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1.
Black phosphorus (BP) is an interesting two‐dimensional material with low‐cost and abundant metal‐free properties and is used as one cocatalyst for photocatalytic H2 production. However, the BP quantum dot (BPQD) is not studied. Herein, for the first time, BPQD is introduced as a hole‐migration cocatalyst of layered g‐C3N4 for visible‐light‐driven photocatalytic hydrogen generation. A high‐vacuum stirring method is developed for BPQD loading without the dissociation of BP. The layered BPQD is coupled on the layered g‐C3N4 surface to form a heterojunction structure. The 7% BPQD–C3N4 samples show similar time‐resolved photoluminescence curves as 0.5% Pt–C3N4. The optimum hydrogen rates of the modified sample (7% BPQD–C3N4) are 190, 133, 90, and 10.4 µmol h?1 under simulated sunlight, LED‐405, LED‐420, and LED‐550 nm irradiation, respectively, which are 3.5, 3.6, and 3 times larger than that of the pristine g‐C3N4. Such low‐cost layered system not only optimizes the optical, electrical, and texture properties of the hybrid materials for photocatalytic water splitting to generate hydrogen but also provides ideas for designing novel or easily oxidized candidates by incorporating different available materials with given carriers.  相似文献   

2.
“Graphitic” (g)‐C3N4 with a layered structure has the potential of forming graphene‐like nanosheets with unusual physicochemical properties due to weak van der Waals forces between layers. Herein is shown that g‐C3N4 nanosheets with a thickness of around 2 nm can be easily obtained by a simple top‐down strategy, namely, thermal oxidation etching of bulk g‐C3N4 in air. Compared to the bulk g‐C3N4, the highly anisotropic 2D‐nanosheets possess a high specific surface area of 306 m2 g?1, a larger bandgap (by 0.2 eV), improved electron transport ability along the in‐plane direction, and increased lifetime of photoexcited charge carriers because of the quantum confinement effect. As a consequence, the photocatalytic activities of g‐C3N4 nanosheets have been remarkably improved in terms of ?OH radical generation and photocatalytic hydrogen evolution.  相似文献   

3.
Controlled scalable assembly of 2D building blocks into macroscopic 3D architectures is highly significant. However, the assembly of g‐C3N4 into tailored, 3D architectures is not yet reported. Here, a 3D printing methodology to enable the programmable construction of carbon nitride–based hybrid aerogel membranes with patterned macroscopic architectures is proposed. g‐C3N4 nanosheets (CNNS) are used as the building block, and sodium alginate (SA) increases the viscosity of the ink to obtain the desired rheological properties. Three printing routes, including printing directly in air and in the supporting reservoirs composed of CaCl2/glycerol solution or Pluronic F127, are demonstrated for printing versatility. The printed Au nanobipyramid–CNNS–SA hybrid aerogels exhibit broadband visible‐light absorption and superior solar wastewater remediation performance with excellent cyclic stability and easy manipulation features. Remarkably, the activity of the 3D‐printed aerogel is about 2.5 times of that of the contrast sample, attributing to the enhanced liquid velocity and solution diffusion efficiency because of the 3D‐printed structure, which is demonstrated by experimental and theoretical simulations. This approach can be extended to the macroscopic assembly of other 2D materials for myriad applications.  相似文献   

4.
The power‐conversion efficiency (PCE) of single‐junction organic solar cells (OSCs) has exceeded 16% thanks to the development of non‐fullerene acceptor materials and morphological optimization of active layer. In addition, interfacial engineering always plays a crucial role in further improving the performance of OSCs based on a well‐established active‐layer system. Doping of graphitic carbon nitride (g‐C3N4) into poly(3,4‐ethylene‐dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) as a hole transport layer (HTL) for PM6:Y6‐based OSCs is reported, boosting the PCE to almost 16.4%. After being added into the PEDOT:PSS, the g‐C3N4 as a Bronsted base can be protonated, weakening the shield effect of insulating PSS on conductive PEDOT, which enables exposures of more PEDOT chains on the surface of PEDOT:PSS core‐shell structure, and thus increasing the conductivity. Therefore, at the interface between g‐C3N4 doped HTL and PM6:Y6 layer, the charge transport is improved and the charge recombination is suppressed, leading to the increases of fill factor and short‐circuit current density of devices. This work demonstrates that doping g‐C3N4 into PEDOT:PSS is an efficient strategy to increase the conductivity of HTL, resulting in higher OSC performance.  相似文献   

5.
To face the increasing demand of self‐healing hydrogels with biocompatibility and high performances, a new class of cellulose‐based self‐healing hydrogels are constructed through dynamic covalent acylhydrazone linkages. The carboxyethyl cellulose‐graft‐dithiodipropionate dihydrazide and dibenzaldehyde‐terminated poly(ethylene glycol) are synthesized, and then the hydrogels are formed from their mixed solutions under 4‐amino‐DL‐phenylalanine (4a‐Phe) catalysis. The chemical structure, as well as microscopic morphologies, gelation times, mechanical and self‐healing performances of the hydrogels are investigated with 1H NMR, Fourier transform infrared spectroscopy, atomic force microscopy, rheological and compression measurements. Their gelation times can be controlled by varying the total polymer concentration or 4a‐Phe content. The resulted hydrogels exhibit excellent self‐healing ability with a high healing efficiency (≈96%) and good mechanical properties. Moreover, the hydrogels display pH/redox dual responsive sol‐gel transition behaviors, and are applied successfully to the controlled release of doxorubicin. Importantly, benefitting from the excellent biocompatibility and the reversibly cross‐linked networks, the hydrogels can function as suitable 3D culture scaffolds for L929 cells, leading to the encapsulated cells maintaining a high viability and proliferative capacity. Therefore, the cellulose‐based self‐healing hydrogels show potential applications in drug delivery and 3D cell culture for tissue engineering.  相似文献   

6.
Smart hybrids of Zn2GeO4 nanoparticles and ultrathin g‐C3N4 layers (Zn2GeO4/g‐C3N4 hybrids) are realized by a facile solution approach, where g‐C3N4 layers act as an effective substrate for the nucleation and subsequent in situ growth of Zn2GeO4 nanoparticles. A synergistic effect is demonstrated on the two building blocks of Zn2GeO4/g‐C3N4 hybrids for lithium storage: Zn2GeO4 nanoparticles contribute high capacity and serve as spacers to isolate the ultrathin g‐C3N4 layers from restacking, resulting in expanded interlayer and exposed vacancies with doubly bonded nitrogen for extra Li‐ion storage and diffusion pathway; 2D g‐C3N4 layers, in turn, minimize the strain of particles expansion and prevent the formation of unstable solid electrolyte interphase, leading to highly reversible lithium storage. Benefiting from the remarkable synergy, the Zn2GeO4/g‐C3N4 hybrids exhibit highly reversible capacity of 1370 mA h g?1 at 200 mA g?1 after 140 cycles and excellent rate capability of 950 mA h g?1 at 2000 mA g?1. The synergistic effect originating from the hybrids brings out excellent electrochemical performance, and thus casts new light on the development of high‐energy and high‐power anode materials.  相似文献   

7.
Polymeric carbon nitride (PCN) has been extensively researched in recent years. This research has mainly focussed on C3N4 because types of PCN are quite limited and other types are not easily synthesized. Therefore developing new types of easily‐synthesized PCN beyond C3N4 offers new opportunities. C3N3 has been predicted but it has not been successfully synthesized before. Herein it is prepared in large scale from cheap cyanuric chloride on a copper surface under nonvacuum conditions. The C3N3 has a good photoelectrochemical (PEC) activity for water splitting and can be exfoliated to 2D polymeric films. This breakthrough work not only enlarges the family of PCN, but also opens the door for large‐scale synthesis of other similar C–C bonded 2D conjugated polymers based on Ullmann polymerization. Similar to graphene and C3N4, follow‐up research related to this C3N3 in different fields may emerge in the near future.  相似文献   

8.
Mesoporous materials have attracted considerable interest due to their huge surface areas and numerous active sites that can be effectively exploited in catalysis. Here, 2D mesoporous graphitic‐C3N4 nanolayers are rationally assembled on 2D mesoporous graphene sheets (g‐CN@G MMs) by in situ selective growth. Benefiting from an abundance of exposed edges and rich defects, fast electron transport, and a multipathway of charge and mass transport from a continuous interconnected mesh network, the mesh‐on‐mesh g‐CN@G MMs hybrid exhibits higher catalytic hydrogen evolution activity and stronger durability than most of the reported nonmetal catalysts and some metal‐based catalysts.  相似文献   

9.
Graphitic carbon nitride (g‐C3N4) has been commonly used as photocatalyst with promising applications in visible‐light photocatalytic water‐splitting. Rare studies are reported in applying g‐C3N4 in polymer solar cells. Here g‐C3N4 is applied in bulk heterojunction (BHJ) polymer solar cells (PSCs) for the first time by doping solution‐processable g‐C3N4 quantum dots (C3N4 QDs) in the active layer, leading to a dramatic efficiency enhancement. Upon C3N4 QDs doping, power conversion efficiencies (PCEs) of the inverted BHJ‐PSC devices based on different active layers including poly(3‐hexylthiophene‐2,5‐diyl):[6,6]‐phenyl‐C61‐butyric acid methyl ester (P3HT:PC61BM), poly(4,8‐bis‐alkyloxybenzo(l,2‐b:4,5‐b′)dithiophene‐2,6‐diylalt‐(alkyl thieno(3,4‐b)thiophene‐2‐carboxylate)‐2,6‐diyl):[6,6]‐phenyl C71‐butyric acid methyl ester (PBDTTT‐C:PC71BM), and poly[4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐co‐3‐fluorothieno [3,4‐b]thiophene‐2‐carboxylate] (PTB7‐Th):PC71BM reach 4.23%, 6.36%, and 9.18%, which are enhanced by ≈17.5%, 11.6%, and 11.8%, respectively, compared to that of the reference (undoped) devices. The PCE enhancement of the C3N4 QDs doped BHJ‐PSC device is found to be primarily attributed to the increase of short‐circuit current (Jsc), and this is confirmed by external quantum efficiency (EQE) measurements. The effects of C3N4 QDs on the surface morphology, optical absorption and photoluminescence (PL) properties of the active layer film as well as the charge transport property of the device are investigated, revealing that the efficiency enhancement of the BHJ‐PSC devices upon C3N4 QDs doping is due to the conjunct effects including the improved interfacial contact between the active layer and the hole transport layer due to the increase of the roughness of the active layer film, the facilitated photoinduced electron transfer from the conducting polymer donor to fullerene acceptor, the improved conductivity of the active layer, and the improved charge (hole and electron) transport.  相似文献   

10.
Controlled morphology modulation of graphene carbon nitride (g‐C3N4) is successfully realized from bulk to 3D loose foam architecture via the blowing effect of a bubble, which can be controlled by heating rate. The loose foam network is comprised by spatially scaffolded few‐atom‐layer interconnected flakes with the large specific surface area, as supporters to prevent agglomeration and provide a pathway for electron/phonon transports. The photocatalytic performance of 3D foam strutted g‐C3N4 toward RhB decomposition and hydrogen evolution is significantly enhanced with the morphology optimization while its excellent optoelectronic properties are maintained simultaneously. Herein, the ultrathin, mono‐, and high‐quality foam g‐C3N4 interconnected flakes with controlled layer are facilely obtained through ultrasonic, thus overcoming the drawbacks of a traditional top–down approach, opening a wide horizon for diverse practical usages. Additionally, the layer control mechanism of 3D hierarchical structure has been explored by means of bubble growth kinetics analysis and the density functional theory calculations.  相似文献   

11.
Fibre‐based materials have received tremendous attention due to their flexibility and wearability. Although great efforts have been devoted to achieve high‐performance fibres over the past several years, it is still challenging for multifunctional macroscopic fibres to satisfy versatile applications. 2D transition metal carbides/nitrides (MXenes) with intriguing physical/chemical properties have been explored in broad application, and may be able to reinforce synthetic fibres. Inspired by natural materials, for the first time, flexible smart fibres and textiles are fabricated using a 3D printing process with hybrid inks of TEMPO (2,2,6,6‐tetramethylpiperidine‐1‐oxylradi‐cal)‐mediated oxidized cellulose nanofibrils (TOCNFs) and Ti3C2 MXene. The hybrid inks display good rheological properties, which allow them to achieve accurate structures and be rapidly printed. TOCNFs/Ti3C2 in hybrid inks self‐assemble to fibres with an aligned structure in ethanol, mimicking the features of the natural structures of plant fibres. In contrast to conventional synthetic fibres with limited functions, smart TOCNFs/Ti3C2 fibres and textiles exhibit significant responsiveness to multiple external stimuli (electrical/photonic/mechanical). TOCNFs/Ti3C2 textiles with electromechanical performance can be processed into sensitive strain sensors. Such multifunctional smart fibres and textiles will be promising in diverse applications, including wearable heating textiles, human health monitoring, and human–machine interfaces.  相似文献   

12.
A 2D/2D heterojunction of black phosphorous (BP)/graphitic carbon nitride (g‐C3N4) is designed and synthesized for photocatalytic H2 evolution. The ice‐assisted exfoliation method developed herein for preparing BP nanosheets from bulk BP, leads to high yield of few‐layer BP nanosheets (≈6 layers on average) with large lateral size at reduced duration and power for liquid exfoliation. The combination of BP with g‐C3N4 protects BP from oxidation and contributes to enhanced activity both under λ > 420 nm and λ > 475 nm light irradiation and to long‐term stability. The H2 production rate of BP/g‐C3N4 (384.17 µmol g?1 h?1) is comparable to, and even surpasses that of the previously reported, precious metal‐loaded photocatalyst under λ > 420 nm light. The efficient charge transfer between BP and g‐C3N4 (likely due to formed N? P bonds) and broadened photon absorption (supported both experimentally and theoretically) contribute to the excellent photocatalytic performance. The possible mechanisms of H2 evolution under various forms of light irradiation is unveiled. This work presents a novel, facile method to prepare 2D nanomaterials and provides a successful paradigm for the design of metal‐free photocatalysts with improved charge‐carrier dynamics for renewable energy conversion.  相似文献   

13.
Introducing solar energy into membrane filtration to decrease energy and chemicals consumption represents a promising direction in membrane fields. In this study, a kind of 0D/2D heterojunction is fabricated by depositing biomineralized titanium dioxide (TiO2) nanoparticles with delaminated graphitic carbon nitride (g‐C3N4) nanosheets, and subsequently a kind of 2D heterostructure membrane is fabricated via intercalating g‐C3N4@TiO2 heterojunctions into adjacent graphene oxide (GO) nanosheets by a vacuum‐assisted self‐assembly process. Due to the enlarged interlayer spacing of GO nanosheets, the initial permeation flux of GO/g‐C3N4@TiO2 membrane reaches to 4536 Lm?2 h?1 bar?1, which is more than 40‐fold of GO membranes (101 Lm?2 h?1 bar?1) when utilized for oil/water separation. To solve the sharp permeation flux decline, arising from the adsorption of oil droplets, the a sunlight‐driven self‐cleaning process is followed, maintaining a flux recovery ratio of more than 95% after ten cycles of filtration experiment. The high permeation flux and excellent sunlight‐driven flux recovery of these heterostructure membranes manifest their attractive potential application in water purification.  相似文献   

14.
In green plants, solar‐powered electrons are transferred through sophistically arranged photosystems and are subsequently channelled into the Calvin cycle to generate chemical energy. Inspired by the natural photosynthetic scheme, a photoelectrochemical cell (PEC) is constructed configured with protonated graphitic carbon nitride (p‐g‐C3N4) and carbon nanotube hybrid (CNT/p‐g‐C3N4) film cathode, and FeOOH‐deposited bismuth vanadate (FeOOH/BiVO4) photoanode for the production of industrially useful chiral alkanes using an old yellow enzyme homologue from Thermus scotoductus (TsOYE). In the biocatalytic PEC platform, photoexcited electrons provided by the FeOOH/BiVO4 photoanode are transferred to the robust and self‐standing CNT/p‐g‐C3N4 hybrid film that electrocatalytically reduces flavin mononucleotide (FMN) mediator. The p‐g‐C3N4 promotes a two‐electron reduction of FMN coupled with an accelerated electron transfer by the conductive CNT network. The reduced FMN subsequently delivers the electrons to TsOYE for the highly enantioselective conversion of ketoisophorone to (R)‐levodione. Under light illumination (>420 nm) and external bias, (R)‐levodione is synthesized with the enantiomeric excess value of above 83%, not influenced by the scale of applied bias, simultaneously exhibiting stable and high current efficiency. The results suggest that the biocatalytic PEC made up of economical materials can selectively synthesize high‐value organic chemicals using water as an electron donor.  相似文献   

15.
Toxic organic pollutants in the aquatic environment cause severe threats to both humans and the global environment. Thus, the development of robust strategies for detection and removal of these organic pollutants is essential. For this purpose, a multifunctional and recyclable membrane by intercalating gold nanoparticles and graphitic carbon nitride into graphene oxide (GNPs/g‐C3N4/GO) is fabricated. The membranes exhibit not only superior surface enhanced Raman scattering (SERS) activity attributed to high preconcentration ability to analytes through π–π and electrostatic interactions, but also excellent catalytic activity due to the enhanced electron–hole separation efficiency. These outstanding properties allow the membrane to be used for highly sensitive detection of rhodamine 6G with a limit of detection of 5.0 × 10?14m and self‐cleaning by photocatalytic degradation of the adsorbed analytes into inorganic small molecules, thus achieving recyclable SERS application. Furthermore, the excellent SERS activity of the membrane is demonstrated by detection of 4‐chlorophenol at less than nanomolar level and no significant SERS or catalytic activity loss was observed when reusability is tested. These results suggest that the GNPs/g‐C3N4/GO membrane provides a new strategy for eliminating traditional, single‐use SERS substrates, and expands practical SERS application to simultaneous detection and removal of environmental pollutants.  相似文献   

16.
Shape‐morphing hydrogels have emerging applications in biomedical devices, soft robotics, and so on. However, successful applications require a combination of excellent mechanical properties and fast responding speed, which are usually a trade‐off in hydrogel‐based devices. Here, a facile approach to fabricate 3D gel constructs by extrusion‐based printing of tough physical hydrogels, which show programmable deformations with high response speed and large output force, is described. Highly viscoelastic poly(acrylic acid‐co‐acrylamide) (P(AAc‐co‐AAm)) and poly(acrylic acid‐coN‐isopropyl acrylamide) (P(AAc‐co‐NIPAm)) solutions or their mixtures are printed into 3D constructs by using multiple nozzles, which are then transferred into FeCl3 solution to gel the structures by forming robust carboxyl–Fe3+ coordination complexes. The printed gel fibers containing poly(N‐isopropyl acrylamide) segment exhibit considerable volume contraction in concentrated saline solution, whereas the P(AAc‐co‐AAm) ones do not contract. The mismatch in responsiveness of the gel fibers affords the integrated 3D gel constructs the shape‐morphing ability. Because of the small diameter of gel fibers, the printed gel structures deform and recover with a fast speed. A four‐armed gripper is designed to clamp plastic balls with considerable holding force, as large as 115 times the weight of the gripper. This strategy should be applicable to other tough hydrogels and broaden their applications.  相似文献   

17.
Developing high‐efficiency and low‐cost photocatalysts by avoiding expensive noble metals, yet remarkably improving H2 evolution performance, is a great challenge. Noble‐metal‐free catalysts containing Co(Fe)?N?C moieties have been widely reported in recent years for electrochemical oxygen reduction reaction and have also gained noticeable interest for organic transformation. However, to date, no prior studies are available in the literature about the activity of N‐coordinated metal centers for photocatalytic H2 evolution. Herein, a new photocatalyst containing g‐C3N4 decorated with CoP nanodots constructed from low‐cost precursors is reported. It is for the first time revealed that the unique P(δ?)?Co(δ+)?N(δ?) surface bonding states lead to much superior H2 evolution activity (96.2 µmol h?1) compared to noble metal (Pt)‐decorated g‐C3N4 photocatalyst (32.3 µmol h?1). The quantum efficiency of 12.4% at 420 nm is also much higher than the record values (≈2%) of other transition metal cocatalysts‐loaded g‐C3N4. It is believed that this work marks an important step toward developing high‐performance and low‐cost photocatalytic materials for H2 evolution.  相似文献   

18.
Graphitic carbon nitride (g‐CN) is a promising heterogeneous metal‐free catalyst for organic photosynthesis, solar energy conversion, and photodegradation of pollutants. Its catalytic performance is easily adjustable by modifying texture, optical, and electronic properties via nanocasting, doping, and copolymerization. However, simultaneous optimization has yet to be achieved. Here, a facile synthesis of mesoporous g‐CN using molecular cooperative assembly between triazine molecules is reported. Flower‐like, layered spherical aggregates of melamine cyanuric acid complex (MCA) are formed by precipitation from equimolecular mixtures in dimethyl sulfoxide (DMSO). Thermal polycondensation of MCA under nitrogen at 550 °C produces mesoporous hollow spheres comprised of tri‐s‐triazine based g‐CN nanosheets (MCA‐CN) with the composition of C3N4.14H1.98. The layered structure succeeded from MCA induces stronger optical absorption, widens the bandgap by 0.16 eV, and increases the lifetime of photoexcited charge carriers by twice compared to that of the bulk g‐CN, while the chemical structure remains similar to that of the bulk g‐CN. As a result of these simultaneous modifications, the photodegradation kinetics of rhodamine B on the catalyst surface can be improved by 10 times.  相似文献   

19.
White light phosphors have many potential applications such as solid‐state lighting, full color displays, light source for plant growth, and crop improvement. However, most of these phosphors are rare‐earth‐based materials which are costly and would be facing the challenge of resource issue due to the extremely low abundance of these elements on earth. A new white color composite consisted of a graphitic‐phase nitrogen carbon (g‐C3N4) treated with nitric acid and copper‐cysteamine Cu3Cl(SR)2 is reported herein. Under a single wavelength excitation at 365 nm, these two materials show a strong blue and red luminescence, respectively. It is interesting to find that the white light emission with a quantum yield of 20% can be obtained by mixing these two self‐activated luminescent materials at the weight ratio of 1:1.67. Using a 365 nm near‐ultraviolet chip for excitation, the composite produces a white light‐emitting diode that exhibits an excellent color rendering index of 94.3. These white‐emitting materials are environment friendly, easy to synthesize, and cost‐effective. More importantly, this will potentially eliminate the challenge of rare earth resources. Furthermore, a single chip is used for excitation instead of a multichip, which can greatly reduce the cost of the devices.  相似文献   

20.
As two‐dimensional (2D) layered materials attract more attention owing to their unique optical, electrical, and thermal properties, there are persistent efforts to grow high‐quality 2D layered materials for fundamental research and device applications. While large‐area 2D layered materials with high crystal quality can be obtained through chemical vapor transport, the strong binding between 2D layered materials and substrates poses a significant challenge for attempts to reveal their intrinsic properties and to use these 2D building blocks for constructing advanced heterostructured devices. Therefore, it would be ideal to grow high‐quality 2D materials with minimized contact and binding with substrate. Through both calculation and experiment, it is demonstrated that by introducing a seed layer at the nucleation stage, the crystallographic disregistry and the corresponding adhesion energy between 2D materials and substrate can be altered, resulting in a change of crystal surface in contact with the substrate, and therefore vertical growth of 2D materials on substrates. As an example, it is demonstrated that with Bi2O3 serving as a seed layer, vertical growth of 2D plates of Bi2O2Se on mica substrates can be realized. These vertically grown 2D nanoplates of Bi2O2Se can be conveniently transferred with their thermal properties investigated for the first time.  相似文献   

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