Latest ArticlesCompared with the widespread exploitation of hot electrons in plasmonic nanoparticles (NPs), hot holes generated from plasmonic metal interband transitions, are often overlooked in photoelectrochemistry, including photoelectrochemical sensing. Motivated by the subtle spectral overlap between the characteristic plasmonic bands of Ag NPs and interband transitions of Au, herein, we construct unusual core-shell Ag@Au NPs via an anti-galvanic reaction to promote the generation of hot holes. Benefiting from the unique plasmon resonances of Ag cores in specific wavelength regimes, Ag@Au can excite multiplied hot holes while Au cannot under the same conditions. With satisfactory accuracy and good practicability, the photoelectrochemical sensing platform based on Ag@Au NPs possesses a detection limit of 77 nmol/L for glucose, exhibiting significantly higher sensitivity compared to that using Au NPs. This work exemplifies the applications of interband hot-hole accumulation initiated by plasmons and may inspire more strategies to explore the utilization of hot holes in photoelectrochemistry.
Electrochemical nitrogen reduction reaction (NRR) is a mild and sustainable method for ammonia synthesis. Therefore, developing high activity, selectivity, and economic efficiency catalysts with considering the synergistic effects between catalysts and carriers to design novel structural models is very important. Considering the non-noble metal NRR catalyst, Mo3, we tried to find a suitable carrier which is stable and economical. Herein, we used the largest atomically precise aluminum-pyrazole ring (AlOC-69) to date (diameter up to 2.3 nm). The larger ring cavities and the presence of abundant hydroxy groups make AlOC-69 an ideal molecular carrier model and provide a basis for studying its structure-activity relationship. The formation energy (−0.76 eV) and stable Mo-O bonds indicate that Mo3 can be stabilized on the Al10O10 surface. Additionally, N2 has fully activated due to the strong interaction between the p-orbital of N and the d-orbital of Mo. The low limiting potential (−0.28 V) emerges that Mo3@Al10O10 has ideal catalytic activity and selectivity. This research provides a promising catalyst model and an understanding of its catalytic process at the atomic level, providing a new approach for the co-design of catalyst and carrier in NRR.
Metal-organic frameworks (MOFs) received considerable attention to adsorption and removal of various environmental pollutants because of some inherent advantages. However, it is challenging but meaningful to design and fabricate hierarchical mixed-dimensional MOFs with synergistic effects to enhance the performance for removal and preconcentration of environmental pollutants. Herein, a new hierarchical two-dimensional (2D)-three-dimensional (3D) mixed-dimensional cactus‐like MOF@MOF hybrid material (PCN-134@Zr-BTB) was prepared by in-situ growth of 2D MOF nanosheets (Zr-BTB) on the surface of 3D MOF (PCN-134). The PCN-134@Zr-BTB composites combine the advantages of 2D and 3D MOFs with extensive mesoporous structures and large surface area for effective removal and enrichment of bisphenols (BPs). In comparison with pristine PCN-134 and Zr-BTB materials, the PCN-134@Zr-BTB hybrid material presented excellent adsorption performance for BPs. The adsorption isotherms are consistent with the Langmuir model, and the maximum adsorption capacity of four bisphenols (BPs) ranged from 135.1 mg/g to 628.9 mg/g. The adsorption kinetics are in accordance with the pseudo-second-order model. The recoveries ranged from 72.8% to 108%. The limits of detection were calculated at 0.02–0.03 ng/mL. The enrichment factors were calculated in the range of 310–374. According to FT-IR and XPS analysis, the main adsorption mechanisms are hydrogen bonding and π-π stacking. Nevertheless, this work provides a new and convenient strategy for the preparation of new hierarchical mixed-dimensional MOF@MOF (PCN-134@Zr-BTB) hybrid material for extraction and enrichment of BPs from aqueous matrix.
Three-dimensional (3D) histology has exhibited tremendous potential in fundamental research and clinical disease grading, but compatible labeling techniques are still lacking. Recently in Science Advances, Pac et al. report a new histological technique termed 3DNFC, which realizes 3D fluorescence imaging of thick tissues via citrate-based in situ fluorophore formation.
DNA-based supramolecular hydrogels are important and promising biomaterials for various applications due to their inherent biocompatibility and tunable physicochemical properties. The three-dimensional supramolecular matrix of DNA formed by non-covalently dynamic cross-linking provides exceptional adaptability, self-healing, injectable and responsive properties for hydrogels. In addition, DNA hydrogels are also ideal bio-scaffold materials owing to their tissue-like mechanics and intrinsic biological functions. Technically, DNA can assemble into supramolecular networks by pure complementary base pairing; it can also be combined with other building blocks to construct hybrid hydrogels. This review focuses on the development and construction strategies of DNA hydrogels. Assembly and synthesis methods, diverse responsiveness and biomedical applications are summarized. Finally, the challenges and prospects of DNA-based supramolecular hydrogels are discussed.
The mitigation of under-coordinated Pb2+ (halide vacancy) defect remains an imperative challenge in the perovskite solar cells, especially printable mesoscopic perovskite solar cells (FP-PSCs). Here we report a commercial-available polyazin anticancer drug Sapanisertib as coordination passivator of halide vacancies in FP-PSCs, thereby achieving the photoelectric conversion efficiency (PCE) to 18.46%, along with a record certified PCE of 18.27%. In polazin Sapanisertib (Sap), there exists two kinds of nitrogen atoms: in-aromatic ring (in purine and oxazole rings, IAR-Ns) and out-aromatic ring (substituted amino groups, OAR-Ns). Through multiple characterizations, and DFT calculations show that substituted amino groups OAR-Ns hardly get interaction with the halide vacancy due to the distribution of charge density in Sapanisertib. Our work suggests that the selective coordination is of great significance for the design of high-performance passivators for printable mesoscopic perovskite solar cells.
Ring-opening copolymerization of CO2 and epoxides is a promising way to manufacture high value-added materials. Despite a variety of catalyst systems have been reported, the reaction is still limited by low activity and polymer selectivity. Herein, a strategy of polymerization-enhanced Lewis acidity is reported to construct a series of highly efficient polymeric aluminum porphyrin catalysts (PAPCs). The characterization of the coordination equilibrium constant (Keq) showed significantly enhanced Lewis acidity of PAPC (Keq = 18.2 L/mol) compared to the monomeric counterpart (Keq = 6.4 L/mol), accompanied with increased turnover frequency (TOF) from 136 h−1 to 5500 h−1. Through detailed regulation of Lewis acidity, the highly Lewis acidic PAPC-OTs displayed a record high TOF of 30,200 h−1 with polymer selectivity of up to 99%.
Transition metal and nitrogen co-doped carbons (M-N-C) have proven to be promising catalysts for CO2 electroreduction into CO because of the high activity and selectivity. Effective enrichment of the active transition metal coordinated nitrogen sites is desirable but is challenging for a practical volumetric productivity. Herein, we report four kinds of model electrocatalysts to unveil this issue, which include the NC structures with surface N-functionalities, Ni-N-C_I with one layer of surface Ni-N3C sites, NC@Ni-N-C_I with surface N-functionalities and underneath Ni-N3C sites as well as Ni-N-C_II with doubled surface Ni-N3C sites. The X-ray absorption spectroscopy indicates the coordination configuration of Ni-N3C. For NC catalysts, when N-doping level increased from 3.5 at% to 8.4 at%, the CO partial current density increased from below 0.1 mA/cm2 to 3 mA/cm2. Introducing one layer of Ni-N3C onto the NC structures leads to a 54 times higher CO partial current density than that of NC, in the meantime the FECO is 66 times higher. Furthermore, doubling the density of surface Ni-N3C sites by a layer-by-layer method doubles the CO partial current density (jCO), indicating its potential to achieve a high density of active coordinated sites and current densities.
Lithium metal batteries (LMBs) are considered to be one of the most promising high-energy-density battery systems. However, their practical application in carbonate electrolytes is hampered by lithium dendrite growth, resulting in short cycle life. Herein, an electrolyte regulation strategy is developed to improve the cyclability of LMBs in carbonate electrolytes by introducing LiNO3 using trimethyl phosphate with a slightly higher donor number compared to NO3− as a solubilizer. This not only allows the formaion of Li+-coordinated NO3− but also achieves the regulation of electrolyte solvation structures, leading to the formation of robust and ion-conductive solid-electrolyte interphase films with inorganic-rich inner and organic-rich outer layers on the Li metal anodes. As a result, high Coulombic efficiency of 99.1% and stable plating/stripping cycling of Li metal anode in Li||Cu cells were realized. Furthermore, excellent performance was also demonstrated in Li||LiNi0.83Co0.11Mn0.06O2 (NCM83) full cells and Cu||NCM83 anode-free cells using high mass-loading cathodes. This work provides a simple interphase engineering strategy through regulating the electrolyte solvation structures for high-energy-density LMBs.
Tetrahydro-γ-carbolines (THγCs) constitute one of the most important subtypes of indole alkaloids. In addition to being substructures of natural products, these structural motifs and moieties can often be found in pharmaceuticals due to their diverse bioactivities such as antiviral, antibacterial, antifungal, antiparasitic, antitumor, anti-inflammatory, and neuropharmacological activities. Beyond the pharmacological and biological aspects of these scaffolds, they have considerable synthetic applications for the construction of further bioactive compounds, too. The aim of this review is to summarize recent developments in the synthesis of this compound class.
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