MOF-derived porous graphitic carbon with optimized plateau capacity and rate capability for high performance lithium-ion capacitors

The development of anode materials with high rate capability and long charge-discharge plateau is the key to improve per-formance of lithium-ion capacitors(LICs).Herein,the porous graphitic carbon(PGC-1300)derived from a new triply interpenetrated co-balt metal-organic framework(Co-MOF)was prepared through the facile and robust carbonization at 1300°C and washing by HCl solu-tion.The as-prepared PGC-1300 featured an optimized graphitization degree and porous framework,which not only contributes to high plateau capacity(105.0 mAh·g^(−1)below 0.2 V at 0.05 A·g^(−1)),but also supplies more convenient pathways for ions and increases the rate capability(128.5 mAh·g^(−1)at 3.2 A·g^(−1)).According to the kinetics analyses,it can be found that diffusion regulated surface induced capa-citive process and Li-ions intercalation process are coexisted for lithium-ion storage.Additionally,LIC PGC-1300//AC constructed with pre-lithiated PGC-1300 anode and activated carbon(AC)cathode exhibited an increased energy density of 102.8 Wh·kg^(−1),a power dens-ity of 6017.1 W·kg^(−1),together with the excellent cyclic stability(91.6%retention after 10000 cycles at 1.0 A·g^(−1)).

Hybrid 2D/3D Graphitic Carbon Nitride-Based High-Temperature Position-Sensitive Detector

Ultraviolet position-sensitive detectors(PSDs)are expected to undergo harsh environments,such as high temperatures,for a wide variety of applications in military,civilian,and aerospace.However,no report on relevant PSDs operating at high temperatures can be found up to now.Herein,we design a new 2D/3D graphitic carbon nitride(g-C_(3)N_(4))/gallium nitride(GaN)hybrid heterojunction to construct the ultraviolet high-temperature-resistant PSD.The g-C_(3)N_(4)/GaN PSD exhibits a high position sensitivity of 355 mV mm^(-1),a rise/fall response time of 1.7/2.3 ms,and a nonlinearity of 0.5%at room temperature.The ultralow formation energy of-0.917 eV atom^(-1)has been obtained via the thermodynamic phase stability calculations,which endows g-C_(3)N_(4)with robust stability against heat.By merits of the strong built-in electric field of the 2D/3D hybrid heterojunction and robust thermo-stability of g-C_(3)N_(4),the g-C_(3)N_(4)/GaN PSD delivers an excellent position sensitivity and angle detection nonlinearity of 315 mV mm^(-1)and 1.4%,respectively,with high repeatability at a high temperature up to 700 K,outperforming most of the other counterparts and even commercial silicon-based devices.This work unveils the high-temperature PSD,and pioneers a new path to constructing g-C_(3)N_(4)-based harsh-environment-tolerant optoelectronic devices.

Preparation of lithium-ion battery anode materials from graphitized spent carbon cathode derived from aluminum electrolysis

Graphitized spent carbon cathode(SCC)is a hazardous solid waste generated in the aluminum electrolysis process.In this study,a flotation-acid leaching process is proposed for the purification of graphitized SCC,and the use of the purified SCC as an anode material for lithium-ion batteries is explored.The flotation and acid leaching processes were separately optimized through one-way experiments.The maximum SCC carbon content(93wt%)was achieved at a 90%proportion of−200-mesh flotation particle size,a slurry concentration of 10wt%,a rotation speed of 1600 r/min,and an inflatable capacity of 0.2 m^(3)/h(referred to as FSCC).In the subsequent acid leaching process,the SCC carbon content reached 99.58wt%at a leaching concentration of 5 mol/L,a leaching time of 100 min,a leaching temperature of 85°C,and an HCl/FSCC volume ratio of 5:1.The purified graphitized SCC(referred to as FSCC-CL)was utilized as an anode material,and it exhibited an initial capacity of 348.2 mAh/g at 0.1 C and a reversible capacity of 347.8 mAh/g after 100 cycles.Moreover,compared with commercial graphite,FSCC-CL exhibited better reversibility and cycle stability.Thus,purified SCC is an important candidate for anode material,and the flotation-acid leaching purification method is suitable for the resourceful recycling of SCC.

Efficient photoreduction strategy for uranium immobilization based on graphite carbon nitride/activated carbon nanocomposites

Uranium removal from aqueous solutions using environmentally friendly photocatalytic technology is a novel approach for resource recovery.Herein,carbon nitride/activated carbon composite materials(CN/AC)were investigated for U(Ⅵ)reduction under visible light.An exceptional boost in photocatalytic activity was observed for CN/AC composites(up to 70 times over the conventional bulk g-C_(3)N_(4)).The strong interactive conjugatedπ-bond structure between g-C_(3)N_(4) and AC accelerated the migration of carriers and then prolonged the electron lifetime.CN/AC composites exhibited excellent compatibility with different water substrates and were resilience to a wide range of p H changes and abundant competitive anions/cations.Quenching experiments and electron microscopy characterization indicated that U(VI)was reduced by photogenerated electrons and deposited on the edge of CN/AC composites.The low-cost,high-performance carbon-based composite material proposed in this work is a potential candidate for the efficient treatment of radioactive wastewater.

Comparative study on tribological properties of isostatic graphite and carbon graphite under dry sliding and water-lubricated conditions

The tribological properties of isostatic graphite and carbon graphite under dry sliding and water lubricated conditions were studied.The friction test was conducted by using a pin-on-disc tribometer.The friction coefficient and the wear rate were employed to evaluate the tribological performances of the two materials,and wear morphology was used to analyze the wear mechanism.The results show that the friction coefficient of the isostatic graphite is larger than that of the carbon graphite under the dry sliding condition,and the wear rate is lower than that of the carbon graphite.Under the water lubricated condition,the friction coefficients and the wear rates of the isostatic graphite decrease obviously.The main wear form of the isostatic graphite is abrasive wear,while the main wear form of the carbon graphite is spalling wear.Finally,the tribological mechanism of the isostatic graphite under dry sliding and water lubricated conditions were systematically analyzed.

Piezoresistivity of Carbon Fiber Graphite Cement-based Composites with CCCW

The electrical conductivity and piezoresistivity of carbon fiber graphite cement-matrix composites（CFGCC） with carbon fiber content（1% by the weight of cement）,graphite powder contents （0%-50% by the weight of cement） and CCCW（cementitious capillary crystalline waterproofing materials,4% by the weight of cement） were studied.The experimental results showed that the relationship between the resistivity of CFGCC and the concentration of graphite powders had typical features of percolation phenomena.The percolation threshold was about 20%.A clear piezoresistive effect was observed in CFGCC with 1wt% of carbon fibers,20wt% or 30wt% of graphite powders under uniaxial compressive tests,indicating that this type of smart composites was a promising candidate for strain sensing.The measured gage factor （defined as the fractional change in resistance per unit strain） of CFGCC with graphite content of 20wt% and 30wt% were 37 and 22,respectively.With the addition of CCCW,the mechanical properties of CFGCC were improved,which benefited CFGCC piezoresistivity of stability.

Highly N-doped carbon with low graphitic-N content as anode material for enhanced initial Coulombic efficiency of lithium-ion batteries

N-doped carbons as one of the most prominent anode materials to replace standard graphite exhibit outstanding Li+storage performance.However,N-doped carbon anodes still suffer from low N-doping levels and low initial Coulombic efficiency(ICE).In this study,high N-doped and low graphitic-N carbons(LGNCs)with enhanced ICE were synthesized by taking advantage of a denitrification strategy for graphitic carbon nitride(g-C_(3)N_(4)).In brief,more than 14.5 at%of N from g-C_(3)N_(4)(55.1 at%N)was retained by reacting graphitic-N with lithium,which was subsequently removed.As graphitic-N is largely responsible for the irreversible capacity,the anode's performance was significantly increased.Compared to general N-doped carbons with high graphitic-N proportion(>50%)and low N content(<15 at%),LGNCs delivered a low proportion of 10.8%-17.2% within the high N-doping content of 14.5-42.7 at%,leading to an enhanced specific capacity of 1499.9mAh g^(-1) at an ICE of 93.7% for the optimal sample of LGNC(4:1).This study provides a facile strategy to control the N content and speciation,achieving both high Li+storage capacity and high ICE,and thus promoting research and application of N-doped carbon materials.

Composite polymer electrolyte reinforced by graphitic carbon nitride nanosheets for room-temperature all-solid-state lithium batteries

By virtue of the flexibility and safety, polyethylene oxide(PEO) based electrolytes are regarded as an appealing candidate for all-solid-state lithium batteries. However, their application is limited by the poor ionic conductivity at room temperature, narrow electrochemical stability window and uncontrolled growth of lithium dendrite. To alleviate these problems, we introduce the ultrathin graphitic carbon nitride nanosheets(GCN) as advanced nanofillers into PEO based electrolytes(GCN-CPE). Benefiting from the high surface area and abundant surface N-active sites of GCN, the GCN-CPE displays decreased crystallinity and enhanced ionic conductivity. Meanwhile, Fourier transform infrared and chronoamperometry studies indicate that GCN can facilitate Li+migration in the composite electrolyte. Additionally, the GCN-CPE displays an extended electrochemical window compared with PEO based electrolytes. As a result, Li symmetric battery assembled with GCN-CPE shows a stable Li plating/stripping cycling performance, and the all-solid-state Li/LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM622) batteries using GCN-CPE exhibit satisfactory cyclability and rate capability in a voltage range of 3-4.2 V at 30 ℃.

Extraordinary Ultrahigh-Capacity and Long Cycle Life Lithium-Ion Batteries Enabled by Graphitic Carbon Nitride-Perylene Polyimide Composites

Graphitic carbon nitride(g-C_(3)N_(4))is widely used in organic metal-ion batteries owing to its high porosity,facile synthesis,stability,and high-rate performance.However,pristine g-C_(3)N_(4)nanosheets exhibit poor electrical conductivity,irreversible metal-ion storage capacity,and short-term cycling owing to their high concentration of graphitic-N species.Herein,a series of 3,4:9,10-perylenetetracarboxylic diimide-coupled g-C_(3)N_(4)composite anode materials,CN-PI_(x)(x=0.2,0.5,0.75,and 1),was investigated,which exhibited an unusually high surface nitrogen content(23.19-39.92 at.%)and the highest pyridinic-N,pyrrolic-N,and graphitic-N contents reported to date.The CN-PI_(1)anode delivers an unprecedented and continuously increasing ultrahigh discharging capacity of exceeding 8400 mAh g^(-1)(1.96 mWh cm^(-2))at 100 mA g^(-1)with high specific energy density(E_(sp))of~7700 Wh kg^(-1)and the volumetric energy density(E_(v))of~14956 Wh L-1 and an excellent long-term stability(414 mAh g^(-1)or 0.579 mWh cm^(-2)at 1 A g^(-1)).Furthermore,the activation of the CN-PI_(x)electrodes contributes to their superior electrochemical performance,resulting from the fact that the Li+is not only stored in the CN-PI_(x)composites but also CN-PI_(x)activated the Li^(0)adlayer on the CN-PI_(1)-Cu heterojunction as an SEI layer to avoid the direct contact of Li^(0)phase and the electrolyte.The CN-PI_(1)full cell with LiCoO_(2)as the cathode delivers a discharge capacity of~587 mAh g^(-1)at a 1 A g^(-1)after 250 cycles with a Coulombic efficiency nearly 99%.This study provides a strategy to develop N-doped g-C_(3)N_(4)-based anode materials for realizing long-lasting energy storage devices.

Smart Interfacing between Co-Fe Layered Double Hydroxide and Graphitic Carbon Nitride for High-efficiency Electrocatalytic Nitrogen Reduction

Bimetallic compounds such as hydrotalcite-type layered double hydroxides(LDHs)are promising electrocatalysts owing to their unique electronic structures.However,their abilities toward nitrogen adsorption and reduction are undermined since the surface-mantled,electronegative-OH groups hinder the charge transfer between transition metal atoms and nitrogen molecules.Herein,a smart interfacing strategy is proposed to construct a coupled heterointerface between LDH and 2D g-C_(3)N_(4),which is proven by density functional theory(DFT)investigations to be favorable for nitrogen adsorption and ammonia desorption compared with neat LDH surface.The interfaced LDH and g-C_(3)N_(4) is further hybridized with a self-standing TiO_(2) nanofibrous membrane(NM)to maximize the interfacial effect owing to its high porosity and large surface area.Profited from the synergistic superiorities of the three components,the LDH@C_(3)N_(4)@TiO_(2) NM delivers superior ammonia yield(2.07×10^(−9) mol s^(−1) cm^(−2))and Faradaic efficiency(25.3%),making it a high-efficiency,noble-metal-free catalyst system toward electrocatalytic nitrogen reduction.

Enhanced visible-light photocatalytic activity of Z-scheme graphitic carbon nitride/oxygen vacancy-rich zinc oxide hybrid photocatalysts

With the objectives of enhancing the stability,optical properties and visible-light photocatalytic activity of photocatalysts,we modified oxygen vacancy-rich zinc oxide（Vo-ZnO） with graphitic carbon nitride（g-C3N4）. The resulting g-C3N4/Vo-ZnO hybrid photocatalysts showed higher visible-light photocatalytic activity than pure Vo-ZnO and g-C3N4. The hybrid photocatalyst with a g-C3N4 content of 1 wt% exhibited the highest photocatalytic degradation activity under visible-light irradiation（λ≥ 400 nm）. In addition,the g-C3N4/Vo-ZnO photocatalyst was not deactivated after five cycles of methyl orange degradation,indicating that it is stable under light irradiation. Finally,a Z-scheme mechanism for the enhanced photocatalytic activity and stability of the g-C3N4/Vo-ZnO hybrid photocatalyst was proposed. The fast charge separation and transport within the g-C3N4/Vo-ZnO hybrid photocatalyst were attributed as the origins of its enhanced photocatalytic performance.

Hot‐electron‐assisted S‐scheme heterojunction of tungsten oxide/graphitic carbon nitride for broad‐spectrum photocatalytic H_(2)generation

Extended light absorption and dynamic charge separation are vital factors that determine the effectivenessof photocatalysts.In this study,a nonmetallic plasmonic S‐scheme photocatalyst was fabricatedby loading 1D plasmonic W_(18)O_(49)nanowires onto 2D g‐C_(3)N_(4)nanosheets.W_(18)O_(49)nanowiresplay the dual role of a light absorption antenna—that extends light adsorption—and a hot electrondonor—that assists the water reduction reaction in a wider light spectrum range.Moreover,S‐scheme charge transfer resulting from the matching bandgaps of W_(18)O_(49)and g‐C_(3)N_(4)can lead tostrong redox capability and high migration speed of the photoinduced charges.Consequently,in thisstudy,W_(18)O_(49)/g‐C_(3)N_(4)hybrids exhibited higher photocatalytic H2 generation than that of pristineg‐C_(3)N_(4)under light irradiation of 420–550 nm.Furthermore,the H2 production rate of thebest‐performing W_(18)O_(49)/g‐C_(3)N_(4)hybrid was 41.5μmol·g^(−1)·h^(−1)upon exposure to monochromaticlight at 550 nm,whereas pure g‐C_(3)N_(4)showed negligible activity.This study promotes novel andenvironmentally friendly hot‐electron‐assisted S‐scheme photocatalysts for the broad‐spectrumutilization of solar light.

Engineering g-C_(3)N_(4)based materials for advanced photocatalysis:Recent advances

Photocatalysis driven by abundant yet intermittent solar energy has considerable potential in renewable energy generation and environmental remediation.The outstanding electronic structure and physicochemical properties of graphitic carbon nitride(g-C_(3)N_(4)),together with unique metal-free characteristic,make them ideal candidates for advanced photocatalysts construction.This review summarizes the up-to-date advances on g-C_(3)N_(4)based photocatalysts from ingenious-design strategies and diversified photocatalytic applications.Notably,the advantages,fabrication methods and limitations of each design strategy are systemically analyzed.In order to deeply comprehend the inner connection of theory–structure–performance upon g-C_(3)N_(4)based photocatalysts,structure/composition designs,corresponding photocatalytic activities and reaction mechanisms are jointly discussed,associated with introducing their photocatalytic applications toward water splitting,carbon dioxide/nitrogen reduction and pollutants degradation,etc.Finally,the current challenges and future perspectives for g-C_(3)N_(4)based materials for photocatalysis are briefly proposed.These design strategies and limitations are also instructive for constructing g-C_(3)N_(4) based materials in other energy and environment-related applications.

Low-temperature graphitization of lignin via Co-assisted electrolysis in molten salt

The ever-growing energy demand and environmental issues have stimulated the development of sustainable energy technologies.Herein,an efficient and environmentally friendly electrochemical transformation technology was proposed to prepare highly graphitized carbon materials from an abundant natural resource-lignin (LG).The preparation process mainly includes pyrolytic carbonization of raw LG material and electrochemical conversion of amorphous carbon precursor.Interestingly,with the assistance of Co catalyst,the graphitization degree of the products was significantly improved,in which the mechanism was the removal of heteroatoms in LG and the rearrangement of carbon atoms into graphite lattice.Furthermore,tunable microstructures (nanoflakes) under catalytic effects could also be observed by controlling the electrolytic parameters.Compared with the products CN1 (without catalyst) and CN5 (with 10%catalyst),the specific surface area are 158.957 and 202.246 m^(2)g^(-1),respectively.When used as the electrode material for lithium-ion batteries,CN5 delivered a competitive specific capacity of~350 m Ah g^(-1)(0.5 C) compared with commercial graphite.The strategy proposed in this work provides an effective way to extract value-added graphite materials from lignin and can be extended to the graphitization conversion of any other amorphous carbon precursor materials.

Marrying luminescent metal nanoclusters to C_(3)N_(4) for efficient photocatalytic hydrogen peroxide production

Photocatalytic oxygen(O_(2))reduction has been considered a promising method for hydrogen peroxide(H_(2)O_(2))production.However,the poor visible light harvesting and low-efficient separation and generation of charge carriers of conventional photocatalysts strongly limited their photocatalytic H_(2)O_(2) generation performance.Herein,we design a highly efficient photocatalyst in this work by marrying luminescent gold-silver nanoclusters(AuAg NCs)to polyethyleneimine(PEI)modified C_(3)N_(4)(C3N4-PEI).The key design in this work is the utilization of highly luminescent AuAg NCs as photosensitizers to promote the generation and separation of charge carriers of C_(3)N_(4)-PEI,thereby ultimately producing abundant e−for O_(2) reduction under visible light illumination(λ≥400 nm).As a result,the as-designed photocatalyst(C3N4-PEI-AuAg NCs)exhibits excellent photocatalytic activity with an H_(2)O_(2) production capability of 82μM in pure water,which is 3.5 times higher than pristine C_(3)N_(4)(23μM).This interesting design provides a paradigm in developing other high-efficient photocatalysts for visible-light-driven H_(2)O_(2) production.

Enhanced photochemical oxidation ability of carbon nitride by π-πstacking interactions with graphene

A one-pot method for the preparation of g-C3N4/reduced graphene oxide（rGO） composite photocatalysts with controllable band structures is presented.The photocatalysts are characterized by Fouirer transform infrared spectroscopy,X-ray diffraction,scanning electron microscope,transmission electron microscope,and Mott-Schottky analysis.The valance band（VB） of g-C3N4 exhibits a noticeable positive shift upon hybridizing with rGO,and thus results in a strong photo-oxidation ability.The g-C3N4/rGO composites show a higher photodegradation activity for 2,4-dichlorophenol（2,4-DCP） and rhodamine B（RhB） under visible light irradiation（λ≥420 ran）.The g-C3N4/rGO-1sample exhibits the highest photocatalytic activity,which is 1.49 and 1.52 times higher than that of bulk g-C3N4 for 2,4-DCP and 1.52 times degradation,respectively.The enhanced photocatalytic activity for g-C3N4 originates from the improved visible light usage,enhanced electronic conductivity and photo-oxidation ability by the formed strong π-π stacking interactions with rGO.

Enhanced visible-light photo-oxidation of nitric oxide using bismuth-coupled graphitic carbon nitride composite heterostructures

Pure bismuth（Bi） metal-modified graphitic carbon nitride（g-C3N4） composites（Bi-CN） with a pomegranate-like structure were prepared by an in situ method.The Bi-CN composites were used as photocatalysts for the oxidation of nitric oxide（NO） under visible-light irradiation.The inclusion of pure Bi metal in the g-C3N4 layers markedly improved the light absorption of the Bi-CN composites from the ultraviolet to the near-infrared region because of the typical surface plasmon resonance of Bi metal.The separation and transfer of photogenerated charge carriers were greatly accelerated by the presence of built-in Mott-Schottky effects at the interface between Bi metal and g-C3N4.As a result,the Bi-CN composite photocatalysts exhibited considerably enhanced efficiency in the photocatalytic removal of NO compared with that of Bi metal or g-C3N4 alone.The pomegranate-like structure of the Bi-CN composites and an explanation for their improved photocatalytic activity were proposed.This work not only provides a design for highly efficient g-C3N4-based photocatalysts through modification with Bi metal,but also offers new insights into the mechanistic understanding of g-C3N4-based photo catalysis.

Interfacial engineering of graphitic carbon nitride(g-C_3N_4)-based metal sulfide heterojunction photocatalysts for energy conversion: A review

As one of the most appealing and attractive technologies, photocatalysis is widely used as a promising method to circumvent the environmental and energy problems. Due to its chemical stability and unique physicochemical, graphitic carbon nitride (g-C3N4) has become research hotspots in the community. However, g-C3N4 photocatalyst still suffers from many problems, resulting in unsatisfactory photocatalytic activity such as low specific surface area, high charge recombination and insufficient visible light utilization. Since 2009, g-C3N4-based heterostructures have attracted the attention of scientists worldwide for their greatly enhanced photocatalytic performance. Overall, this review summarizes the recent advances of g-C3N4-based nanocomposites modified with transition metal sulfide (TMS), including (1) preparation of pristine g-C3N4,(2) modification strategies of g-C3N4,(3) design principles of TMS-modified g-C3N4 heterostructured photocatalysts, and (4) applications in energy conversion. What is more, the characteristics and transfer mechanisms of each classification of the metal sulfide heterojunction system will be critically reviewed, spanning from the following categories:(1) Type I heterojunction,(2) Type II heterojunction,(3) p-n heterojunction,(4) Schottky junction and (5) Z-scheme heterojunction. Apart from that, the application of g-C3N4-based heterostructured photocatalysts in H2 evolution, CO2 reduction, N2 fixation and pollutant degradation will also be systematically presented. Last but not least, this review will conclude with invigorating perspectives, limitations and prospects for further advancing g-C3N4-based heterostructured photocatalysts toward practical benefits for a sustainable future.

Highly crystalline carbon nitride hollow spheres with enhanced photocatalytic performance

Graphitic carbon nitride(g-C_(3)N_(4))has emerged as a remarkably promising photocatalyst for addressing environmental and energy issues;however,it exhibits only moderate photocatalytic activity because of its low specific surface area and high recombination of carriers.Preparation of crystalline g-C_(3)N_(4) by the molten salt method has proven to be an effective method to improve the photocatalytic activity.However,crystalline g-C_(3)N_(4) prepared by the conventional molten salt method exhibits a less regular morphology.Herein,highly crystalline g-C_(3)N_(4) hollow spheres(CCNHS)were successfully prepared by the molten salt method using cyanuric acid-melamine as a precursor.The higher crystallization of the CCNHS samples not only repaired the structural defects at the surface of the CCNHS samples but also established a built-in electric field between heptazine-based g-C_(3)N_(4) and triazine-based g-C_(3)N_(4).The hollow structure improved the level of light energy utilization and increased the number of active sites for photocatalytic reactions.Because of the above characteristics,the as-prepared CCNHS samples simultaneously realized photocatalytic hydrogen evolution with the degradation of the plasticizer bisphenol A.This research offers a new perspective on the structural optimization of supramolecular self-assembly.

Recent Advances of Graphitic Carbon Nitride-Based Structures and Applications in Catalyst, Sensing, Imaging, and LEDs

The graphitic carbon nitride(g-C_3N_4) which is a two-dimensional conjugated polymer has drawn broad interdisciplinary attention as a low-cost, metal-free, and visible-light-responsive photocatalyst in the area of environmental remediation. The g-C_3N_4-based materials have excellent electronic band structures, electron-rich properties, basic surface functionalities, high physicochemical stabilities and are ‘‘earth-abundant.'' This review summarizes the latest progress related to the design and construction of g-C_3N_4-based materials and their applications including catalysis, sensing,imaging, and white-light-emitting diodes. An outlook on possible further developments in g-C_3N_4-based research for emerging properties and applications is also included.