Alkali Etching of Porous PdCoZn Nanosheets for Boosting C-C Bond Cleavage of Ethylene Glycol Oxidation.

Pd-based electrocatalysts are the most effective catalysts for ethylene glycol oxidation reaction (EGOR), while the disadvantages of poor stability, low resistance to neutrophilic, and low catalytic activity seriously hamper the development of direct ethylene glycol fuel cells (DEGFCs). In this work, defect-riched PdCoZn nanosheets (D-PdCoZn NSs) with ultrathin 2D NSs and porous structures are fabricated through the solvothermal and alkali etching processes. Benefiting from the presence of defects and ultrathin 2D structures, D-PdCoZn NSs demonstrate excellent electrocatalytic activity and good durability against EGOR in alkaline media. The mass activity and specific activity of D-PdCoZn NSs for EGOR are 9.5 A mg-1 and 15.7 mA cm-2 , respectively, which are higher than that of PdCoZn NSs, PdCo NSs, and Pd black. The D-PdCoZn NSs still maintain satisfactory mass activity after long-term durability tests. Meanwhile, in situ IR spectroscopy demonstrates that the presence of defects attenuated the adsorption of intermediates, which improves the selectivity of the C1 pathway with excellent anti-CO poisoning performance. This work not only provides an effective synthetic strategy for the preparation of Pd-based nanomaterials with defective structures but also indicates significant guidance for optimum C1 pathway selectivity of ethylene glycol and other challenging chemical transformations.

Excitation-Selective and Double-Emissive Lead-Free Binary Hybrid Metal Halides for White Light-Emitting Diode and X-Ray Scintillation.

Zero-dimensional (0D) organic metal halides comprising heterogeneous metal cations in single phase can achieve multiple luminous emissions enabling them toward multifunctional light-emitting applications. Herein, A novel single crystal of (C8H20N)4SbMnCl9 containing two luminescent centers of [SbCl5]2- pentahedrons and [MnCl4]2- tetrahedrons is reported. The large distance between Sb-Sb, Mn-Mn, and Sb-Mn as well as theory calculation indicate negligible interaction between individual centers, thus endowing (C8H20N)4SbMnCl9 with excitation-dependable and efficient luminescence. Under near-UV excitation, only orange emission originates from self-trapped excitons recombination in [SbCl5]2- pentahedron occurs with photoluminescence quantum yield (PLQY) of 91.5%. Under blue-light excitation, only green emission originating from 4T1-6A1 transition of Mn2+ in [MnCl4]2- tetrahedrons occurs with PLQY of 66.8%. Interestingly, upon X-ray illumination, both emissions can be fully achieved due to the high-energy photon absorption. Consequently, (C8H20N)4SbMnCl9 is employed as phosphors to fabricate white light-emitting diodes optically pumped by n-UV chip and blue-chip thanks to its excitation-dependable property. Moreover, it also shows promising performance as X-ray scintillator with low detection limit of 60.79 nGyair S-1, steady-state light yield ≈54% of commerical scintillaotr LuAG:Ce, high resolution of 13.5 lp mm-1 for X-ray imaging. This work presents a new structural design to fabricate 0D hybrids with multicolor emissions.

Scalable Synthesis of Ir Cluster Anchored on Porous Hollow Carbon Nanobowls for Enhancing pH-Universal Hydrogen Evolution.

Design high-loading with superior activity and high atomic efficiency has consistently been a new frontier of heterogeneous catalysis while challenging in synthetic technology. In this work, a universal solid-state strategy is proposed for large scalable production of high-loading Ir clusters on porous hollow carbon nanobowls (Ir CSs/PHCNBs). The strong electronic interaction between metallic Ir cluster and C on PHCNBs leads to electron redistribution, which significantly improves the electron transfer rate on the interface. The obtained Ir CSs/PHCNBs only require overpotentials of 35, 34, and 37 mV for the hydrogen evolution reaction (HER) with stable outputting of 10 mA cm-2 under acidic, alkaline, and neutral conditions, respectively, which exceeds the state-of-the-art HER electrocatalysts. Meanwhile, the Tafel slopes of Ir CSs/PHCNBs for the HER process are 23.07, 48.76, and 28.95 mV dec-1 , greatly lower than that of PHCNBs (152.73, 227.96, and 140.29 mV dec-1 ) and commercial Pt/C (20%) (36.33, 66.10, and 36.61 mV dec-1 ). These results provide a new strategy for the universal synthesis of clusters catalysts and insight into understanding the interface effects between clusters and carbon substrate, facilitating the industrial application of hydrogen production.

Bioinspired Metalation of the Metal-Organic Framework MIL-125-NH2 for Photocatalytic NADH Regeneration and Gas-Liquid-Solid Three-Phase Enzymatic CO2 Reduction.

Coenzyme NADH regeneration is crucial for sustained photoenzymatic catalysis of CO2 reduction. However, light-driven NADH regeneration still suffers from the low regeneration efficiency and requires the use of a homogeneous Rh complex. Herein, a Rh complex-based electron transfer unit was chemically attached onto the linker of the MIL-125-NH2 . The coupling between the light-harvesting iminopyridine unit and electron-transferring Rh-complex facilitated the photo-induced electron transfer for the NADH regeneration with the yield of 66.4 % in 60 mins for 5 cycles. The formate dehydrogenase was further deposited onto the hydrophobic layer of the membrane by a reverse filtering technique, which forms the gas-liquid-solid reaction interface around the enzyme site. It gave an enhanced formic acid yield of 9.5 mM in 24 hours coupled with the in situ regenerated NADH. The work could shed light on the construction of integrated inorganic-enzyme hybrid systems for artificial photosynthesis.

Thermochromism Perovskite (COOH(CH2)3NH3)2PbI4 Crystals: Single-Crystal to Single-Crystal Phase Transition and Excitation-Wavelength-Dependent Emission.

As a potential multifunctional phase transition material, the organic-inorganic hybrid perovskite has attracted extensive attention in recent years. Here, we report the single-crystal to single-crystal phase transition and excitation-wavelength-dependent emission (EDE) of layered perovskite (COOH(CH2)3NH3)2PbI4. Single-crystal X-ray diffraction indicated that the crystal structure changes from layered Ruddlesden-Popper (RP) at 302 K to "X" network composed of face-sharing and corner-sharing [PbX6]4- octahedra at 425 K. The material exhibits thermochromic change from orange to yellow at higher temperature. Considering the thermochromism of the material, we apply it for anticounterfeiting and information encryption. The material exhibits EDE properties with a fluorescence color changing from green to red upon 420 and 546 nm excitation, respectively. Time-dependent density functional theory indicated that this phenomenon is mainly related to the laser-induced crystal structural transfer. Our research shows that the (COOH(CH2)3NH3)2PbI4 crystal has a potential application for multifunctional devices.

Efficient and synergistic decolourization and nitrate removal using a single-chamber with a coupled biocathode-photoanode system.

With the continuous development of the chemical industries, synergistic removal of carbon and nitrogen contaminants has drawn much attention. In this work, a novel strategy for the synergistic removal of methyl orange (MO) and nitrate was developed in a single reactor by combining a TiO2/g-C3N4 nanosheet/graphene photoanode and denitrifying biofilm cathode. Under xenon light illumination, the photocatalytic MO decolorization rate exceeded 90% (the initial concentration of MO was as high as 100 mg·L-1) with a biocathode potential bias of -0.5 V vs Ag/AgCl; additionally, the decolourization rate apparently followed first-order kinetics with a constant of 0.11 ± 0.02 h-1. The improved MO decolourization rate was mainly because the biocathode effectively enhanced the charge separation of the photogenerated charge at the TiO2/g-C3N4 nanosheet/graphene photoanode interface. In the meantime, the effluent nitrate was lower than 1 mg·N·L-1 at a biocathode potential of -0.5 V vs Ag/AgCl. The results indicated that the coupled biocathode-photoanode system could serve the purpose of simultaneously degrading MO and accomplishing nitrate reduction. Considering the sustainability of sunlight and the use of a biocathode, the coupled biocathode-photoanode system is a promising alternative for the simultaneous removal of biorefractory organics and nitrate.

Exploring Organic Metal Halides with Reversible Temperature-Responsive Dual-Emissive Photoluminescence.

The exceptional structural tunability of organic metal halides endows them with fascinating electronic and photophysical properties, providing much scope for applications. In this work, single crystals of the organic metal halide (C4 H9 NH3 )2 MnI4 are found to show reversible thermo-induced luminescent chromism within a wide temperature range. The (C4 H9 NH3 )2 MnI4 single crystal exhibits two emission peaks at 550 and 672 nm, which are assigned to a d-d transition of Mn2+ -centered tetrahedra and self-trapped excitons, respectively. The temperature-dependent emission color change is attributed to the thermo-induced trapping and detrapping process of the self-trapped exciton. (C4 H9 NH3 )2 MnI4 exhibits a maximum photoluminescence quantum efficiency of up to 68 % at 70 °C. The disclosed interacted photoluminescence decay mechanisms may prove useful for the further design of organic metal halides for optical thermometry.

Reversible Band Gap Narrowing of Sn-Based Hybrid Perovskite Single Crystal with Excellent Phase Stability.

An intriguing reversible band gap narrowing behavior of the lead-free hybrid perovskite single crystal DMASnI3 (DMA=CH3 NH2 CH3 + ) from yellow to black is observed without phase transformation. We discuss the transformation mechanism in detail. More interestingly, the transformed samples in black can rapidly self-heal into yellow ones when exposed to deionized water (DI water). Contrary to other hybrid perovskites, DMASnI3 crystals exhibit excellent water phase stability. For example, DMASnI3 was immersed in DI water for 16 h and no decomposition was observed. Inspired by its excellent water phase stability, we demonstrate a potential eco-friendly application of DMASnI3 in photo-catalysis for H2 evolution in DI water. We present the first H2 evolution rate of 0.64 µmol h-1 with good recycling properties for pure DMASnI3 crystals. After the narrowing process, the optical band gap of DMASnI3 can be lowered from 2.48 eV to 1.32 eV. Systematical characterizations are applied to investigate their structures and optoelectronic properties. The reversible band gap narrowing behavior and outstanding electrical properties, such as higher carrier mobility and long carrier lifetime show that DMASnI3 has a great potential for optoelectronic applications.

Anisotropic Optoelectronic Properties of Melt-Grown Bulk CsPbBr3 Single Crystal.

All-inorganic perovskite CsPbBr3 has been considered as one of the star semiconductors due to its inspiring optoelectronic properties and higher stability than the organic-inorganic hybrid counterparts. The preparation of large-size single crystals with low trap density and the performance optimization on the devices still challenge the commercial application of this material. Here the large transparent CsPbBr3 single crystal (ϕ 24 mm × 90 mm) was grown by a modified Bridgman method. With the determination of crystallographic directions, the anisotropic optoelectronic properties were investigated for the first time. The result shows a high electron mobility (11.61 cm2/(V s)) along the b axis, one order of magnitude higher than that along the c axis. Moreover, the photoresponse measurement yields a high responsivity (5.83 A/W) and external quantum efficiency (1360%) on the (001) plane irradiated by the 532 nm laser diode with 1 mW/cm2 under 10 V bias, which is a 305% enhancement compared with the (010) plane. Our study on anisotropic optoelectronic properties of CsPbBr3 will provide a significant approach to enhance the performance of single-crystalline devices.

Formation of Hybrid Perovskite Tin Iodide Single Crystals by Top-Seeded Solution Growth.

Hybrid perovskites have generated a great deal of interest because of their potential in photovoltaic applications. However, the toxicity of lead means that there is interest in finding a nontoxic substitute. Bulk single crystals of both cubic CH3NH3 SnI3 and CH(NH2)2 SnI3 were obtained by using the top-seeded solution growth method under an ambient atmosphere. Structural refinement, band gap, thermal properties, and XPS measurements of CH3NH3 SnI3 and CH(NH2)2 SnI3 single crystals are also reported in detail. These results should pave the way for further applications of CH3NH3 SnI3 and CH(NH2)2 SnI3.

Near Room Temperature, Fast-Response, and Highly Sensitive Triethylamine Sensor Assembled with Au-Loaded ZnO/SnO2 Core-Shell Nanorods on Flat Alumina Substrates.

Chemiresistive gas sensors with low power consumption, fast response, and reliable fabrication process for a specific target gas have been now created for many applications. They require both sensitive nanomaterials and an efficient substrate chip for heating and electrical addressing. Herein, a near room working temperature and fast response triethylamine (TEA) gas sensor has been fabricated successfully by designing gold (Au)-loaded ZnO/SnO2 core-shell nanorods. ZnO nanorods grew directly on Al2O3 flat electrodes with a cost-effective hydrothermal process. By employing pulsed laser deposition (PLD) and DC-sputtering methods, the construction of Au nanoparticle-loaded ZnO/SnO2 core/shell nanorod heterostructure is highly controllable and reproducible. In comparison with pristine ZnO, SnO2, and Au-loaded ZnO, SnO2 sensors, Au-ZnO/SnO2 nanorod sensors exhibit a remarkably high and fast response to TEA gas at working temperatures as low as 40 °C. The enhanced sensing property of the Au-ZnO/SnO2 sensor is also discussed with the semiconductor depletion layer model introduced by Au-SnO2 Schottky contact and ZnO/SnO2 N-N heterojunction.

Morphology-modulation of SnO2 hierarchical architectures by Zn doping for glycol gas sensing and photocatalytic applications.

The morphology of SnO2 nanospheres was transformed into ultrathin nanosheets assembled architectures after Zn doping by one-step hydrothermal route. The as-prepared samples were characterized in detail by various analytical techniques including scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and nitrogen adsorption-desorption technique. The Zn-doped SnO2 nanostructures proved to be the efficient gas sensing materials for a series of flammable and explosive gases detection, and photocatalysts for the degradation of methyl orange (MO) under UV irradiation. It was observed that both of the undoped and Zn-doped SnO2 after calcination exhibited tremendous gas sensing performance toward glycol. The response (S = Ra/Rg) of Zn-doped SnO2 can reach to 90 when the glycol concentration is 100 ppm, which is about 2 times and 3 times higher than that of undoped SnO2 sensor with and without calcinations, respectively. The result of photocatalytic activities demonstrated that MO dye was almost completely degraded (~92%) by Zn-doped SnO2 in 150 min, which is higher than that of others (MO without photocatalyst was 23%, undoped SnO2 without and with calcination were 55% and 75%, respectively).