One step from nanofiber to functional hybrid structure: Pd doped ZnO/SnO2 heterojunction nanofibers with hexagonal ZnO columns for enhanced low-temperature hydrogen gas sensing

In this paper, a novel hybrid structure of Pd doped ZnO/SnO₂ heterojunction nanofibers with hexagonal ZnO columns was one step synthesized from electrospun precursor nanofibers. Due to the synergistic effect of hexagonal ZnO, SnO₂ and Pd, the structure exhibited excellent hydrogen (H₂) gas sensing properties. At low-temperature of 120 °C, the response (R_a/R_g) to 100 ppm H₂ gas exceeded 160, the response/recovery time was only 20 s and 6 s respectively and the limit of detection was only 0.5 ppm. Meanwhile, it also had good selectivity for H₂ gas and excellent linearity. In addition, the materials were characterized by XRD, FESEM, HRTEM, XPS, and the synthesis mechanism and gas sensing mechanism were proposed.     

Polyaniline encapsulated Ti-MOF/CoS for efficient photocatalytic hydrogen evolution

We report the study of conductive polyaniline (PANI) chain embedded Ti-MOF functionalized with CoS as a cocatalyst for hydrogen evolution reaction (HER) application. The post synthetically modified hybrid photocatalyst PANI/Ti-MOF/CoS greatly influences the redox and e^? ? h⁺ separation process and exhibits an impressive rate of HER (～1322 μmol h^?1g^?1), suppressing the pristine Ti-MOF (～62 μmol h^?1g^?1) with apparent quantum yield (AQY) of ～3.2 and transient current response of ～46.4 μA cm^?2. In this system, Ti-MOF provides the circulation of Ti³⁺ and Ti⁴⁺ to the reaction of photocatalytic H₂ generation, where the additional PANI and CoS amended the performance of H₂ production through electron enrichment and thereby improving the stability and integrity of Ti-MOF. The Electrochemical studies demonstrated increased photocurrent by interweaving Ti-MOF crystal with PANI through cation-π interaction thereby enhancing interface connection and then promoting electron transfers. The charge dynamics revealed the initial charge transfer from photoexcited PANI to encapsulated MOF framework to boost the photocatalytic performance of the system. Further, the electron movement at the Ti-MOF/CoS interface is investigated through work function and electrochemical potential of electrons (Fermi level). DFT results demonstrate the importance of CoS in improving the photocatalytic performance of hybrid Ti-MOF catalyst, which leads to superior catalytic behaviour. These results establish that the encapsulation of catalytic active sites inside MOFs with desirable energy band gaps would be an ideal choice for the production of solar fuels.     

Current trends in structural development and modification strategies for metal-organic frameworks (MOFs) towards photocatalytic H2 production: A review

Photocatalytic H₂ generation using semiconductor photocatalysts is considered as a cost-effective and eco-friendly technology for solar to energy conversion; however, the present photocatalysts have been recognized to depict low efficiency. Currently, porous coordination polymers known as metal-organic frameworks (MOFs) constituting flexible and modifiable porous structure and having excess active sites are considered to be appropriate for photocatalytic H₂ production. This review highlights current progress in structural development of MOF materials along with modification strategies for enhanced photoactivity. Initially, the review discusses the photocatalytic H₂ production mechanism with the concepts of thermodynamics and mass transfer with particular focus on MOFs. Elaboration of the structural categories of MOFs into Type I, Type II, Type III and classification of MOFs for H₂ generation into transition metal based, post-transition metal based, noble-metal based and hetero-metal based has been systematically discussed. The review also critically deliberate various modification approaches of band engineering, improvement of charge separation, efficient irradiation utilization and overall efficiency of MOFs including metal modification, heterojunction formation, Z-scheme formation, by introducing electron mediator, and dye based composites. Also, the MOF synthesized derivatives for photocatalytic H₂ generation are elaborated. Finally, future perspectives of MOFs for H₂ generation and approaches for efficiency improvement have been suggested.     

Enhanced photo-electrochemical activity of ZnO/Cu2S nanotube arrays photocathodes

ZnO/Cu₂S nanotube arrays are fabricated firstly by a facile and capping-agent-free method, and the photo-electrochemical performance has been studied systematically. The results show that ZnO/Cu₂S nanotube arrays achieve enhanced photo-electrochemical water splitting performance and the photocurrent densities of ZnO/Cu₂S are 7.9 times than that of ZnO at 0 V versus Ag/AgCl. The performance of the ZnO/Cu₂S nanotube arrays can be adjusted by changing the amount of Cu₂S microcrystals. The results confirm that the enhanced photo-electrochemical performance of ZnO/Cu₂S is due to the significantly improved visible light absorption, effective separation of photo-induced carriers due to the well band energy match and the formed p-n junction between ZnO and Cu₂S.     

Graded Heterojunction of AIGalnP High-brightness Light Emitting Diodes

A simple model of the graded heterojunction in AIGalnP compound semiconductors was introduced to analyze the band profile. The band profiles are analyzed with the different grading ways but the same grading length and under the different doping densities. The effect of the different grading lengths on the surplus of the potential of the spike to the potential of N region are also analyzed under the different doping densities. Through the experiments, it proves that the performances of high brightness light emitting diodes can be improved by the effects of the graded heterojunction.     

Synthesis and photocatalytic performance of MoS2/Polycrystalline black phosphorus heterojunction composite

As a promising catalyst for solar hydrogen production, black phosphorus (BP) has received widespread attention due to variable band gaps, high carrier mobility, and strong light absorption performance. Herein, we use MoS₂ as a cocatalyst to synthesize BP/MoS₂ catalyst with polycrystalline BP to improve photocatalytic performance under visible light irradiation. A small amount of MoS₂ can reduce the recombination of electron-hole pairs in the composite, increase carrier transport efficiency, and then improve photocatalytic performance. As expected, the 10/0.5 ratio of BP/MoS₂ catalyst exhibits the highest photocatalytic hydrogen evolution performance with a hydrogen evolution rate of 575.4 μmol h^?1 g^?1, which is 2.5 times of pure BP. Based on the results above, a simple method is provided to synthesize low-cost black phosphorus-based photocatalysts.     

NiSe as an effective co-catalyst coupled with TiO2 for enhanced photocatalytic hydrogen evolution

Construction of semiconductor heterojunctions can effectively accelerate the separation of photo-induced charge carriers and thereby enhance photocatalytic activity. Here, NiSe was used as an effective co-catalyst to construct an active NiSe/TiO₂ heterojunction for improving the photocatalytic H₂ production of TiO₂. The resultant 10%NiSe/TiO₂ heterojunction exhibited 11 times higher photocatalytic H₂-production activity than that of bare TiO₂. The NiSe/TiO₂ heterojunction and the photo-reduction of partial Ni²⁺ to Ni⁰ notably accelerated the separation and transfer of photo-excited electron-hole pairs, and thus resulted in obvious improvement of H₂-evolution activity. This work holds promise for the application of NiSe in photocatalysis as a high-efficiency photocatalytic cocatalyst.     

High-efficiency photoelectrochemical water splitting with heterojunction photoanode of In2O3-x nanorods/black Ti–Si–O nanotubes

Constructing heterojunction was an efficient way to promote photoelectrochemical (PEC) water splitting performance of TiO₂-based nano-photoanode. In this work, we demonstrated the feasible preparation of oxygen vacancies-induced In₂O₃ (In₂O_3-x) nanorods/black Si-doped TiO₂ (Ti–Si–O) nanotubes heterojunction photoanode for enhanced PEC water splitting. Black Ti–Si–O nanotubes were fabricated through Zn reduction of the as-annealed Ti–Si–O nanotubes, followed by In₂O_3-x nanorods coupling by a facile electrodepositing and Ar heat treatment. Solar to hydrogen conversion efficiency of the heterojunction photoanode reached as high as 1.96%, which was almost 10 times that of undoped TiO₂. The improved PEC properties were mainly attributed to co-doping effects of Si and Ti³⁺/oxygen vacancy as well as In₂O_3-x decoration, which resulted in enhanced optical absorption and facilitated separation-transport process of photogenerated charge carriers. Charge transfer process in the composite system and hydrogen production mechanism were proposed. This work will facilitate designing TiO₂-based nano-photoanodes for promoting water splitting by integrating with elements doping, oxygen vacancies self-doping and semiconductors coupling.     

Spin-filter silicene devices induced by asymmetric electrodes

Using nonequilibrium Green's function in combination with the density functional theory, we investigate the spin-dependent transport properties of three silicene-based heterojunctions. The calculated results show that the heterojunctions are promising multifunctional devices in spintronics due to their nearly perfect bipolar spin-filter effect and high rectification ratio. Also shown are the obvious negative differential resistance behaviors for both spin channels. By analyzing the spin-resolved transmission spectra and the band structure of ZSiNR electrodes, as well as the spatial resolved local density of states, the mechanisms for these intriguing properties are demonstrated in detail.     

Ti3C2@TiO2/g-C3N4 heterojunction photocatalyst with improved charge transfer for enhancing visible-light NO selective removal

Control of Nitrogen dioxide (NO₂) byproducts is of great importance for the photocatalytic NO removal and environmental remedy. However, individual semiconductor photocatalysts generally show limited capabilities for selective NO removal due to severe charge recombination and inadequate redox potentials. Herein, the cotton-like g-C₃N₄ was modified with Ti₃C₂@TiO₂ to construct a heterojunction photocatalyst Ti₃C₂@TiO₂/g-C₃N₄, which showed outperformed photocatalytic NO removal and MB degradation abilities compared to the individual photocatalysts under visible light irradiation. The UV–vis absorption spectra and photoluminescence (PL) spectra confirmed that Ti₃C₂@TiO₂/g-C₃N₄ photocatalyst was endowed with superior light utilization and separation/transfer ability of charge carriers due to the presence of n-n heterojunction and Schottky barrier. Furthermore, the g-C₃N₄, Ti₃C₂, and TiO₂ were closely contacted showing a high specific surface area, which promoted the charge transfer and the exposure of more active sites, further inducing the formation of more active species. Therefore, the designed photocatalyst delivered a high removal rate of NO and a suppressed discharge of NO₂. Notably, the photocatalyst Ti₃C₂@TiO₂/g-C₃N₄ also presented superior NO removal ability during the cycling experiment, indicating their outstanding stability and recyclability. Besides, the effects of active species were monitored using a trapping experiment to propose probable photocatalytic mechanism. This study could shed a new light to the design of photocatalyst for air purification in the future.