Nanoconfinement effect of nanoporous carbon electrodes for ionic liquid-based aluminum metal anode

Rechargeable aluminum batteries(RABs),which use earth-abundant and high-volumetric-capacity metal anodes(8040 m Ah cm-3),have great potential as next-generation power sources because they use cheaper resources to deliver higher energies,compared to current lithium ion batteries.However,the mechanism of charge delivery in the newly developed,ionic liquid-based electrolytic system for RABs differs from that in conventional organic electrolytes.Thus,targeted research efforts are required to address the large overpotentials and cycling decay encountered in the ionic liquid-based electrolytic system.In this study,a nanoporous carbon(NPC)electrode with well-developed nanopores is used to develop a high-performance aluminum anode.The negatively charged nanopores can provide quenched dynamics of electrolyte molecules in the aluminum deposition process,resulting in an increased collision rate.The fast chemical equilibrium of anionic species induced by the facilitated anionic collisions leads to more favorable reduction reactions that form aluminum metals.The nanoconfinement effect causes separated nucleation and growth of aluminum nanoparticles in the multiple confined nanopores,leading to higher coulombic efficiencies and more stable cycling performance compared with macroporous carbon black and 2D stainless steel electrodes.

Nanoporous carbons as promising novel methane adsorbents for natural gas technology

Nanoporous carbons were synthesized using furfuryl alcohol and sucrose as precursors and MCM-41 and mordenite as nanoporous templates.The produced nanoporous carbons were used as adsorbent for methane storage.The average pore diameter of the samples varied from 3.9 nm to 5.9 nm and the BET surface area varied from 320m2/g to 824m2/g.The volumetric adsorption experiments revealed that MCM-41 and sucrose had better performance compared with mordenite and furfuryl alcohol,correspondingly.Also,the effect of precursor to template ratio on the structure of nanoporous carbons and their adsorption capacities was investigated.The nanoporous carbon produced from MCM-41 mesoporous molecular sieve partially filled by sucrose shows the best methane adsorption capacity among the tested samples.

Template sacrificial controlled synthesis of hierarchical nanoporous carbon@NiCo_(2)S_(4)microspheres for high-performance hybrid supercapacitors

Binary transition metal sulfides are hotly investigated in advanced energy storage devices because of their ultra-high reversible capacity.Nevertheless,the unsatisfied rate capability and cycling stability still hinder their practical application.Herein,hierarchical nanoporous carbon@NiCo_(2)S_(4)(HNCMs@NCS)composites with coreshell flower-like structures were prepared by in situ growing of NiCo_(2)S_(4) nanosheets on HNCMs through a hydro thermal-as sis ted template sacrificial method.Benefiting from a synergistic effect between the NiCo_(2)S_(4)shell with high specific capacity and the HNCMs with unique porous structure,the synthesized flower-like HNCMs@NCS composites exhibit extraordinary electrochemical performances,including a high capacity of 346.9 mAh·g^(-1)at 1 A·g^(-1),superb rate property with86.4%initial capacity at 30 A·g^(-1)and predominant cycle stability with 81.2%capacity retention after 5000 cycles.Furthermore,the resulting HNCMs@NCS cathode was coupled with the chemical-activated HNCMs(AHNCMs)anode to construct a hybrid supercapacitor device.The asfabricated device exhibits superior energy density(49.9 Wh·kg^(-1)at 802 W·kg^(-1))and ultra-high power density(24 kW·kg^(-1)at 29.5 Wh·kg^(-1)).This fascinating result further demonstrates the tremendous prospect of the synthesized HNCMs@NCS composites as high-performance supercapacitor electrode materials.

Effective adsorption of sulfamethoxazole, bisphenol A and methyl orange on nanoporous carbon derived from metal-organic frameworks

Nanoporous carbons（NPCs） derived from metal–organic frameworks（MOFs） are attracting increasing attention in many areas by virtue of their high specific surface area, large pore volume and unique porosity. The present work reports the preparation of an NPC with high surface area（1731 m^2/g） and pore volume（1.68 cm^3/g） by direct carbonization of MOF-5. We examined the adsorption of three typical contaminants from aqueous solutions, i.e., sulfamethoxazole（SMX）,bisphenol A（BPA） and methyl orange（MO）, by using the as-prepared NPC. The results demonstrated that NPC could adsorb the contaminants effectively, with adsorption capacity（qm） of 625 mg/g（SMX）, 757 mg/g（BPA） and 872 mg/g（MO）, respectively. These values were approximately 1.0-3.2 times higher than those obtained for single-walled carbon nanotubes（SWCNTs） and commercial powder active carbon（PAC） under the same conditions. With its high surface area and unique meso/macropore structure, the enhanced adsorption of NPC most likely originates from the cooperative interaction of a pore-filling mechanism, electrostatic interaction,and hydrogen bonding. In particular, the p H value has a crucial impact on adsorption, suggesting the significant contribution of electrostatic interaction between NPC and the contaminants. This study provides a proof-of-concept demonstration of MOF-derived nanoporous carbons as effective adsorbents of contaminants for water treatment.

Metal-organic framework derived magnetic nanoporous carbon as an adsorbent for the magnetic solid-phase extraction of chlorophenols from mushroom sample

In this work, a metal-organic framework derived nanoporous carbon （MOF-5-C） was fabricated and modified with Fe3O4 magnetic nanoparticles. The resulting magnetic MOF-5-derived porous carbon （Fe304@MOF-5-C） was then used for the magnetic solid-phase extraction of chlorophenols （CPs） from mushroom samples prior to high performance liquid chromatography-ultraviolet detection. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and N2 adsorption were used to characterize the adsorbent. After experimental optimization, the amount of the adsorbent was chosen as 8.0 mg, extraction time as 10 min, sample volume as 50 mL, desorption solvent as 0.4 mL （0.2 mL × 2） of alkaline methanol, and sample pH as 6. Under the above optimized conditions, good linearity for the analytes was obtained in the range of 0.8-100.0 ng g 1 with the correlation coefficients between 0.9923 and 0.9963. The limits of detection （SIN= 3） were in the range of 0.25-0.30 ng g-1, and the relative standard deviations were below 6.8%. The result showed that the Fe304@MOF-5-C has an excellent adsorption capacity for the analytes.

Nitrogen-Doped Nanoporous Carbons through Direct Carbonization of a MetaI-Biomolecule Framework for Supercapacitor

Nitrogen-doped nanoporous carbons have been successfully synthesized by direct carbonization of a nitrogen- rich metal-biomolecule framework, zinc glutamate （Zn（HzO）（CsHyNO4）-H20）, as a template without any additional carbon or nitrogen sources. The surface area and pore size distribution of the resultant carbon materials were studied based on the carbonization temperature. These carbons exhibited high specific surface area （as high as 1619.2 m2og i for ZGC-1000）. Furthermore, ZGC-1000 also provided a large specific capacitance of 140.8 F·g^- 1 at a current density of 0.25 A·g^-1 when measured in a three-electrode system. It is believed that the presence of the nitro- gen-doped nanoporous carbons prepared from the metal-organic frameworks will further facilitate the exploration of such materials as supercapacitors.

Preparation of Nanoporous Carbon/Graphene Composites and Its Application in Direct Methanol Fuel Cell

Nanoporous carbon/graphene composites （NCGC） are synthesized via one-step hydrothermal approach com- bining carbonization, where phenol and formaldehyde are used as carbon sources and triblock copolymers F 127 as template. Transmission electron microscopy （TEM） and nitrogen adsorption measurements show that the synthe- sized NCGC samples possess high surface area over 400 m2·g-1 and mesoporous structures with interconnected pores. The electrochemical studies demonstrate that Pt catalyst with NCGC as support exhibits better eletrocatalytic activity for methanol oxidation as compared to the catalyst taking widely-used VulcanXC-72 as support. In addition, the potential formation mechanism of NCGC is discussed.

Synthesis ofγ-MnS/nanoporous carbon/reduced graphene oxide composites for high-performance supercapacitor

In the present work,nanoporous carbon(NPC)was prepared from a metal-organic framework(zeolite imidazolate framework 8,ZIF-8).Different concentrations of graphene oxide(GO)were used to make NPC/reduced graphene oxide(NPC/rGO-x,x=0.5,1.0,1.5,and 2.0)composites,and thenγ-MnS/NPC/rGO-1 composite was synthesized via a simple hydrothermal technique.The electrochemical characteristics of porous carbon composites(NPC/rGO-x)andγ-MnS/NPC/rGO-1 electrodes were investigated by galvanostatic charge and discharge,cyclic voltammetry,and electrochemical impedance spectroscopy.NPC/rGO-1 showed the highest specific capacitance of 207 F/g at 0.5 A/g.Also,theγ-MnS/NPC/rGO-1 electrode demonstrates exceptional electrochemical performance with a high specific capacitance of 300 F/g at 0.5 A/g and impressive cyclic stability of 70%capacitance retention after 10,000 cycles at 1 A/g.As a result,this study demonstrates thatγ-MnS/NPC/rGO-1 electrode can be considered a promising candidate for high-performance supercapacitors.

Effects of nanopores and sulfur doping on hierarchically bunched carbon fibers to protect lithium metal anode

Studies on three-dimensional structured carbon templates have focused on how to guide homogeneous lithium metal nucleation and growth for lithium metal anodes(LMAs).However,there is still insufficient evidence for a key factor to achieve their high electrochemical performance.Here,the effects of nanopores and sulfur doping on carbon-based nanoporous host(CNH)electrode materials for LMAs were investigated using natural polymer-derived CNHs.Homogeneous pore-filling behaviors of lithium metal in the nanopores of the CNH electrode materials were first observed by ex situ scanning electron microscopy analysis,where the protective lithium metal nucleation and growth process led to significantly high Coulombic efficiency(CE)of~99.4%and stable 600 cycles.In addition,a comparison study of CNH and sulfurdoped CNH(S-CNH)electrodes,which differ only in the presence or absence of sulfur,revealed that sulfur doping can cause lower electrochemical series resistance,higher CE value,and better cycling stability in a wide range of current densities and number of cycles.Moreover,S-CNH-based LMAs showed high electrochemical performance in full-cell Li-S battery tests using a sulfur copolymer cathode,where a high energy density of 1370Wh kgelectrode−1 and an excellent power density of 4120Wkgelectrode−1 were obtained.

Symmetrizing cathode-anode response to speed up charging of nanoporous supercapacitors

Asymmetric behaviors of capacitance and charging dynamics in the cathode and anode are general for nanoporous supercapacitors.Understanding this behavior is essential for the optimal design of supercapacitors.Herein,we perform constant-potential molecular dynamics simulations to reveal asymmetric features of porous supercapacitors and their effects on capacitance and charging dynamics.Our simulations show that,counterintuitively,charging dynamics can be fast in pores providing slow ion diffusion and vice versa.Unlike electrodes with singlesize pores,multi-pore electrodes show overcharging and accelerated co-ion desorption,which can be attributed to the subtle interplay between the dynamics and charging mechanisms.We find that capacitance and charging dynamics correlate with how the ions respond to an applied cell voltage in the cathode and anode.We demonstrate that symmetrizing this response can help boost power density,which may find practical applications in supercapacitor optimization.

纳米孔碳负载Fe_3O_4催化剂上苯直接羟基化制苯酚(英文)

Fe3O4/CMK-3 was prepared by impregnation and used as a catalyst for the direct hydroxylation of benzene to phenol with hydro-gen peroxide. The iron species in the prepared catalyst was Fe3O4 because of the partial reduction of iron(III) to iron(II) on the surface of CMK-3. The high catalytic activity of the catalyst arises from the formation of Fe3O4 on the surface of CMK-3 and the high selectivity for phenol is attributed to the consumption of excess hydroxyl radicals by CMK-3. The effect of temperature,reaction time,volume of H2O2,and amount of catalyst on the catalytic performance of the prepared catalyst were investigated. Under optimized conditions,the catalyst showed excellent catalytic performance for the hydroxylation of benzene to phenol and 18% benzene conversion was achieved with 92% selectivity for phenol and with a TOF value of 8.7 h-1. The stability of catalyst was investigated by determining its activity after the fourth run and it was found to have decreased to 80% of the fresh catalyst's activity.

Oxygen-doped carbon host with enhanced bonding and electron attraction abilities for efficient and stable SnO_2/carbon composite battery anode

The coupling between electrochemically active material and conductive matrix is vitally important for high efficiency lithium ion batteries （LIBs）. By introducing oxygen groups into the nanoporous carbon framework, we accom- plish sustainably enhanced electrochemical performance for a SnO2/carbon LIB. 2-5 nm SnO2 nanoparticles are hydro- thermally grown in different nanoporous carbon frameworks, which are pristine, nitrogen- or oxygen-doped carbons. Compared with pristine and nitrogen-doped carbon hosts, the SnO2/oxygen-doped activated carbon （OAC） composite ex- hibits a higher discharge capacity of 1,122mAhg^-1 at 500 mA g^-1 after 320 cycles operation and a larger lithium storage capacity up to 680 mAhg-I at a high rate of 2,000 mA g^-1. The exceptional electrochemical performance originated from the oxygen groups, which could act as Lewis acid sites to attract electrons effectively from Sn during the charge process, thus accelerating reversible conversion of Sn to SnO2. Meanwhile, SnO2 nanoparticles are effectively bonded with carbon through such oxygen groups, thus preventing the electrochemical sintering and maintaining the cycling stability of the SnO2/OAC composite anode. The high electrochemical performance, low biomass cost, and facile preparation renders the SnO2/OAC composites a promising candidate for anode materials.

Carbon electrodes with ionophobic characteristics in organic electrolyte for high-performance electric double-layer capacitors

Activated carbon(AC)in organic electrolytebased electric double-layer capacitors(EDLCs)usually suffers from low specific capacitance.Most studies on AC focus on improving its surface area and optimizing pore structures to enhance its electrochemical performance in EDLCs.Unfortunately,the interfacial microenvironment,which is composed of nanoporous carbon and the organic electrolyte confined in it,is always ignored.Herein,a simple and powerful strategy to create AC with an ionophobic surface is proposed to address the poor efficiency of the electric doublelayer process.The polar C±F bonds formed in the AC material are characterized through near-edge X-ray absorption fine structure and X-ray photoelectron spectroscopy.The ionophobic characteristic of YP-F60 s in an organic electrolyte is extensively studied via contact angle measurements and smallangle X-ray scattering spectroscopy.An EDLC constructed with YP-F60 s as the electrode and 1 mol L^(-1) tetraethylammonium tetrafluoroborate/propylene carbonate as the electrolyte demonstrates high specific capacitance,low internal resistance,and excellent cycling stability.Our results successfully demonstrate the importance of the interfacial microenvironment of AC and its confined electrolyte to the electrochemical performance of EDLCs.Our work also offers new perspectives on the use of the CF;plasma technique to fabricate low-cost superior carbon for EDLCs.

N-Doped porous carbon supported palladium nanoparticles as a highly efficient and recyclable catalyst for the Suzuki coupling reaction

A new catalyst, Pd particles supported on the N-doped porous carbon（PC） derived from Zn-based metal-organic frameworks（zeolitic imidazolate framework： ZIF-8）, was successfully prepared for the first time.The as-prepared catalyst was designated as N-doped PC-Pd, and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscope, N_2 adsorption and inductively coupled plasma atomic emission spectroscopy. The N-doped PC-Pd composite exhibited high catalytic activity toward the Suzuki-Miyaura cross-coupling reactions. The yields of the products were in the range of 90%-99%. The catalyst could be readily recycled and reused at least 6 consecutive cycles without a significant loss of its catalytic activity.

A sustainable aqueous Zn-I2 battery

Rechargeable metal-iodine batteries are an emerging attractive electrochemical energy storage technology that combines metallic anodes with halogen cathodes. Such batteries using aqueous electrolytes represent a viable solution for the safety and cost issues associated with organic electrolytes. A hybrid-electrolyte battery architecture has been adopted in a lithium-iodine battery using a solid ceramic membrane that protects the metallic anode from contacting the aqueous electrolyte. Here we demonstrate an eco-friendly, low-cost zinc-iodine battery with an aqueous electrolyte, wherein active I2 is confined in a nanoporous carbon cloth substrate. The electrochemical reaction is confined in the nanopores as a single conversion reaction, thus avoiding the production of I3- intermediates. The cathode architecture fully utilizes the active I2, showing a capacity of 255 mAh·g^-1 and low capacity cycling fading. The battery provides an energy density of -151 Wh·kg^-1 and exhibits an ultrastable cycle life of more than 1,500 cycles.

H2S gas sensor based on integrated resonant dual-microcantilevers with high sensitivity and identification capability

Detection of trace-level hydrogen sulfide(H2 S)gas is of great importance whether in industrial production or disease diagnosis.This research presents a novel H2 S gas sensor based on integrated resonant dual-microcantilevers which can identify and detect trace-level H2 S in real-time.The sensor consists of two integrated resonant microcantilever sensors with different functions.One cantilever sensor can identify H2 S by outputting positive frequency shift signals,while the other cantilever sensor will detect H2 S as a normally used cantilever sensor with negative frequency shifts.Combined the two cantilever sensors,the proposed gas sensor can distinguish H2 S from a variety of common gases,and the detection limit to H2 S of the sensor is as sensitive as below 1 ppb.

Molecular dynamics simulation of methane gas flow in nanopores

The transport properties of fluids in nanopores are a fundamental scientific issue in the development of tight reservoirs such as shale gas.The flow of gas in nanosized pores is affected by a size effect,therefore,the conventional fluid mechanics theory cannot be applied.Based on the molecular dynamics theory,the transport process of methane in carbon nanopores was studied,including simulation of the arrangement of the wall atoms,slip and transitional flow of methane in the supercritical state and application of different driving forces.The research of this paper revealed that the configuration of the wall carbon atoms,at the microscale,has a greater influence on the density distribution and velocity distribution of methane molecules in the pores,while the change in the driving force has a greater impact on the slippage of methane at the boundary.Particularly,the theoretical model we proposed can predict the transport properties in carbon nanopores,demonstrating the sensitivity of driving force,pore configuration and the state of flow for methane gas transport,which can provide the characteristic parameters for the establishment of the seepage mathematical model.