NiCS3: A cocatalyst surpassing Pt for photocatalytic hydrogen production.

Cocatalysts play a key role in improving photocatalytic performance by enhancing conductivity and providing an enormous number of active sites simultaneously. However, cocatalysts are usually made of noble metals such as Pt, which are expensive and rare. Therefore, cocatalysts derived from cheap and abundant elements are highly desirable. Here, for the first time, we demonstrate that NiCS3, which is made from nickel that is abundant and costs less than 0.04 % of Pt, is an effective substitute for Pt cocatalysts for the photocatalytic activity of CdS nanorods in hydrogen evolution reaction (HER). Under visible light, the NiCS3/CdS composite with NiCS3 as the cocatalyst achieved an astonishing H2 production of 61.9 mmol·g-1·h-1 while maintaining high stability, which is 14 times higher than that observed when using CdS alone and nearly 2 times higher than that of Pt/CdS. We also established that the metallicity of NiCS3 results in good carrier conductivity, which promotes the electron transfer and the separation of photo-induced carriers. Due to the appropriate adsorption energy ΔGH*, NiCS3 more readily adsorbs hydrogen protons and desorbs molecular hydrogen during the photocatalytic process compared with Pt. Additionally, NiCS3 can effectively inhibit the photo-corrosion effect of CdS itself, ensuring a good stability of HER. These results suggest that NiCS3 is a promising substitute for Pt cocatalysts.

Tuning ferroelectric photovoltaic performance in R3c-CuNbO3 through compressive strain engineering: a first-principles study.

Most ferroelectric oxides exhibit relatively wide bandgaps, which pose limitations on their suitability for photovoltaics application. CuNbO3 possesses potential ferroelectric properties with an R3c polar structure that facilitate the separation of charge carriers under illumination, promoting the generation of photovoltaic effects. The optical and ferroelectric properties of R3c-CuNbO3, as well as the effect of strain on the properties are investigated by first-principles calculation in this paper. The calculated results indicate that R3c-CuNbO3 possesses a moderate band gap to absorb visible light. The interaction of Cu-O and Nb-O bonds is considered to have a crucial role in the photovoltaic properties of CuNbO3, contributing to the efficient absorption of visible light. The bandgap of CuNbO3 becomes smaller and the density of states near the conduction and valence bands becomes relatively uniform in distribution under compressive conditions, which improves the photoelectric conversion efficiency to 29.9% under conditions of bulk absorption saturation. The ferroelectric properties of CuNbO3 are driven by the Nb-O bond interactions, which are not significantly weakened by the compressive strain. CuNbO3 is expected to be an excellent ferroelectric photovoltaic material by modulation of compressive strain due to the stronger visible light absorption and excellent ferroelectric behavior.

High-Performance and Polarization-Sensitive Imaging Photodetector Based on WS2 /Te Tunneling Heterostructure.

Next-generation imaging systems require photodetectors with high sensitivity, polarization sensitivity, miniaturization, and integration. By virtue of their intriguing attributes, emerging 2D materials offer innovative avenues to meet these requirements. However, the current performance of 2D photodetectors is still below the requirements for practical application owing to the severe interfacial recombination, the lack of photoconductive gain, and insufficient photocarrier collection. Here, a tunneling dominant imaging photodetector based on WS2 /Te heterostructure is reported. This device demonstrates competitive performance, including a remarkable responsivity of 402 A W-1 , an outstanding detectivity of 9.28 × 1013 Jones, a fast rise/decay time of 1.7/3.2 ms, and a high photocurrent anisotropic ratio of 2.5. These outstanding performances can be attributed to the type-I band alignment with carrier transmission barriers and photoinduced tunneling mechanism, allowing reduced interfacial trapping effect, effective photoconductive gains, and anisotropic collection of photocarriers. Significantly, the constructed photodetector is successfully integrated into a polarized light imaging system and an ultra-weak light imaging system to illustrate the imaging capability. These results suggest the promising application prospect of the device in future imaging systems.

The kinked structure and interchain van der Waals interaction of carbyne nanocrystals.

Carbyne with one-dimensional sp-hybridized carbon atoms is the third form of carbon following diamond and graphite. Although carbyne nanocrystals have been synthesized, little is known about its structural details. Here, we report experimental evidence of the kinked structure of carbon chains and interchain van der Waals interaction of carbyne nanocrystals by near edge X-ray absorption fine structure (NEXAFS) spectroscopy. We measure the resonance and the feature peaks of the kinked configuration of carbon chains and the van der Waals interaction between chains of carbyne nanocrystals using NEXAFS spectroscopy. We also perform theoretical calculations of density functional theory and simulations based on the super-cell core-hole method for carbon K-edge NEXAFS. The theoretical results are in good agreement with the experimental measurements, which demonstrates that carbyne nanocrystals are van der Waals crystals with kinked chains as structural units. Note that the peak at 288.5 eV in the simulated NEXAFS spectrum implies the possible presence of hydrogen-terminated kinks or hydrogen-terminated chains in carbyne nanocrystals, which clarifies the understanding of the C-H bond in carbyne nanocrystals. These findings are enlightening and significant for pursuing physics and potential applications of carbyne.

Theoretical study on ferroelectric nitrides with super-wurtzite structures for solar energy conversion applications.

Polarized structured nitride semiconductors are attractive due to their unique and environment-friendly electronic properties. The stability, ferroelectricity and photocatalytic and photovoltaic properties of super-wurtzite Mg2XN3 (X = Bi, Mo, Nb, Sb, Ta, Tc and W) were determined based on first principles calculations in this study. The calculated results indicate that Mg2XN3 (X = Sb, Ta, Bi and Nb) are stable polar nitrides by phonon frequencies, elastic coefficients and ferroelectric analysis. Mg2XN3 (X = Sb, Ta and Nb) with large ferroelectric polarization strength could absorb ultraviolet light to promote photocatalytic water splitting for hydrogen production. Mg2BiN3 is a new excellent photovoltaic candidate due to its ideal energy band, high electron mobility, high absorption coefficient and large ferroelectric polarization strength.

Theoretical study on the ferroelectric and light absorption properties of Li2SbBiO6 for harvesting visible light.

Ferroelectric oxides with large bandgaps have restricted applications in photovoltaic and photocatalytic fields. Based on recent experiments with the ferroelectric compound, LiSbO3, the stability and optoelectronic properties of a new ferroelectric compound, namely Li2SbBiO6, are investigated in this study. The calculated results demonstrate that Li2SbBiO6 satisfies the stability conditions of the elastic coefficients and phonon dynamics. Li2SbBiO6 maintains the ferroelectric polarization strength of LiSbO3 and significantly reduces the bandgap, and thus has been explored for applications in photovoltaic and photocatalytic fields. Li2SbBiO6 is a new potential ferroelectric oxide for harvesting visible light owing to its suitable bandgap and a large hole-electron effective mass ratio.

Theoretical study on the stability, ferroelectricity and photocatalytic properties of CaBiO3.

Materials with high ferroelectric polarization strength and sufficient absorption of visible light have unique advantages in photocatalysis. Based on the results of structure search, phonon frequency, and elasticity coefficient calculations, CaBiO3 has a stable R3 polar structure. First-principles calculations indicate that R3-CaBiO3 is a potentially efficient ferroelectric visible-light photocatalytic material for hydrogen production. CaBiO3 under slight strain can maintain high ferroelectric polarization strength, strong visible light absorption capacity and small effective mass. CaBiO3 under tensile strain has potentially ferroelectric photogeneration of hydrogen with a band edge position that crosses the redox potential of water. These results can expand the application of Bi-based materials in photocatalytic hydrogen production.

Recent advances in metal-organic frameworks for gas adsorption/separation.

The unique structural advantage of metal-organic frameworks (MOFs) determines the great prospect and developability in gas adsorption and separation. Both ligand design and microporous engineering based on crystal structure are significant lever for coping with new application exploration and requirements. Focusing on the designable pore and modifiable frameworks of MOFs, this review discussed the recent advances in the field of gas adsorption and separation, and analyzed the host-guest interaction, structure-performance relations, and the adsorption/separation mechanism from ligand design, skeleton optimization, metal node regulation, and active sites construction. Based on the function-oriented perspective, we summarized the main research recently, and made an outlook based on the focus of microporous MOFs that require further attention in the structure design and industrial application.

2D coordination polymer-derived CoSe2-NiSe2/CN nanosheets: the dual-phase synergistic effect and ultrathin structure to enhance the hydrogen evolution reaction.

The evolution of cost-effective hydrogen evolution reaction (HER) electrocatalysts is of great significance for the development of clean energy. Exploring effective synthesis strategies to optimize the performance of non-noble metal electrocatalysts has always attracted our attention. Herein, ultrathin coordination polymers were used as precursors to controllably synthesize two-dimensional (2D) ultrathin dual-phase transition metal selenide (TMSs)/carbon-nitrogen (CN) composites (CoSe2-NiSe2/CN) by a two-step method (first a low temperature hydrothermal method for selenization, and then high temperature calcination selenization). Benefiting from its large specific surface area (49 m2 g-1), abundant catalytically active sites and synergistic effects, CoSe2-NiSe2/CN can significantly enhance the HER catalytic activity and exhibits good electrocatalytic activity with an overpotential of 150 mV at -10 mA cm-2, and a small Tafel slope of 42 mV dec-1 in an acidic electrolyte for the HER. This work provides a new strategy for optimizing the HER catalytic activity of TMSs by preparing 2D ultrathin dual-phase TMS composite materials.