Accelerated Charge Separation Research Articles

ZIF-8 derived hierarchical ZnO@ZnFe2O4 hollow polyhedrons anchored with CdS for efficient photocatalytic CO2 reduction

Converting CO2 into chemical energy by efficient photocatalysts is a promising strategy to meet the increasing energy demand and decrease greenhouse gases. In this work, hierarchical ZnO@ZnFe2O4 hollow polyhedrons decorated with CdS quantum dots were designed and prepared to improve photocatalytic CO2 reduction performance. The facile strategy for the synthesis of hierarchical ZnO@ZnFe2O4 hollow polyhedrons involves the synthesis of ZnO hollow polyhedrons derived from the thermal decomposition of 2-Methylimidazole zinc salt (ZIF-8) precursor and in situ generating Zn-Fe layer double hydroxide nanosheets on the surface of ZnO hollow polyhedrons and subsequent thermal treatment. More importantly, the in situ formation of ZnFe2O4 nanosheets can form strong interaction between ZnO hollow polyhedrons and ZnFe2O4 nanosheets. The hierarchical hollow polyhedral structure of the ZnO@ZnFe2O4 sample possesses more preferable active sites to promote CO2 adsorption and reduction process. The prepared hierarchical ZnO@ZnFe2O4 hollow polyhedron sample shows a significantly enhanced performance for photocatalytic CO2 reduction compared with single-component catalysts (ZnO, ZnFe2O4, and CdS) with a CO evolution rate of 95.84 μmol g−1h−1. The decoration of CdS quantum dots makes the ternary heterostructure hybrid form multichannel charge transfer path, which further accelerate charge separation and enhance electrons utilization, resulting in a significant improvement of photocatalytic activity. Noticeably, the CO evolution rate reaches 197.66 μmol g−1h−1, 3 and 2 times higher than that of the bare ZnO and binary ZnO@ZnFe2O4 hollow polyhedrons, respectively. This work gives a promising direction to prepare high-active photocatalysts for solar fuel production.

Incorporating Ni-Polyoxometalate into the S-Scheme Heterojunction to Accelerate Charge Separation and Resist Photocorrosion for Promoting Photocatalytic Activity and Stability.

The emerging polyoxometalate (POM) nanomaterials are transition metal oxygen anion clusters with d0 electronic configurations, which could be attractive and potential photocatalysts. Hence, a nickel (Ni)-substituted polyoxometalate K6Na4[Ni4(H2O)2(PW9O34)2]·32H2O (Ni4POM)-incorporating step (S)-scheme heterojunction was developed to promote photocatalytic activity and stability in H2 and H2O2 production. The multielectron transfer through variable valence metal centers in Ni4POM would facilitate the recombination of invalid charges through the S-scheme pathway. Moreover, incorporating Ni4POM into the S-scheme heterojunction can broaden the light absorption range and meanwhile lead to resistance to photocorrosion to promote the optical and chemical stability of Cd0.5Zn0.5S (CZS). The optimized CZSNi-70 exhibited a H2 evolution rate of 42.32 mmol g-1 h-1 under visible-light irradiation with an apparent quantum yield of 32.27% at 420 nm and a H2O2 production rate of 295.4 μmol L-1 h-1 under 420 nm light-emitting diode irradiation. This work can provide a new view for the development of transition metal-substituted POM-based stable and efficient S-scheme photocatalysts.

Boosting interfacial S-scheme charge transfer and photocatalytic H2-production activity of 1D/2D WO3/g-C3N4 heterojunction by molecular benzene-rings integration

A novel benzene-ring engineered 1D/2D WO3/g-C3N4 S-scheme photocatalyst (BCNW) was rationally designed and successfully synthesized by the electrostatic self-assembly method. Experimental and Density Functional Theory results reveal that the integration of molecular benzene-ring in the framework of g-C3N4 can not only narrow its bandgap and accelerate charge separation by forming a mid-state at the top of its valence band but more importantly open up a new additional bridge for speeding up the interfacial S-scheme charge transfer in BCNW. Benefitting from those multiple positive effects of benzene-ring integration, as expected, BCNW S-scheme photocatalysts show superior photocatalytic H2-production activity and reach 2971 μmol h–1 g–1 under visible-light illumination, which is 3.35 times WO3/g-C3N4 S-scheme photocatalyst without benzene-ring integration. This work supplies an innovative strategy for the design of a high-efficiency S-scheme photocatalytic system by constructing a facile and additional molecular charge transfer channel at the interface.

Facilitated charge transfer in ZnIn2S4@CuInP2S6 heterojunctions towards efficient photocatalytic H2 generation

Accelerating charge separation and migration in semiconductor photocatalysts is the key for acquiring high performance in the photocatalytic hydrogen generation reaction. In this work, a new ZnIn2S4/CuInP2S6 hetero-structured system (ZIS/CIPS) is designed and constructed. Owing to the presence of face-to-face hetero-interface with high charge-transport capability, the photocatalytic hydrogen generation rate of ZIS/CIPS dramatically enhanced (76.2 μmol h−1) under the visible-light irradiation, which is up to 13 and 190 times compared to that of ZnIn2S4 and CuInP2S6 (CIPS), respectively.

Electron-Deficient Zn-N6 Configuration Enabling Polymeric Carbon Nitride for Visible-Light Photocatalytic Overall Water Splitting

HighlightsAtomically dispersed Zn-anchored 3D sponge-like polymeric carbon nitride (Zn-PCN) characteristic of a unique Zn-N6 electron-deficient configuration is synthesized via an intermediate coordination strategy.The electron-deficient Zn-N6 configuration contributes to enhanced electron excitation, accelerated charge separation and transfer as well as reduced overpotentials of water redox reactions.The obtained Zn-PCN realizes photocatalytic overall water splitting to stoichiometrically produce H2 and O2 with good durability under visible light.

The effect of CO2-doped spiro-OMeTAD hole transport layer on FA(1−x)CsxPbI3 perovskite solar cells

Black-phase formamidinium lead iodine with 1.48 eV bandgap is considered to be the most promising material for improving the near-theoretical limit efficiency of perovskite solar cells, but at room temperature, black-phase formamidinium lead iodine easily transforms into the yellow non-perovskite phase formamidinium lead iodine. Here, different ratios of Cs+-incorporated formamidinium lead iodine prepared by one-step processing with the stability and power conversion efficiency of formamidinium lead iodine perovskite solar cells are investigated. FA0.85Cs0.15PbI3 shows the highest power conversion efficiency of 10.63% (Voc = 1.04 V, Jsc = 16.81 mA cm−2, and fill factor = 0.60), and the unencapsulated device maintained 60% of the initial power conversion efficiency after storage in air with 40% humidity for 186 h with an active area of 0.1 cm2, when the ratios of Cs+ reached 15% ( x = 0.15) in formamidinium lead iodine. However, the efficiency of perovskite solar cell–based formamidinium lead iodine is still low. In this work, a simple but an effective strategy was carried out to rapidly and fully oxidize hole transport layer solution by doping CO2 or O2 under ultraviolet light irradiation to increase the conductivity of hole transport layer, thereby improving the power conversion efficiency of solar cells. The results show that FA0.85Cs0.15PbI3 solar cells by CO2-doped hole transport layer for 90 s exhibited the highest power conversion efficiency of 16.11% (VOC = 1.11 V, JSC = 19.73 mA cm−2, and fill factor = 0.74). The improved photovoltaic performance is attributed to CO2-doped spiro-OMeTAD increasing charge carrier density and accelerating charge separation, thereby inducing higher conductivity. CO2 or O2 doped can rapidly and fully oxidize spiro-OMeTAD, and reduce the solar cell fabrication time; it is beneficial to the commercial use of perovskite solar cells.

An in situ defect engineering approach for light-driven methane dry reforming over atomically distributed nickel

Dry reforming of methane economically converts methane and carbon dioxide into syngas (hydrogen and carbon monoxide) but requires high energy and often suffers from catalyst instability. Here, a surface-modulation strategy is demonstrated via decorating in situ defects on isolated nickel (Ni) atoms over La2O3 for boosting light-driven dry reforming of methane activity. Atomically dispersed 0.5Ni/La2O3 achieves a hydrogen evolution rate of 170.9 mol gNi−1 h−1. The reactivity is mainly attributed to photogenerated electrons, which overcome the limitations of a purely thermal system. The in situ generation of oxygen vacancies increases the initial-stage reactivity, where oxygen vacancies act as electron traps to accelerate charge separation and promote the adsorption/activation of reactants. The 0.5Ni/La2O3 catalyst exhibits strong inhibition of carbon coking and is sintering resistant, benefiting from the synergy between in situ oxygen vacancies and isolated nickel atoms.

Ferroelectric nano-heterojunctions for piezoelectricity-enhanced photocatalysis

Nanoscale heterojunctions of high dielectric constant piezoelectrics and optoelectronic semiconductors are attractive for photocatalytic degradation of hazardous organic compounds. In this work, such a nano-heterojunction was prepared by mixing of surface-carboxylated ferroelectric BaTiO3 nanoparticles (BTO NPs) and protonated graphitic carbon nitride (g-C3N4). Due to strong electrostatic interactions, intimate contact between BTO NPs and g-C3N4 was achieved for efficient charge separation and transfer. Two piezoelectric BTO NPs were used to prepare the BaTiO3/g-C3N4 heterojunctions: as-received BTO (arBTO) and 950 °C-annealed BTO (anBTO) with larger ferroelectric domains. Under ultrasonication, the photocatalytic degradation rate of levofloxacin by anBTO/g-C3N4 heterojunctions were 0.0462 min−1, which were 9.2 times of arBTO and 3.6 times of those in the absence of ultrasonication. The underlying mechanism was attributed to the higher current density, the accelerated charge separation of photo-activated excitons, and the reduced charge recombination via a synergistic effect of heterostructures and the local piezo-potential generated by the ferroelectric BTO NPs. By combination of thermal annealing of arBTO to enlarge the ferroelectric domains and construction of heterostructures, a highly efficient photocatalyst could be obtained. This study provides us a simple yet effective method to achieve highly efficient photocatalysts using the piezoelectric effect of ferroelectric BTO NPs.

A novel co-catalyst of CoFeOOH for greatly improving the solar water splitting performance over Mo-doped bismuth vanadate

BiVO4 stands out among many semiconductor photoanodes because of its appropriate band gap and high valence band value, and is widely used in the field of photo (electro) catalytic water decomposition. However, its low photocurrent density due to its low carrier mobility and short hole distance hinders its application and development. Therefore, we prepared a new type of CoFeOOH/Mo-BiVO4 photoanode, which increased the carrier density by doping Mo element in BiVO4 and then deposited CoFeOOH co-catalyst on the surface of Mo-BiVO4 in room temperature chemical bath, which accelerated charge separation and inhibited electron-hole recombination as a passivation layer. The results show that the prepared composite photoanode has a high photocurrent density (2.45 mA·cm−2), and the initial potential of oxygen evolution has also shifted negatively by 430 mV. This study provides a new idea for photoanode in doping and co-catalyst.

Facile Chemical Vapor Modification Strategy to Construct Surface Cyano-Rich Polymer Carbon Nitrides for Highly Efficient Photocatalytic H2 Evolution.

The surface grafting of electro-negative cyano groups on polymer carbon nitrides (PCNs) is an effective way to tail their electronic structure. Despite the significant progress in the synthesis of cyano group-enriched PCN, developing a simple and efficient method remains challenging. Here, a facile strategy was developed for fabricating surface cyano-rich PCN (PCN-DM) with a porous structure via chemical vapor modification using diaminomaleonitrile. The cyano groups of diaminomaleonitrile substituted the amino groups on PCN surface via a deamination. The hydrogen production rate of the PCN-DM was approximately 17 times higher than that of pristine PCN. This significant increase in photocatalytic performance could be assigned to the fusion of cyano groups in the surface of PCN, forming new gap states that broadened the visible-light harvesting and accelerated charge separation for photoredox reactions. This study unveils a promising approach for incorporating functional units in the design of novel photocatalysts for efficient hydrogen production.

Bismuth Gadolinium Oxychloride with a Remarkable Visible-Light-Responsive O2 Evolution Activity Promoted by Iodine Doping.

Visible-light-responsive bismuth-based oxyhalide has recently attracted extensive attention, however, the promotion of its charge separation is still challenging. Herein, we introduce iodine into Bi2 GdO4 Cl to synthetize I-doped Bi2 GdO4 Cl (denoted as yI-Bi2 GdO4 Cl, 0≤y≤2). The incorporation of I- ions is found to enhance light absorption and to accelerate charge separation by combining various characterizations such as density functional theory calculation, photoelectrochemical test, electrochemical impedance spectroscopy, photoluminescence spectrum, and open-circuit voltage decay. The O2 -evolving performances of 1I-Bi2 GdO4 Cl with optimized dopant concentration of I- ion and IrO2 loaded 1I-Bi2 GdO4 Cl are tremendously enhanced by ca. 4 and 45 times compared to pristine Bi2 GdO4 Cl. Notably, The O2 evolution rate reaches as high as 154.8 μmol ⋅ h-1 with an apparent quantum efficiency of ∼1.1 % at 420 nm. The synthetic iodine-doped photocatalyst remains stable after long-term photoreaction, demonstrating its potential in the field of photocatalysis.

Hierarchical porous TiO2 with a uniform distribution of anchored gold nanoparticles for enhanced photocatalytic efficiency and accelerated charge separation for the degradation of antibiotics.

A novel approach to synthesize porous Au/TiO2 nanocomposites has been achieved through a pyrolytic strategy by employing NH2-MIL-125(Ti) as a TiO2 precursor, and photo-deposition of Au nanoparticles (NPs) onto porous nanocrystalline TiO2 with varying Au contents (0.05-0.5%). TEM images of Au/TiO2 nanocomposites showed that TiO2 particles were spherical structures, highly dispersed, and homogeneous with diameters of 10-15nm, and Au NPs (20-30nm) were anchored onto porous TiO2 matrices with a uniform distribution. The synthesized Au/TiO2 nanocomposites were assessed through the degradation of two antibiotic models, metronidazole (MNZ), and trimethoprim (TMP), under visible light and compared with undoped TiO2 and commercial TiO2 (P-25). The synthesized Au/TiO2 photocatalyst revealed enhanced photocatalytic performance in the mineralization (80%) and degradation (100%) of MNZ and TMP in both water matrices compared to undoped TiO2 (60%, 76%) and commercial P-25 (48%, 65%). The obtained 0.1% Au/TiO2 nanocomposite could complete the mineralization of TMP and MNZ with rate constant values (4.47 × 10-3min-1 and 5.23 × 10-1min-1) owing to the large well-developed porosity and high surface area of TiO2 and the small size of Au NPs with high dispersity, surface plasmon resonance, and stability. The recyclability of the 0.1% Au/TiO2 nanocomposite exhibited high durability without the leaching or loss of photocatalytic performance after four cycles. Complete degradation was achieved within 100min in the water matrix from real wastewater, indicating promising results for the degradation of pharmaceuticals in the different water matrices. The present work opens a new route to synthesize low-cost, effective, and high photocatalytic performance nanocomposites with a small Au content as a cocatalyst onto semiconductor materials.

Two-dimensional Janus like scandium-based MXenes as photocatalysts for overall water splitting: A first-principles study

The potential of monolayer and bilayer Sc2CO2 and Sc2CF2/Sc2CO2 heterostructures as photocatalysts for water splitting was investigated through first-principles calculations. It was confirmed that the most stable configuration of monolayer Sc2CO2 was the Janus structure, and its intrinsic electric field accelerated charge separation. The calculated band structure and band edge position revealed the electronic structures of Sc-based MXenes were suitable for the photocatalytic water splitting reaction under alkaline conditions. Overpotentials for the hydrogen and oxygen evolution reaction with photoexcited electrons and holes were verified via energy diagrams for adsorption Gibbs free energy on the surface of Sc-based MXenes. It was confirmed that the light absorption efficiency of bilayer Sc2CO2 and Sc2CF2/Sc2CO2 heterostructures are substantially higher than monolayer Sc2CO2 via dielectric function and absorption coefficient calculations. As a result, various optimized photocatalysts can be designed through surface engineering of Sc-based MXenes depending on applied conditions.

Optimizing the Reaction Pathway by Active Site Regulation in the CdS/Fe2O3 Z-Scheme Heterojunction System for Highly Selective Photocatalytic Benzylamine Oxidation Integrated with H2 Production

Simultaneous photocatalytic H2 production and preparation of high-value chemicals by the selective oxidation of organic substances is of great significance for solar energy utilization and conversion. Herein, a Pt-modified 2D/2D CdS/Fe2O3 Z-scheme heterojunction was dexterously designed for photocatalytic dehydrogenation coupling of benzylamine with high performance and product selectivity. The Z-scheme charge transfer in CdS/Fe2O3 greatly boosts charge separation and maintains the strong redox capacity of photogenerated electrons and holes. Impressively, the loading of the Pt cocatalyst not only provides rich H2 production active sites to further accelerate charge separation and H2 production kinetics but also facilitates the condensation of N-benzylideneamine with benzylamine for N-benzylidenebenzylamine production and NH3 releasing. The selectivity for C═N coupling products is significantly enhanced and the C–C coupling side reaction is greatly suppressed. With sufficient benzylamine substrate and visible light irradiation, the optimal Pt/CdS/Fe2O3 composite displays a high H2 production rate of 39.4 mmol h–1 g–1 with a quantum efficiency of 32.81% at 420 nm, and the selectivity of benzylamine oxidation to N-benzylidenebenzylamine is above 90%.

Rational fabrication of cadmium-sulfide/graphitic-carbon-nitride/hematite photocatalyst with type II and Z-scheme tandem heterojunctions to promote photocatalytic carbon dioxide reduction

Artificial photosynthesis has become one of the most attractive strategies for lowering atmospheric carbon dioxide (CO2) level and achieving the carbon balance; whereas, the fast electron–hole recombination and sluggish charge transfer in photocatalysts are themain stumbling blocks to the applications. Constructing semiconductor nano-heterostructures provides a promising strategy to accelerate the separation and transfer of photoinduced charge carriers for promoting the multielectron CO2 reduction reaction. Herein, a CdS/g-C3N4/α-Fe2O3 three-component photocatalyst consisting of type II and Z-scheme tandem heterojunctions is skillfully fabricated via the solvothermal synthesis followed with photoinduced deposition. The CdS/g-C3N4/α-Fe2O3 tandem-heterojunction photocatalyst exhibits superior performance toward the conversion of CO2 to fuels (CO and CH4), compared with the single- and binary-component systems, owing to the favorable energy-level alignment, accelerated charge separation, facilitated water dissociation and sufficient reactive-hydrogen provision. The total consumed electron number of CdS/g-C3N4/α-Fe2O3 catalyst for CO2 reduction is about 10.5 times that of pure g-C3N4. The photocatalytic mechanism is elucidated according to detailed characterizations and in-situ spectroscopy analyses. This work sheds light on the rational construction of heterojunction photocatalysts to promote the conversion of CO2 to solar fuels, without using any sacrifice reagent or noble-metal cocatalysts.

Improved carrier dynamics in nickel/urea-functionalized carbon nitride for ethanol photoreforming.

Photoreforming has been shown to accelerate the H2 evolution rate compared to water splitting due to thermodynamically favorable organic oxidation. In addition, the potential to simultaneously produce solar fuel and value-added chemicals is a significant benefit of photoreforming. To achieve an efficient and economically viable photoreforming process, the selection and design of an appropriate photocatalyst is essential. Carbon nitride is promising as a metal-free photocatalyst with visible light activity, high stability, and low fabrication cost. However, it typically exhibits poor photogenerated charge carrier dynamics, thereby resulting in low photocatalytic performance. Herein, we demonstrate improved carrier dynamics in urea-functionalized carbon nitride with in situ photodeposited Ni cocatalyst (Ni/Urea-CN) for ethanol photoreforming. In the presence of 1mM Ni2+ precursor, an H2 evolution rate of 760.5µmolh-1g-1 and an acetaldehyde production rate of 888.2µmolh-1g-1 were obtained for Ni/Urea-CN. The enhanced activity is ascribed to the significantly improved carrier dynamics in Urea-CN. The ability of oxygen moieties in the urea group to attract electrons and to increase the hole mobility via a positive shift in the valence band promotes an improvement in the overall carrier dynamics. In addition, high crystallinity and specific surface area of the Urea-CN contributed to accelerating charge separation and transfer. As a result, the electrons were efficiently transferred from Urea-CN to the Ni cocatalyst for H2 evolution while the holes were consumed during ethanol oxidation. The work demonstrates a means by which carrier dynamics can be tuned by engineering carbon nitride via edge functionalization.

Construction of rGO-coupled C3N4/C3N5 2D/2D Z-scheme heterojunction to accelerate charge separation for efficient visible light H2 evolution

As a fascinating two-dimensional (2D) conjugated polymer, graphitic carbon nitride (C3N4) has drawn broad attention as metal-free photocatalyst, but it’s further utilization is confined by the limited visible light harvesting and severe charge recombination. Herein, N-rich carbon nitride (C3N5) with an azo-linked two s-heptazine units, different from C3N4 with a tertiary N-atom linked three s-heptazines, is prepared for constructing a novel sandwich heterojunction composed of reduced graphene oxide (rGO)-coupled C3N5 and C3N4. The introduced rGO in C3N4/rGO/C3N5 heterojunction can accelerate the interfacial charge separation and promote a rGO-mediated solid-state Z-scheme mechanism with an obvious synergistic effect, whereby C3N4 and C3N5 serve as electron-rich and hole-rich reservoirs, respectively. The resultant 2D/2D heterojunction delivers efficient visible-light-responsive activity with H2 evolution rate of 319 μmol h−1, 5.6 and 2.7 times higher than that of C3N4 and C3N5 alone, respectively. This work presents a new concept to design highly efficient carbon nitride-based artificial photosynthetic system.

Interface Cd-N bond bridge accelerating charge separation to the enhanced visible light driven hydrogen production from water splitting on polyaniline@Cd-Zn-S photocatalyst

The key to the industrialization of eco-friendly hydrogen production from visible light driven water splitting is the development of photocatalyst with high performance and superior stability. Herein, a novel core-shell structure polyaniline@Cd-Zn-S (Cd/Zn = 0.8/0.2) nanorod photocatalyst with the shell thickness at ∼3 nm was constructed successfully. With polyaniline served as core, the construction of polyaniline@Cd-Zn-S reduced the charge transfer resistance and released reactive sites maximumly which could benefit the hydrogen production. The constructed polyaniline@Cd-Zn-S exhibited excellent photocatalytic hydrogen production efficiency and stability with the assistance of interface Cd-N bonds. The introduction of Cd-N bonds at the interface was inferred by both experimental and DFT simulated results. It served as the bridge between shell Cd-Zn-S and core polyaniline and promoted the directional transmission and efficient separation of photo generated charge carriers. Meanwhile, the improved directional transmission of photogenerated holes restricted photo corrosion effect of the Cd-Zn-S effectively and contributed to the photocatalytic stability. The hydrogen production without any cocatalyst increased more than 6 times to 721 μmol·h−1 after the construction of core-shell structure, and remain stable for 12 consecutive hours without photocatalytic performance reduction. This work proposed a new inspiring structural model for hetero junction construction of photocatalyst, and brought an interesting enlightenment to the development of eco-friendly hydrogen production technology.

(Invited) A Carbon Nanotube Binding Bis(pyrenylstyryl)Bodipy-C60 Nano Tweezer: Formation and Photoinduced Charge Separation in Supramolecular C60-Bodipy-SWCNT Triads

Electron donor-acceptor hybrids comprised of single-wall carbon nanotubes (SWCNT) are promising functional structures having direct applications in energy conversion schemes and molecular optoelectronics. For building such hybrids and exfoliation of SWCNTs, the p-stacking ability of large aromatic compounds such as pyrene is one of the commonly employed approaches. Often, the desired donor or acceptor entities are functionalized to carry one or more pyrene entities and allowed to interact with CNTs. As a suitable electron donor, BODIPYs stand out owing to their ease of structural modifications and rich spectral and redox properties. Consequently, several donor-acceptor conjugates comprised of BF2-chelated dipyrromethene, BODIPY, and the well-known electron acceptor, C60 have been developed. In the present study, we have newly synthesized a nano tweezer comprised of covalently linked BODIPY-C60 carrying two pyrenylstyryl arms, 1. Compound 1 is further allowed to interact with SWCNT(6,5) and SWCNT(7,6) to form the supramolecular C60-BODIPY-SWCNT triads. Upon spectral, electrochemical, and computational characterization, pump-probe spectroscopic studies covering a wide femto-to-millisecond time scale have been performed to establish the occurrence of photoinduced charge separation. The presence of CNT prolonged the lifetime of the charge-separated states revealing the success of the present molecular design strategy for energy harvesting applications. D’Souza, F.; Sandanayaka, A. S. D.; Ito, O. ‘SWNT-Based Supramolecular Nanoarchitectures with Photosensitizing Donor and Acceptor Molecules’ Phys. Chem. Letts. 2010, 1. 2586-2593.B. KC, G. N. Lim, and F. D’Souza, ‘Accelerated Charge Separation in Graphene Decorated Multi-Modular Tripyrene-Subphthalocyanine-Fullerene Donor-Acceptor Hybrids,’ Angew. Chem. Int. Ed. 2015, 54, 5088-5092.Barrejon, L. M. Arellano, F. D’Souza, F. Langa, ‘Bidirectional charge transfer in carbon-based hybrid nanomaterials’ Nanoscale, 2019, 11, 14978-14992. Figure 1

Plasmonic TiN nanobelts assisted broad spectrum photocatalytic H2 generation

The conversion of solar energy in a wide spectrum region to clean fuel, H2, remains a challenge in the field of photocatalysis. Herein, plasmonic TiN nanobelts, as a novel cocatalyst, were coupled with CdS nanoparticles to construct a 0D/1D CdS/TiN heterojunction. Utilization of the localized surface plasmon resonance (LSPR) effect generated from TiN nanobelts was effective in promoting light absorption in the near-infrared region, accelerating charge separation, and generating hot electrons, which can effectively improve the photocatalytic H2 generation activity of the 0D/1D CdS/TiN heterojunction over a wide spectral range. Furthermore, owing to the high metallicity and low work function, an ohmic-junction was formed between the CdS and TiN, favoring the transfer of hot electrons generated from TiN nanobelts the CdS nanoparticles, followed by the reaction with water to generate H2. Consequently, the 0D/1D CdS/TiN heterojunction demonstrated H2 generation activity even under light irradiation at 760 nm, while the pure CdS and Pt nanoparticles modified CdS presented no activity. This work opens a new insight into coupling plasmonic cocatalysts to realize full spectrum H2 production.