Vacancy-Induced Symmetry Breaking in Titanium Dioxide Boosts the Photocatalytic Hydrogen Production from Methanol Aqueous Solution.

The key to optimizing photocatalysts lies in the efficient separation and oriented migration of the photogenerated carriers. Herein, we report that breaking continuous TiO tetragonal () symmetry in titanium dioxide material by oxygen vacancy engineering could induce a dipole field within the bulk phase and thus facilitate the separation and transfer of photogenerated electron-hole pairs. After further loading of Cu single-atom co-catalysts, the obtained catalyst attained a hydrogen (H) yield rate of 15.

Bidentate Coordination Structure Facilitates High-Voltage and High-Utilization Aqueous Zn-I Batteries.

The aqueous zinc-iodine battery is a promising energy storage device, but the conventional two-electron reaction potential and energy density of the iodine cathode are far from meeting practical application requirements. Given that iodine is rich in redox reactions, activating the high-valence iodine cathode reaction has become a promising research direction for developing high-voltage zinc-iodine batteries. In this work, by designing a multifunctional electrolyte additive trimethylamine hydrochloride (TAH), a stable high-valence iodine cathode in four-electron-transfer I/I/I reactions with a high theoretical specific capacity is achieved through a unique amine group, Cl bidentate coordination structure of (TA)ICl.

Synergy of Photogenerated Electrons and Holes toward Efficient Photocatalytic Urea Synthesis from CO and N.

Directly coupling N and CO to synthesize urea by photocatalysis paves a sustainable route for urea synthesis, but its performance is limited by the competition of photogenerated electrons between N and CO, as well as the underutilized photogenerated holes. Herein, we report an efficient urea synthesis process involving photogenerated electrons and holes in respectively converting CO and N over a redox heterojunction consisting of WO and Ni single-atom-decorated CdS (Ni-CdS/WO). For the photocatalytic urea synthesis from N and CO in pure water, Ni-CdS/WO attained a urea yield rate of 78 μM h and an apparent quantum yield of 0.

Unraveling the Unique Strong Metal-Support Interaction in Titanium Dioxide Supported Platinum Clusters for the Hydrogen Evolution Reaction.

Strong metal-support interaction (SMSI) is crucial to modulating the nature of metal species, yet the SMSI behaviors of sub-nanometer metal clusters remain unknown due to the difficulties in constructing SMSI at cluster scale. Herein, we achieve the successful construction of the SMSI between Pt clusters and amorphous TiO nanosheets by vacuum annealing, which requires a relatively low temperature that avoids the aggregation of small clusters. In situ scanning transmission electron microscopy observation is employed to explore the SMSI behaviors, and the results reveal the dynamic rearrangement of Pt atoms upon annealing for the first time.

Element-dependent effects of alkali cations on nitrate reduction to ammonia.

Catalytic conversion of nitrate (NO) pollutants into ammonia (NH) offers a sustainable and promising route for both wastewater treatment and NH synthesis. Alkali cations are prevalent in nitrate solutions, but their roles beyond charge balance in catalytic NO conversion have been generally ignored. Herein, we report the promotion effect of K cations in KNO solution for NO reduction over a TiO-supported Ni single-atom catalyst (Ni/TiO).

Structurally diverse rearranged sesquiterpenoids, including a pair of rare tautomers, from the aerial parts of Daphne penicillata.

Eight structurally diverse rearranged sesquiterpenoids, including seven undescribed sesquiterpenoids (1a/1b and 3-8) were obtained from the aerial parts of Daphne penicillata. 1a/1b, 3, 5 and 6 possess rare rearranged guaiane skeletons and 4 represents the first example of rearranged carotene sesquiterpenoids. Their structures and absolute configurations were determined by extensive spectroscopic analyses, NMR and ECD calculations.

Six undescribed guaianolide-type sesquiterpenes from the aerial parts of Daphne penicillata.

Six undescribed guaianolide sesquiterpenes (1-6) were obtained from the aerial parts of Daphne penicillata. Their structures and absolute configuration were elucidated by HRESIMS, NMR analyses, ECD calculations and single-crystal X-ray diffraction analysis. Structurally, all compounds possess the typical 5,7-fused system of 8,12-guaianolides and this guaianolide-type was first reported to be isolated from Daphne penicillata.

Spin state modulation on dual Fe center by adjacent Ni sites enabling the boosted activities and ultra-long stability in Zn-air batteries.

Breakthrough in developing cost-effective Fe-based catalysts with superior oxygen reduction reaction (ORR) activities and ultra-long-term stability for application in Zn-air batteries (ZABs) remain a priority but still full of challenges. Herein, the neighboring NiN single-metal-atom and FeN dual-metal-atoms on the N-doped hollow carbon sphere (Fe/Ni-NHCS) were deliberately constructed as the efficient and robust ORR catalyst for ZABs. Both theory calculations and magnetic measurements demonstrate that the introduction of NiN provides a significant role on optimizing the electron spin state of FeN sites and reducing the energy barrier for the adsorption and conversion of the oxygen-containing intermediates, enabling the Fe/Ni-NHCS with excellent ORR performance and ultralow byproduct HO yield (0.

Spiral Square Nanosheets Assembled from Ru Clusters.

Spiral two-dimensional (2D) nanosheets exhibit unique physical and chemical phenomena due to their twisted structures. While self-assembly of clusters is an ideal strategy to form hierarchical 2D structures, it is challenging to form spiral nanosheets. Herein, we first report a screw dislocation involved assembled method to obtain 2D spiral cluster assembled nanosheets (CANs) with uniform square morphology.

Atomically Strained Metal Sites for Highly Efficient and Selective Photooxidation.

Strain engineering is an attractive strategy for improving the intrinsic catalytic performance of heterogeneous catalysts. Manipulating strain on the short-range atomic scale to the local structure of the catalytic sites is still challenging. Herein, we successfully achieved atomic strain modulation on ultrathin layered vanadium oxide nanoribbons by an ingenious intercalation chemistry method.

Chouchunsteride A-D, four new steroids from the leaves of Ailanthus altissima (Mill.) Swingle.

Four new steroids, chouchunsteride A-D (1-4), together with four known steroids (5-8), were isolated from the leaves of Ailanthus altissima (Mill.) Swingle. Their structures were elucidated based on spectroscopic data analysis, while the relative and absolute configurations were determined via acetonide analysis and quantum chemical ECD calculations.

Influences of split application and nitrification inhibitor on nitrogen losses, grain yield, and net income for summer maize production.

The application of nitrogen (N) fertilizer combined with nitrification inhibitor is considered to be one of the effective strategies to improve N efficiency and reduce N loss. While the chemical and physical properties of nitrapyrin (CP) in fertilizers have been evaluated to increase N efficiency, a lack of comprehensive evaluation of the effects of adding CP on summer maize yield, environmental benefits and economic income under different fertilization methods. In this study, two fertilization methods were used: split-N application and one-time basal N fertilizer before sowing.

Light-Induced Selective Hydrogenation over PdAg Nanocages in Hollow MOF Microenvironment.

Selective hydrogenation with high efficiency under ambient conditions remains a long-standing challenge. Here, a yolk-shell nanostructured catalyst, PdAg@ZIF-8, featuring plasmonic PdAg nanocages encompassed by a metal-organic framework (MOF, namely, ZIF-8) shell, has been rationally fabricated. PdAg@ZIF-8 achieves selective (97.

Nitrapyrin Mitigates Nitrous Oxide Emissions, and Improves Maize Yield and Nitrogen Efficiency under Waterlogged Field.

In order to explore the effects of nitrapyrin (N-Serve) application on greenhouse gas emission and nitrogen (N) leaching of a waterlogged maize ( L.) field, we investigated the effects of applying nitrapyrin on soil ammonium (NH-N) and nitrate nitrogen (NO-N) content, nitrous oxide (NO) fluxes, and the warming potential (GWP) in a waterlogged maize field. The design included three treatments: waterlogging treatment with only urea application (V-3WL), waterlogging treatment with urea and nitrapyrin application (V-3WL+N), and no waterlogging treatment applying only urea (CK).

A DNA-Based Plasmonic Nanodevice for Cascade Signal Amplification.

Here, we describe a DNA circuit-aided, origami nanodevice-based plasmonic system, which performs DNA-regulated, cascade amplification of faint chemical/biological signals. In this system, two gold-nanorods (GNRs) are co-assembled onto a DNA lock-containing, tweezer-like DNA origami template. Logic circuits serve as recognition and amplification elements for specific messengers, producing DNA keys for driving conformational changes of the plasmonic nanodevices.

Fluctuation analysis in the dynamic characteristics of continental glacier based on Full-Stokes model.

Ice thickness has a great influence on glacial movement and ablation. Over the course of the change in thickness, area and external climate, the dynamic process of how glaciers change and whether a glacier's changes in melting tend to be stable or irregular is a problem that needs to be studied in depth. In our study, the changes in the dynamic process of the No.