatment and purifcation.

In-situ self-templating synthesis of 3D hierarchical porous carbonsfrom oxygen-bridged porous organic polymers for highperformance supercapacitors

It is a big challenge to well control the porous structure of carbon materials for supercapacitor application.Herein,a simple in-situ self-templating strategy is developed to prepare three-dimensional(3D)hierarchical porous carbons with good combination of micro and meso-porous architecture derived from a new oxygen-bridged porous organic polymer(OPOP).The OPOP is produced by the condensation polymerization of cyanuric chloride and hydroquinone in NaOH ethanol solution and NaCl is in-situ formed as by-product that will serve as template to construct an interconnected 3D hierarchical porous architecture upon carbonization.The large interface pore architecture,and rich doping of N and O heteroatoms effectively promote the electrolyte accessibility and electronic conductivity,and provide abundant active sites for energy storage.Consequently,the supercapacitors based on the optimized OPOP-800 sample display an energy density of 8.44 and 27.28 Wh·kg^(−1)in 6.0 M KOH and 1.0 M Na2SO4 electrolytes,respectively.The capacitance retention is more than 94%after 10,000 cycles.Furthermore,density functional theory(DFT)calculations have been employed to unveil the charge storage mechanism in the OPOP-800.The results presented in this job are inspiring in finely tuning the porous structure to optimize the supercapacitive performance of carbon materials.

Easily Separated and Recyclable Amino-functionalized Porous SiO2 Beads with 3D Continuous Meso/Macropore Channels

Amino-fimctionalized porous SiO2 beads with a diameter of 200--800 μm（PSB-NH2） have been success- fully synthesized by grafting 3-ammopropyl-triethoxysilane onto meso/macroporous silica beads（PSB）, in which the PSB was prepared by hydrothermal synthetic method with a porous hard template anion-exchange resin. The as-prepared materials were characterized by means of nitrogen sorption and transmission electron micrographs（TEM）, showing the presence of 3D interconnected and continuous large mesopores and macropores inside. The beads were used to catalyze Knoevenagel condensation and proved to be highly active and selective due to the high accessibility of the reactants to the amino groups via the continuous 3D meso/macopores. Notably, such material in bead format facilitates the extremely straightforward separation from reaction solution without any centrifugation or filtration. Moreover, PSB-NH2 proved to be a stable catalyst via leaching experiment test, and can be easily recovered and reused without significant loss of activity in successive catalytic cycles.