Polyoxometalates-Mediated Selectivity in Pt Single-Atoms on Ceria for Environmental Catalysis.

Optimizing the reactivity and selectivity of single-atom catalysts (SACs) remains a crucial yet challenging issue in heterogeneous catalysis. This study demonstrates selective catalysis facilitated by a polyoxometalates-mediated electronic interaction (PMEI) in a Pt single-atom catalyst supported on CeO2 modified with Keggin-type phosphotungstate acid (HPW), labeled as Pt1/CeO2-HPW. The PMEI effect originates from the unique arrangement of isolated Pt atoms and HPW clusters on CeO2 surface. Electrons are transferred from ceria support to the electrophilic tungsten in HPW clusters, and subsequently, Pt atoms donate electrons to the now electron-deficient ceria. This phenomenon enhances the positive charge of Pt atoms, moderating O2 activation and limiting lattice oxygen mobility compared to the conventional Pt1/CeO2 catalyst. The resulting electronic structure of Pt combined with the strong and local acidic environment of HPW on Pt1/CeO2-HPW leads to improved degradation of NH3, N2 selectivity in the NO conversion, and CO2 yield when inputting volatile organic compounds. This study sheds the light on the design of SACs with balanced reactivity and selectivity for environmental catalysis applications.

Cobalt-Phthalocyanine-Derived Molecular Isolation Layer for Highly Stable Lithium Anode.

The uneven consumption of anions during the lithium (Li) deposition process triggers a space charge effect that generates Li dendrites, seriously hindering the practical application of Li-metal batteries. We report on a cobalt phthalocyanine electrolyte additive with a planar molecular structure, which can be tightly adsorbed on the Li anode surface to form a dense molecular layer. Such a planar molecular layer cannot only complex with Li ions to reduce the space charge effect, but also suppress side reactions between the anode and the electrolyte, producing a stable solid electrolyte interphase composed of amorphous lithium fluoride (LiF) and lithium carbonate (LiCO3 ), as verified by X-ray absorption near-edge spectroscopy. As a result, the Li|Li symmetric cell exhibits excellent cycling stability above 700 h under a high plating capacity of 3 mAh cm-2 . Moreover, the assembled Li|lithium iron phosphate (LiFePO4 , LFP) full-cell can also deliver excellent cycling over 200 cycles under lean electrolyte conditions (3 µL mg-1 ).

Enhanced Regulation of Selectivity by the Coupling Effects of Surface Acidity and Strain Effects via Precisely Controlling the Location of Pt.

Loading a sensitizer and constructing a rational nanostructure have been reported to be effective approaches for enhancing the catalytic/sensing performance. However, the impact of the precise loading position on the catalytic/sensing performance is always overlooked. Here, we discovered that precisely changing the location of Pt clusters from the outside of Al2O3-ZnO nanocoils (O-PtAlZnNCs) to the inner side of the nanocoils (I-PtAlZnNCs) could change the sensing performance of the sensor from H2S to acetone. Furthermore, precisely loading Pt inside of the confined space led to a high sensing performance and reduced the limit of detection (LOD) of acetone by a factor of 50 times (from 100 to 2 ppb). Combining X-ray photoelectron spectroscopy (XPS), NH3-diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), in situ X-ray absorption spectroscopy (XAS), and density functional theory (DFT) simulations, the enhancement of sensitivity and regulation of sensing selectivity are attributed to the coupling effects from enrichment of confined space and Al2O3 acid-base active sites as well as the regulation of electronic structure by location-dominated strain effects. This work not only provides a novel sight to precisely regulate the selectivity and obtain ultrasensitive materials but also serves as a useful instruction for further understanding and precisely designing specific sensors and catalysts with high performance.

Multishell SnO2 Hollow Microspheres Loaded with Bimetal PdPt Nanoparticles for Ultrasensitive and Rapid Formaldehyde MEMS Sensors.

Low-cost and real-time formaldehyde (HCHO) monitoring is of great importance due to its volatility, extreme toxicity, and ready accessibility. In this work, a low-cost and integrated microelectromechanical system (MEMS) HCHO sensor is developed based on SnO2 multishell hollow microspheres loaded with a bimetallic PdPt (PdPt/SnO2-M) sensitizer. The MEMS sensor exhibits a high sensitivity to HCHO ((Ra/Rg - 1) % = 83.7 @ 1 ppm), ultralow detection limit of 50 ppb, and ultrashort response/recovery time (5.0/7.0 s @ 1 ppm). These excellent HCHO sensing properties are attributed to its unique multishell hollow structure with a large and accessible surface, abundant interfaces, suitable mesoporous structure, and synergistic catalytic effects of bimetal PdPt. The well-defined multishell hollow structure also shows fascinating capacities as good hosts for noble metal loading. Therefore, PdPt bimetallic nanoparticles can be employed to construct a synergistic sensitizer with a high content and good dispersity on this multishell hollow structure, further exhibiting a reduced working temperature and ultrasensitive detection of HCHO. This PdPt/SnO2-M-based MEMS sensor presents a unique and highly sensitive means to detect HCHO, establishing its great promise for potential application in environmental monitoring.

Bimetallic Nanocrystals: Structure, Controllable Synthesis and Applications in Catalysis, Energy and Sensing.

In recent years, bimetallic nanocrystals have attracted great interest from many researchers. Bimetallic nanocrystals are expected to exhibit improved physical and chemical properties due to the synergistic effect between the two metals, not just a combination of two monometallic properties. More importantly, the properties of bimetallic nanocrystals are significantly affected by their morphology, structure, and atomic arrangement. Reasonable regulation of these parameters of nanocrystals can effectively control their properties and enhance their practicality in a given application. This review summarizes some recent research progress in the controlled synthesis of shape, composition and structure, as well as some important applications of bimetallic nanocrystals. We first give a brief introduction to the development of bimetals, followed by the architectural diversity of bimetallic nanocrystals. The most commonly used and typical synthesis methods are also summarized, and the possible morphologies under different conditions are also discussed. Finally, we discuss the composition-dependent and shape-dependent properties of bimetals in terms of highlighting applications such as catalysis, energy conversion, gas sensing and bio-detection applications.