Integration of a Cu2O/ZnO heterojunction and Ag@SiO2 into a photoanode for enhanced solar water oxidation.

Photoelectrochemical water splitting (PEC-WS) has attracted considerable attention owing to its low energy consumption and sustainable nature. Constructing semiconductor heterojunctions with controllable band structure can effectively facilitate photogenerated carrier separation. In this study, a FTO/ZnO/Cu2O/Ag@SiO2 photoanode with a Cu2O/ZnO p-n heterojunction and Ag@SiO2 nanoparticles is constructed to investigate its PEC-WS performance. Compared with a bare ZnO photoanode, the photocurrent density of the FTO/ZnO/Cu2O/Ag@SiO2 photoanode (0.77 mA cm-2) at 1.23 VRHE exhibits an increment of 88%, and a cathodic shift of 0.1 V for the on-set potential (0.4 VRHE). Detailed photoelectrochemical analyses reveal that the Cu2O/ZnO p-n heterojunction formed between Cu2O and ZnO can effectively promote photogenerated carrier separation. The surface plasmonic effect of the Ag@SiO2 nanoparticles can further promote the photogenerated carrier transfer efficiency, which synergistically improves the PEC-WS performance.

Photomodulation of Proton Conductivity by Nitro-Nitroso Transformation in a Metal-Organic Framework.

The design of a highly and photomodulated proton conductor is important for advanced potential applications in chemical sensors and bioionic functions. In this work, a metal-organic framework (MOF; Gd-NO2) with high proton conductivity is synthesized with a photosensitive ligand of 5-nitroisophthalic acid (BDC-NO2), and it provides remote-control photomodulated proton-conducting behavior. The proton conduction of Gd-NO2 reaches 3.66 × 10-2 S cm-1 at 98% relative humidity (RH) and 25 °C, while it decreases by ∼400 times after irradiation with a 355 nm laser. The newly generated and disappearing FT-IR characteristic peaks reveal that this photomodulated process is realized by the photoinduced transformation from BDC-NO2 to 5-nitroso-isophthalic acid (BDC-NO). According to density functional theory, the smaller electronegativity of the -NO group, the longer distance of the hydrogen bond between BDC-NO and H2O molecules, and the lower water adsorption energy of BDC-NO indicate that the irradiated sample possesses a poorer hydrophilicity and has difficulty forming rich hydrogen-bonded networks, which results in the remarkable decrease of proton conductivity.

Investigation of in situ sulfide/nitride/phosphide treatments of hematite photoanodes for improved solar water oxidation.

Surface catalyst engineering can effectively improve the photoelectrochemical water splitting (PEC-WS) performance of semiconductor photoelectrodes. In situ surface functional treatments can effectively reduce interface defects and improve photogenerated carrier transport. In this study, FTO/Sn@α-Fe2O3/FeOOH photoanodes were modified with in situ sulfide/nitride/phosphide treatments to improve their PEC-WS performance. Compared with the pure α-Fe2O3 photoanode, the photocurrent densities of FTO/Sn@α-Fe2O3/FeOOH photoanodes after sulfide/nitride/phosphide treatments increased from 0.88 to 3.38 mA cm-2 at 1.23 VRHE. The onset potential showed a cathode shift of 0.1 V. Photoelectrochemical analyses and theoretical calculation demonstrated that the surface engineering by sulfide/nitride/phosphide treatments can significantly reduce surface defects, enhance electrical conductivity and promote photogenerated carrier separation and transfer efficiency by regulating interface charge transfer, binding energy and internal electric field. The formation of an FeSx catalyst and N/P coordination complexes in the sulfide/nitride/phosphide processes on the surface of α-Fe2O3 photoanodes can effectively reduce photogenerated carrier recombination. This work provides experimental and theoretical support for surface structure design and improved photoelectric conversion performance of semiconductor photoelectrode materials.

Regulating a Zn/Co bimetallic catalyst in a metal-organic framework and oxyhydroxide for improved photoelectrochemical water oxidation.

As one of the most popular photoanode materials, hematite (α-Fe2O3) has obvious advantages in the field of photoelectrochemical water splitting (PEC-WS). However, it is difficult to achieve excellent PEC-WS performance without loading a cocatalyst serving as an electron/hole collector to promote photogenerated carrier separation. In this work, FTO/Sn@α-Fe2O3 photoanodes are modified with ZnCo-ZIF and ZnCoOOH bimetallic catalysts to obtain FTO/Sn@α-Fe2O3/Zn0.5Co0.5-ZIF and FTO/Sn@α-Fe2O3/Zn0.46Co0.54OOH photoanodes. Their photocurrent densities reach 2.6 mA cm-2 and 2.3 mA cm-2 at 1.23 VRHE, respectively. The detailed mechanism studies demonstrate that both ZnCoOOH and ZnCo-ZIF can effectively decrease the transfer resistance, increase the Fe2+/Fe3+ ratio and reduce the charge recombination of the α-Fe2O3 film, which synergistically improves the PEC-WS performance. Compared with ZnCoOOH, the ZnCo-ZIF exhibits better photogenerated carrier transfer efficiency and catalytic performance, which mainly can be attributed to the improved binding energy between the ZnCo-ZIF catalyst and the α-Fe2O3 film. This work provides a simple and feasible strategy for constructing bimetallic catalysts and deepens the understanding of different types of bimetallic catalysts for high-performance PEC-WS systems.

Understanding the varying mechanisms between the conformal interlayer and overlayer in the silicon/hematite dual-absorber photoanode for solar water splitting.

Dual-absorber photoelectrodes have been proved to have great potential in the photoelectrochemical (PEC) water splitting application due to their broadband absorption and suitable energy-band position, while the surface/interface issues are still not clearly resolved and understood. Here, during the preparation of a silicon/hematite dual-absorber photoanode achieved via synthesizing a Sn-doped hematite film on the silicon nanowire (SiNW) substrate, we separately introduced the conformal overlayer and interlayer of an Al2O3 thin film by atomic layer deposition. With the thickness-optimized interlayer (overlayer) of the Al2O3 thin film, the photocurrent density at 1.23VRHE can be enhanced from 0.85 mA cm-2 to 1.51 mA cm-2 (1.25 mA cm-2), and the on-set potential has a cathodic shift of ∼0.32 V. Although both the overlayer and interlayer modification can substantially improve the PEC performance, the underlying mechanisms are obviously different. The overlayer can only reduce the carrier recombination on the top surface and in the bulk of the hematite film; in contrast, the interlayer not only passivates the SiNW surface and bottom surface of the hematite film, but also the top surface of the photoanode due to Al3+ thermal diffusion from the bottom to the top surface of the hematite film and the resultant Al2O3 formation. This work deepens our understanding for the roles of the surface and interface engineering in the achievement of high-performance PEC systems based on dual or more absorbers.

Luminescent Thermochromic Silver Iodides as Wavelength-Dependent Thermometers.

Luminescent thermochromic materials with a dramatic shift of emission band under different temperatures are highly desirable in temperature sensing fields. However, the design of the synthesis of such compounds remains a great challenge. In this work, two new luminescent thermochromic silver iodides, (emIm)Ag3I4 (1) and (emIm)Ag2I3 (2) (emIm = 1-ethyl-3-methyl imidazole), have been synthesized under solvothermal conditions. Compound 1 features a [Ag3I4]- anionic layer, while compound 2 possesses an infinite [Ag2I3]- chain structure, both of which are charge balanced by emIm+ cations. Particularly, they display luminescent thermochromism with a significant wavelength shift of emission maximum with temperature change. They represent rare examples of infinite layered or chain silver iodides that show luminescent thermochromism. Furthermore, the results indicate that compounds 1 and 2 are promising wavelength-dependent luminescent thermometers.

High proton conduction in an excellent water-stable gadolinium metal-organic framework.

A new metal-organic framework with excellent water stability, {H[(N(CH3)4)2][Gd3(NIPA)6]}·3H2O (1, H2NIPA = 5-nitroisophthalic acid), displays a proton conductivity of 7.17 × 10-2 S cm-1 (at 75 °C and 98% relative humidity), which is among the highest values for proton-conducting MOFs.

Single-component small-molecule white light organic phosphors.

White light emission from single-component small organic triazole molecules in the solid state was observed for the first time. This unusual intrinsic broadband emission, stemming from the supramolecular aggregate instead of the excimer, can be tuned by controlling the degree of electron delocalization and intensities of intermolecular interactions.

Second-order nonlinear optical switching with a record-high contrast for a photochromic and thermochromic bistable crystal.

Nonlinear optical (NLO) switchable materials are important for photonic and optoelectronic technologies. One important issue for NLO photoswitching, the most studied physical switching approach, is how to improve the switching contrast of second harmonic generation (SHG) in crystals, because the known values are generally below 3 times. Thermoswitching, as another approach, has shown impressive high SHG-switching contrasts (4-∞ times), but the fast decay of thermally induced states demands constant heat sources to maintain specific SHG intensities. We have synthesized a photochromic and thermochromic bistable acentric compound, ß-[(MQ)ZnCl3] (MQ+ = N-methyl-4,4'-bipyridinium), which represents the first crystalline compound with both photo- and heat-induced SHG-switching behavior and the first example of a thermoswitchable NLO crystal that can maintain its expected second-order NLO intensity without any heat source. The SHG-switching contrast can reach about 8 times after laser irradiation or 2 times after thermal annealing. The former value is the highest recorded for photoswitchable NLO crystals. This work also indicates that higher SHG-switching contrasts may be obtained through increasing electron-transfer efficiency, variation of permanent dipole moment, and self-absorption.

Grinding size-dependent mechanoresponsive luminescent Cd(ii) coordination polymer.

In this work, we report a new mechanoresponsive luminescent Cd(ii) coordination polymer that exhibits a sensitivity to mechanical stimulation. The luminescence colour changed gradually from weak yellowish-green to bright cyan in response to different grinding sizes, thereby showing interesting mechanochromic properties, namely a grinding-enhanced luminescence and good crystalline maintenance ability.

Microporous Lanthanide Metal-Organic Frameworks with Multiple 1D Channels: Tunable Colors, White-Light Emission, and Luminescent Sensing for Iron(II) and Iron(III).

A new series of isostructural lanthanide-based metal-organic frameworks, [H3 O][HN(CH3 )3 ]2 [Ln3 L6 ] (Ln=Gd (1), Eu (2), and Tb (3); H2 L=1,3-benzenedicarboxylic acid), was prepared under solvothermal conditions. Single-crystal XRD studies reveal that these compounds are 3D microporous frameworks with 1D channels distributed in four different directions. The 1D channels contain protonated water molecules and trimethylammonium cations, which can be partially exchanged with different metal ions. Notably, these compounds do not contain any coordinated solvent molecules because the coordination sphere of the Ln3+ ion is fully occupied by chelating and bridging carboxylate oxygen atoms. Tunable colors and white-light emission can be achieved by encapsulating different molar ratios of Eu3+ and Tb3+ ions in the Gd framework through cation exchange. In addition, the Eu framework can act as a sensitive and selective luminescence sensor for both Fe2+ and Fe3+ .

Chiral template induced homochiral MOFs built from achiral components: SHG enhancement and enantioselective sensing of chiral alkamines by ion-exchange.

A pair of chiral template induced anionic homochiral frameworks constructed from achiral components has been synthesized. Ion-exchange of counter cations with polar or chiral organic cations enhances the SHG efficiency of the frameworks. The enantioselective sensing of chiral alkamines can be achieved by the SHG response.