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1.
Photocatalysis is the most promising method for achieving artificial photosynthesis, but a bottleneck is encountered in finding materials that could efficiently promote the water splitting reaction. The nontoxicity, low cost, and versatility of photocatalysts make them especially attractive for this application. This study demonstrates that small amounts of α‐Fe2O3 nanosheets can actively promote exfoliation of g‐C3N4, producing 2D hybrid that exhibits tight interfaces and an all‐solid‐state Z‐scheme junction. These nanostructured hybrids present a high H2 evolution rate >3 × 104 µmol g‐1 h‐1 and external quantum efficiency of 44.35% at λ = 420 nm, the highest value so far reported among the family of g‐C3N4 photocatalysts. Besides effectively suppressing the recombination of electron–hole pairs, this Z‐scheme junction also exhibits activity toward overall water splitting without any sacrificial donor. The proposed synthetic route for controlled production of 2D g‐C3N4‐based structures provides a scalable alternative toward the development of highly efficient and active photocatalysts.  相似文献   

2.
Tantalum nitride (Ta3N5) with a suitable bandgap (≈2 eV) is regarded as one of the most promising photocatalysts for efficient solar energy harvesting and conversion. However, Ta3N5 suffers from low hydrogen production activity due to the low carrier mobility and fast carrier recombination. Thus, the design of Ta3N5 nanostructures to facilitate charge carrier transport and improve photocatalytic performance remains a challenge. This study reports a new type of ultrathin (≈2 nm) Ta3N5 nanomesh with high specific surface area (284.6 m2 g?1) and excellent crystallinity by an innovative bottom‐up graphene oxide templated strategy. The resulting Ta3N5 nanomeshes demonstrate drastically improved electron transport ability and prolonged lifetime of charge carriers, due to the nature of high surface area and excellent crystallinity. As a result, when used as photocatalysts, the Ta3N5 nanomeshes exhibit a greater than tenfold improvement in solar hydrogen production compared to bulk counterparts. This work provides an effective and generic strategy for designing 2D ultrathin nanomesh structures for nonlayered materials with improved catalytic activity.  相似文献   

3.
Green plants use solar energy efficiently in nature. Simulating the exquisite structure of a natural photosynthesis system may open a new approach for the construction of desirable photocatalysts with high light harvesting efficiency and performance. Herein, inspired by the excellent light utilization of “leaf mosaic” in plants, a novel vine‐like g‐C3N4 (V‐CN) is synthesized for the first time by copolymerizing urea with dicyandiamide‐formaldehyde (DF) resin. The as‐prepared V‐CN exhibits ultrahigh photocatalytic hydrogen production of 13.6 mmol g?1 h?1 under visible light and an apparent quantum yield of 12.7% at 420 nm, which is ≈38 times higher than that of traditional g‐C3N4, representing one of the highest‐activity g‐C3N4‐based photocatalysts. This super photocatalytic performance is derived from the unique leaf mosaic structure of V‐CN, which effectively improves its light utilization and affords a larger specific surface area. In addition, the introduction of DF resin further optimizes the energy band of V‐CN, extends its light absorption, and improves its crystallinity and interfacial charge transport, resulting in high performance. It is an easy and green strategy for the preparation of broad‐spectrum, high‐performance g‐C3N4, which presents significant advancement for the design of other nanophotocatalysts by simulating the fine structure of natural photosynthesis.  相似文献   

4.
A series of narrow‐bandgap π‐conjugated oligomers based on diketopyrrolopyrrole chromophoric units coupled with benzodithiophene, indacenodithiophene, thiophene, and isoindigo cores are designed and synthesized for application as donor materials in solution‐processed small‐molecule organic solar cells. The impacts of these different central cores on the optoelectronic and morphological properties, carrier mobility, and photovoltaic performance are investigated. These π‐extended oligomers possess broad and intense optical absorption covering the range from 550 to 750 nm, narrow optical bandgaps of 1.52–1.69 eV, and relatively low‐lying highest occupied molecular orbital (HOMO) energy levels ranging from ?5.24 to ?5.46 eV in their thin films. A high power conversion efficiency of 5.9% under simulated AM 1.5G illumination is achieved for inverted organic solar cells based on a small‐molecule bulk‐heterojunction system consisting of a benzodithiophene‐diketopyrrolopyrrole‐containing oligomer as a donor and [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM) as an acceptor. Transmission electron microscopy and energy‐dispersive X‐ray spectroscopy reveal that interpenetrating and interconnected donor/acceptor domains with pronounced mesoscopic phase segregation are formed within the photoactive binary blends, which is ideal for efficient exciton dissociation and charge transport in the bulk‐heterojunction devices.  相似文献   

5.
The primary amine groups on the heptazine‐based polymer melon, also known as graphitic carbon nitride (g‐C3N4), can be replaced by urea groups using a two‐step postsynthetic functionalization. Under simulated sunlight and optimum Pt loading, this urea‐functionalized carbon nitride has one of the highest activities among organic and polymeric photocatalysts for hydrogen evolution with methanol as sacrificial donor, reaching an apparent quantum efficiency of 18% and nearly 30 times the hydrogen evolution rate compared to the nonfunctionalized counterpart. In the absence of Pt, the urea‐derivatized material evolves hydrogen at a rate over four times that of the nonfunctionalized one. Since “defects” are conventionally accepted to be the active sites in graphitic carbon nitride for photocatalysis, the work here is a demonstrated example of “defect engineering,” where the catalytically relevant defect is inserted rationally for improving the intrinsic, rather than extrinsic, photocatalytic performance. Furthermore, the work provides a retrodictive explanation for the general observation that g‐C3N4 prepared from urea performs better than those prepared from dicyandiamide and melamine. In‐depth analyses of the spent photocatalysts and computational modeling suggest that inserting the urea group causes a metal‐support interaction with the Pt cocatalyst, thus facilitating interfacial charge transfer to the hydrogen evolving centers.  相似文献   

6.
Photocatalysis is considered as one of the promising routes to solve the energy and environmental crises by utilizing solar energy. Graphitic carbon nitride (g‐C3N4) has attracted worldwide attention due to its visible‐light activity, facile synthesis from low‐cost materials, chemical stability, and unique layered structure. However, the pure g‐C3N4 photocatalyst still suffers from its low separation efficiency of photogenerated charge carriers, which results in unsatisfactory photocatalytic activity. Recently, g‐C3N4‐based heterostructures have become research hotspots for their greatly enhanced charge carrier separation efficiency and photocatalytic performance. According to the different transfer mechanisms of photogenerated charge carriers between g‐C3N4 and the coupled components, the g‐C3N4‐based heterostructured photocatalysts can be divided into the following categories: g‐C3N4‐based conventional type II heterojunction, g‐C3N4‐based Z‐scheme heterojunction, g‐C3N4‐based p–n heterojunction, g‐C3N4/metal heterostructure, and g‐C3N4/carbon heterostructure. This review summarizes the recent significant progress on the design of g‐C3N4‐based heterostructured photocatalysts and their special separation/transfer mechanisms of photogenerated charge carriers. Moreover, their applications in environmental and energy fields, e.g., water splitting, carbon dioxide reduction, and degradation of pollutants, are also reviewed. Finally, some concluding remarks and perspectives on the challenges and opportunities for exploring advanced g‐C3N4‐based heterostructured photocatalysts are presented.  相似文献   

7.
Solar‐driven water splitting is in urgent need for sustainable energy research, for which accelerating oxygen evolution kinetics along with charge migration is the key issue. Herein, Mn3+ within π‐conjugated carbon nitride (C3N4) in form of Mn–N–C motifs is coordinated. The spin state (eg orbital filling) of Mn centers is regulated by controlling the bond strength of Mn–N. It is demonstrated that Mn serves as intrinsic oxygen evolution reaction (OER) site and the kinetics is dependent on its spin state with an optimized eg occupancy of ≈0.95. Specifically, the governing role of eg occupancy originates from the varied binding strength between Mn and OER intermediates. Benefiting from the rapid spin state‐mediated OER kinetics, as well as extended optical absorption (to 600 nm) and accelerated charge separation by intercalated metal‐to‐ligand state, Mn–C3N4 stoichiometrically splits pure water with H2 production rate up to 695.1 µmol g?1 h?1 under simulated sunlight irradiation (AM1.5), and achieves an apparent quantum efficiency of 4.0% at 420 nm, superior to most solid‐state based photocatalysts to date. This work for the first time correlates photocatalytic redox kinetics with the spin state of active sites, and suggests a nexus between photocatalysis and spin theory.  相似文献   

8.
A microwave‐induced metal dissolution strategy is developed for in situ synthesis of copper nanowires/ZnS (CuNWs/ZnS) hybrids with core–shell structure. The CuNWs are used as microwave antennas to create local “super‐hot” surfaces to further initiate ZnS crystallization with full coverage on CuNWs. With the help of S2?, the hot metal surface further results in the CuNWs dissolution with promoted Cu+ diffusion and incorporation into the ZnS lattice. With the narrowed bandgap of ZnS and the strongly coupled interface between CuNWs and ZnS created by microwaves, the as‐prepared hybrid composites exhibit an enhanced activity and stability in visible light for the photocatalytic H2 evolution. The corresponding H2 evolution rate reaches up to 10722 µmol h?1 g?1 with apparent quantum efficiency (AQE) of 69% under 420 nm LED irradiation, showing a remarkably high AQE among the noble‐metal free visible light‐driven photocatalysts and demonstrating a promising potential in practical applications to deal with the energy crisis.  相似文献   

9.
Perovskite‐organic tandem solar cells are attracting more attention due to their potential for highly efficient and flexible photovoltaic device. In this work, efficient perovskite‐organic monolithic tandem solar cells integrating the wide bandgap perovskite (1.74 eV) and low bandgap organic active PBDB‐T:SN6IC‐4F (1.30 eV) layer, which serve as the top and bottom subcell, respectively, are developed. The resulting perovskite‐organic tandem solar cells with passivated wide‐bandgap perovskite show a remarkable power conversion efficiency (PCE) of 15.13%, with an open‐circuit voltage (Voc) of 1.85 V, a short‐circuit photocurrent (Jsc) of 11.52 mA cm?2, and a fill factor (FF) of 70.98%. Thanks to the advantages of low temperature fabrication processes and the flexibility properties of the device, a flexible tandem solar cell which obtain a PCE of 13.61%, with Voc of 1.80 V, Jsc of 11.07 mA cm?2, and FF of 68.31% is fabricated. Moreover, to demonstrate the achieved high Voc in the tandem solar cells for potential applications, a photovoltaic (PV)‐driven electrolysis system combing the tandem solar cell and water splitting electrocatalysis is assembled. The integrated device demonstrates a solar‐to‐hydrogen efficiency of 12.30% and 11.21% for rigid, and flexible perovskite‐organic tandem solar cell based PV‐driven electrolysis systems, respectively.  相似文献   

10.
In this work, plasmonic Au/SnO2/g‐C3N4 (Au/SO/CN) nanocomposites have been successfully synthesized and applied in the H2 evolution as photocatalysts, which exhibit superior photocatalytic activities and favorable stability without any cocatalyst under visible‐light irradiation. The amount‐optimized 2Au/6SO/CN nanocomposite capable of producing approximately 770 μmol g?1 h?1 H2 gas under λ > 400 nm light illumination far surpasses the H2 gas output of SO/CN (130 μmol g?1), Au/CN (112 μmol g?1 h?1), and CN (11 μmol g?1 h?1) as a contrast. In addition, the photocatalytic activity of 2Au/6SO/CN maintains unchanged for 5 runs in 5 h. The enhanced photoactivity for H2 evolution is attributed to the prominently promoted photogenerated charge separation via the excited electron transfer from plasmonic Au (≈520 nm) and CN (470 nm > λ > 400 nm) to SO, as indicated by the surface photovoltage spectra, photoelectrochemical IV curves, electrochemical impedance spectra, examination of formed hydroxyl radicals, and photocurrent action spectra. Moreover, the Kelvin probe test indicates that the newly aligned conduction band of SO in the fabricated 2Au/6SO/CN is indispensable to assist developing a proper energy platform for the photocatalytic H2 evolution. This work distinctly provides a feasible strategy to synthesize highly efficient plasmonic‐assisted CN‐based photocatalysts utilized for solar fuel production.  相似文献   

11.
Efficient spatial charge separation is critical for solar energy conversion over solid photocatalysts. The development of efficient visible‐light photocatalysts has been of immense interest, but with limited success. Here, multiband core–shell oxynitride nanocube heterojunctions composed of a tantalum nitride (Ta3N5) core and nitrogen‐doped sodium tantalate (NaTaON) shell have been constructed via an in situ phase‐induced etching chemical strategy. The photocatalytic water splitting performance of sub‐20‐nm Ta3N5@NaTaON junctions exhibits an extraordinarily high photocatalytic activity toward oxygen and hydrogen evolution. Most importantly, the combined experimental results and theoretical calculations reveal that the strong interfacial Ta? O? N bonding connection as a touchstone among Ta3N5@NaTaON junctions provides a continuous charge transport pathway rather than a random charge accumulation. The prolonged photoexcited charge carrier lifetime and suitable band matching between the Ta3N5 core and NaTaON shell facilitate the separation of photoinduced electron–hole pairs, accounting for the highly efficient photocatalytic performance. This work establishes the use of (oxy)nitride heterojunctions as viable photocatalysts for the conversion of solar energy into fuels.  相似文献   

12.
As wide range of light absorption and suitable redox potentials are prerequisites for photocatalytic water splitting, exploring new semiconductor‐based materials with proper band structures for water splitting still calls for longstanding efforts. In this work, a series of photocatalysts, bismuth tantalum oxyhalide, Bi4TaO8X (X = Cl, Br), with valence band and conduction band positions at ≈?0.70 and ≈1.80 eV versus the reversible hydrogen electrode (RHE), respectively, are found to be capable for both water oxidation and reduction under visible light irradiation. Using flux synthetic methods, Bi4TaO8X (X = Cl, Br) with microplatelet morphology can be successfully prepared. The photocatalyst based on these materials shows an apparent quantum efficiency as high as 20% at 420 nm for water oxidation. In addition, a Z‐scheme system coupling Bi4TaO8Br with Ru/SrTiO3:Rh is successfully achieved for overall water splitting with a stoichiometric ratio of H2 and O2 evolutions. This work demonstrates a new series of semiconductors Bi4TaO8X (X = Cl, Br) with the promising application in the field of solar energy utilization.  相似文献   

13.
In this work, the authors realize stable and highly efficient wide‐bandgap perovskite solar cells that promise high power conversion efficiencies (PCE) and are likely to play a key role in next generation multi‐junction photovoltaics (PV). This work reports on wide‐bandgap (≈1.72 eV) perovskite solar cells exhibiting stable PCEs of up to 19.4% and a remarkably high open‐circuit voltage (VOC) of 1.31 V. The VOC‐to‐bandgap ratio is the highest reported for wide‐bandgap organic?inorganic hybrid perovskite solar cells and the VOC also exceeds 90% of the theoretical maximum, defined by the Shockley–Queisser limit. This advance is based on creating a hybrid 2D/3D perovskite heterostructure. By spin coating n‐butylammonium bromide on the double‐cation perovskite absorber layer, a thin 2D Ruddlesden–Popper perovskite layer of intermediate phases is formed, which mitigates nonradiative recombination in the perovskite absorber layer. As a result, VOC is enhanced by 80 mV.  相似文献   

14.
A series of narrow bandgap electron acceptors is designed and synthesized for efficient near‐infrared (NIR) organic solar cells. Extending π‐conjugation of donor frameworks leads to an intense intramolecular charge transfer, resulting in broad absorption profiles with band edge reaching 950 nm. When blended with an electron donor polymer PTB7‐Th, IOTIC‐2F exhibits efficient charge transfer even with a small energetic offset, so as to achieve a large photogenerated current over 22 mA cm?2 with small energy losses (≈0.49 eV) in solar cell devices. With an intense NIR absorbance, PTB7‐Th:IOTIC‐2F‐based cells achieve a power conversion efficiency of 12.1% with good visible transparency (52% transmittance from 370 to 740 nm). Analysis of film morphology reveals that processing with solvent additives enhances crystalline features of acceptor components, while keeping an appropriate level of donor:acceptor intermixing in the binary blends. The incorporation of the third component, ITIC‐2F, into the PTB7‐Th:IOTIC‐2F blends increases the device efficiency up to 12.9%. The improvement is assigned to the cascaded energy‐level structure and desirable nanoscale phase separation of the ternary blends, which is beneficial to the photocurrent generation. This work provides an efficient molecular design strategy to optimize nonfullerene acceptor properties for efficient NIR organic photovoltaics.  相似文献   

15.
Two narrow bandgap non‐fullerene acceptors (NBG‐NFAs), namely, COTIC‐4F and SiOTIC‐4F, are designed and synthesized for the fabrication of efficient near‐infrared organic solar cells (OSCs). The chemical structures of the NBG‐NFAs contain a D′‐D‐D′ electron‐rich internal core based on a cyclopentadithiophene (or dithienosilole) (D) and alkoxythienyl (D′) core, end‐capped with the highly electron‐deficient unit 2‐(5,6‐difluoro‐3‐oxo‐2,3‐dihydro‐1H‐inden‐1‐ylidene)malononitrile (A), ultimately providing a A‐D′‐D‐D′‐A molecular configuration that enhances the intramolecular charge transfer characteristics of the excited states. One can thereby reduce the optical bandgap (Egopt) to as low as ≈1.10 eV, one of the smallest values for NFAs reported to date. In bulk‐heterojunction (BHJ) OSCs, NBG‐NFA blends with the polymer donor PTB7‐Th yield power conversion efficiencies (PCE) of up to 9.0%, which is particularly high when compared against a range of NBG BHJ blends. Most significantly, it is found that, despite the small energy loss (Egopt ? eVOC) of 0.52 eV, the PTB7‐Th/NBG‐NFA bulk heterojunction blends can yield short‐circuit current densities of up to 22.8 mA cm?2, suggesting that the design and application of NBG‐NFA materials have substantial potential to further improve the PCE of OSCs.  相似文献   

16.
All‐perovskite multijunction photovoltaics, combining a wide‐bandgap (WBG) perovskite top solar cell (EG ≈1.6–1.8 eV) with a low‐bandgap (LBG) perovskite bottom solar cell (EG < 1.3 eV), promise power conversion efficiencies (PCEs) >33%. While the research on WBG perovskite solar cells has advanced rapidly over the past decade, LBG perovskite solar cells lack PCE as well as stability. In this work, vacuum‐assisted growth control (VAGC) of solution‐processed LBG perovskite thin films based on mixed Sn–Pb perovskite compositions is reported. The reported perovskite thin films processed by VAGC exhibit large columnar crystals. Compared to the well‐established processing of LBG perovskites via antisolvent deposition, the VAGC approach results in a significantly enhanced charge‐carrier lifetime. The improved optoelectronic characteristics enable high‐performance LBG perovskite solar cells (1.27 eV) with PCEs up to 18.2% as well as very efficient four‐terminal all‐perovskite tandem solar cells with PCEs up to 23%. Moreover, VAGC leads to promising reproducibility and potential in the fabrication of larger active‐area solar cells up to 1 cm2.  相似文献   

17.
Periodically patterned zinc oxide nanorod (P‐ZnO NR) layers are directly prepared from a pre‐patterned ZnO seed layer using a polydimethylsiloxane (PDMS) elastomeric stamp and then applied in inverted organic photovoltaic devices (IOPVs). The IOPV is assembled with a hydrothermally grown zinc oxide nanorod patterns with a (100) preferential crystal orientation as an electron transport buffer layer (ETBL) and photoactive bilayer consisting of methacylate end‐functionalized poly(3‐hexylthiophene) (P3HT‐MA), phenyl‐C60‐butyric acid methyl ester (PC60BM) and indene‐C60 bis‐adduct (IC60BA). In te IOPVs, the P‐ZnO NR is found to induce efficient light harvesting and the photocrosslinkable P3HTs afford solution‐processed bilayer architecture in IOPVs to show improved device stability and performance (PCEmax= 5.95%), as the bilayered structure allowed direct exciton splitting, thus reducing the charge recombination.  相似文献   

18.
Nonfullerene polymer solar cells (PSCs) are fabricated by using one wide bandgap donor PBDB‐T and one ultranarrow bandgap acceptor IEICO‐4F as the active layers. One medium bandgap donor PTB7‐Th is selected as the third component due to the similar highest occupied molecular orbital level compared to that of PBDB‐T and their complementary absorption spectra. The champion power conversion efficiency (PCE) of PSCs is increased from 10.25% to 11.62% via incorporating 20 wt% PTB7‐Th in donors, with enhanced short‐circuit current (JSC) of 24.14 mA cm?2 and fill factor (FF) of 65.03%. The 11.62% PCE should be the highest value for ternary nonfullerene PSCs. The main contribution of PTB7‐Th can be summarized as the improved photon harvesting and enhanced exciton utilization of PBDB‐T due to the efficient energy transfer from PBDB‐T to PTB7‐Th. Meanwhile, PTB7‐Th can also act as a regulator to adjust PBDB‐T molecular arrangement for optimizing charge transport, resulting in the enhanced FF of ternary PSCs. This experimental result may provide new insight for developing high‐performance ternary nonfullerene PSCs by selecting two well‐compatible donors with different bandgap and one ultranarrow bandgap acceptor.  相似文献   

19.
Developing efficient and affordable catalysts is of great significance for energy and environmental sustainability. Heterostructure photocatalysts exhibit a better performance than either of the parent phases as it changes the band bending at the interfaces and provides a driving force for carrier separation, thus mitigating the effects of carrier recombination and back‐reaction. Herein, the photo/electrochemical applications of a variety of metal sulfides (MSx) (MoS2, CdS, CuS, PbS, SnS2, ZnS, Ag2S, Bi2S3, and In2S3)/TiO2 heterojunctions are summarized, including organic degradation, water splitting, and CO2 reduction conversion. First, a general introduction on each MSx material (especially bandgap structures) will be given. Then the photo/electrochemical applications based on MSx/TiO2 heterostructures are reviewed from the perspective of light harvesting ability, charge carrier separation and transportation, and surface chemical reactions. Special focus is given to CdS/TiO2 and PbS/TiO2‐based quantum dot sensitized solar cells. Ternary composites by taking advantages of positive synergetic effects are also well summarized. Finally, conclusions are made regarding approaches for structure design, and the authors' perspective on future architectural design and electrode construction is given. This work will make up the gap for TiO2 nanocomposites and shed light on the fabrication of more efficient MSx‐metal oxide junctions in photo/electrochemical applications.  相似文献   

20.
Copper(I) oxide (Cu2O) is an attractive photocatalyst because of its abundance, low toxicity, environmental compatibility, and narrow direct band gap, which allows efficient light harvesting. However, Cu2O exhibits poor photocatalytic performance and photostability because of its short electron diffusion length and low hole mobility. Here, it is demonstrated that nanodiamond (ND) can greatly improve the photocatalytic hydrogen evolution reaction (HER) of the p‐type photocatalyst Cu2O nanocrystals by nanocomposition. Compared with pure Cu2O nanocrystals, this composite shows a tremendous improvement in HER performance and photostability. HER rates of 100.0 mg NDs‐Cu2O nanocrystals are 1597 and 824 under the simulated solar light irradiation (AM 1.5, 100 mW cm?2) and visible light irradiation (420–760 nm, 77.5 mW cm?2), respectively. The solar‐to‐hydrogen conversion efficiency of this composite is 0.85%, which is nearly ten times higher than that of pure Cu2O. The quantum efficiency of the composite is high, with values of 0.17% at and 0.23% at . The broad spectral response of ND provides numerous carriers for the subsequent reactions. The electron‐donating ability of ND and suitable band structures of the two components promote electron injection from ND to Cu2O. These results suggest the broad applicability of ND to ameliorate the photoelectric properties of semiconductors.  相似文献   

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