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Palladium (Pd)-catalyzed cross-coupling reaction is a widely studied process with significant economic interest and represents one of the most successful nanocatalytic examples. Owing to the observ...

Au@RhPd ultrathin nanowires are designed as a highly reactive and selective catalyst for the hydrogenation of phenol under ambient conditions. Au NWs modulate the electronic state of Rh atoms to enhance the adsorption of phenol and desorption of cyclohexanone. Pd works as a cocatalyst to activate H

Electrochemical reduction (ER) is a promising approach to safely remove pollutants. However, sluggish reaction kinetics and significant side reactions considerably limit the applicability of this green process. Herein, we uncovered the previously ignored role of interfacial hydrophilicity in determining the ER performance through electron microscopy observations, contact angle (CA) analysis, and electrochemical measurements. A Pd/C electrocatalyst forms dense nanopores on the electrode surface, rendering it highly hydrophobic and achieving a CA of up to 145°. This imposes a large mass-transfer barrier for the diffusion of water and pollutants into Pd sites. Moreover, the release of H

Sulfur mustard (SM) is a notorious blistering chemical warfare agent. Rapid field screening for trace SM is of vital significance for the detection of antiterrorism and timely treatment. Here, a visual assay for SM was constructed on the basis of its inhibition for the G-quadruplexes/hemin DNAzyme. Specifically, multiple guanine (G)-rich single stranded oligonucleotides (ssODN) named S1 (80% of G in the total bases), i.e., the precursor for G-quadruplex, which could oxide tetramethylbenzidine (TMB) to its green product, were conjugated on the nonfouling polymer brush grafted magnetic beads (MB@P(C-H)). SM could specifically alkylate the N7 and O6 sites of G in the S1; thus, it failed to form the DNAzyme based signal reporter. It was demonstrated that the nonfouling P(C-H) interface on the magnetic bead (MB) could protect the conjugated ssODN from nuclease degradation, thus ensuring its well sensing performance in complex samples. Under the optimized conditions, this method achieved good sensitivity and selectivity with a limit of detection (LOD) as low as 0.26 μmol L

Understanding the reactive site/CO

Rapid screening monofluoroacetic acid (FAcOH) is responsible for preventing chemical poisoning and food safety events. Whereas surface enhanced Raman scattering (SERS) spectra is an effective tool for detecting forbidden chemicals, it is difficult to directly detect FAcOH due to its small Raman scattering cross section as well as weak adsorption on SERS substrates. In this work, the metal phenolic supramolecular networks (MPNs, i.e., the tannic acid and Fe3+ complex) were fabricated on the commercial nanoanodic aluminum oxide film (NAAO) for assisting in situ chemical deposition highly uniform Ag nanostructure over large areas (the NAAO@AgNS). The low cost and simple fabrication process made the NAAO@AgNS a single-use consumable. For FAcOH detection, a specific derivative reaction between FAcOH and thiosalicylic acid (TSA) was introduced. By taking TSA as the Raman probe, its SERS signal attenuated constantly with the increasing amount of FAcOH. For improving quantitative accuracy, thiocyanate (SCN-) was introduced on the NAAO@AgNS as an internal standard; thus, the characteristic peak intensity ratios associated with TSA and SCN- (I1035/I2125) were fitted to the concentration of FAcOH. It was demonstrated that the SERS assay achieved good sensitivity and selection toward FAcOH with the limit of quantitation (LOD) as low as 50 nmol L-1. The NAAO@AgNS featured with highly sensitive, uniform, and consistent SERS performances could easily extend to wide SERS applications.

The catalyzed reduction process plays an important role in the safe handling of environmental contaminants. It is generally believed that the adsorption of pollutants and cleavage of chemical bonds...

The electrocatalytic reduction of CO2 (CO2ER) to liquid fuels is important for solving fossil fuel depletion. However, insufficient insight into the reaction mechanisms renders a lack of effective regulation of liquid product selectivity. Here, in situ surface-enhanced Raman spectroscopy (SERS) empowered by 13C/12C isotope exchange is applied to probing the CO2ER process on nanoporous silver (np-Ag). Direct spectroscopic evidence of the preliminary intermediates, *COOH and *OCO-, indicates that CO2 is coordinated to the catalyst via diverse adsorption modes. Further, the relative Raman intensities of the above intermediates vary notably on np-Ag modified by Cu or Pd, and the liquid product selectivity also changes accordingly. Combined with density functional theory calculations, this study demonstrates that the CO2 adsorption configuration is a critical factor governing the reaction selectivity. Meanwhile, *COOH and *OCO- are key targets in the initial stage regulating liquid product selectivity, which could facilitate future selective catalyst design.

Anodic electrocatalyst plays the core role in direct alcohol fuel cells (DAFCs), while traditional Pt-catalysts suffer from limited catalytic activity, high over potential and severe CO poisoning. Herein, by selectively depositing Rh atoms on the defective-sites of Pt nanowires (NWs), we developed a new Pt@Rh NW electrocatalyst that exhibited enhanced electrocatalytic performance for both methanol oxidation (MOR) and ethanol oxidation (EOR). Both cyclic voltammetry (CV) and in-situ infrared spectroscopy revealed that the presence of Rh atoms suppressed the generation of poisonous intermediates and completely oxidized alcohols molecule into CO2. Atomic resolusion spherical aberration corrected high-angle annular dark field scanning transmission electron microscopy (CS-HAADF-STEM) and energy-dispersive X-ray spectroscopy (EDS) mapping analysis revealed that Rh atoms were primarily deposited on the defective sites of Pt NWs. Meanwhile, the presence of Rh atoms also modified the electronic state of Pt atoms and therefore lowered the onset potential for alcohols oxidation potential. This work gives the first clear clue on the role of the defective sites of Pt nanocatalyst poisoning, and propose that selectively blocking these sites with trace amount of Rh is an effective strategy in designing advantageous electrocatalysts.

Here, a new designed core/satellite gold nanoprobe was developed for detecting trace mount of benzoyl peroxide (BPO) based on its deboronation. This gold nanoassembly (the BE-AuNPs12/65) was constructed via borate ester formation between large 4-mercaptophenylboronic acid (MPBA) modified AuNPs (the MPBA-AuNPs65, as cores) and small dopamine modified AuNPs (the DPA-AuNPs12, as satellites). Particularly, upon addition of BPO, it would trigger the deboronation for the BE-AuNPs12/65 probes accompanying with distinct color changes from blue, purple to wine red, which implied the disassembly of the core/satellite nanostructure after the breakage of carbon to boron chemical bond. By measuring the absorbance ratio at 665 nm and 545 nm, quantification of BPO was achieved in the range of 10.0–100.0 nmol/L, which could also be easily observed by naked eyes. The nanoprobe utilized a boronate deprotection mechanism and the LSPR properties of AuNPs to provide high selectivity for detecting BPO over similar ROS/RNS with the limit of detection as low as 7.2 nmol/L. The practical applicability of this assay was verified through successful determining BPO in flour samples, which demonstrated its great potentials in food safety field.

Video game-based therapies are widely used in rehabilitation. Compared with conventional bilateral upper limb training (CBULT), the effects of video game-based bilateral upper limb training (VGBULT) on brain cortical activation and functional connectivity, still not fully clear. We have developed a VGBULT system, and measured the brain activity of 20 elderly subjects (10 male, mean age = 62.4 ± 5.8) while performing CBULT and VGBULT tasks by using functional near infrared spectroscopy (fNIRS). The results showed that the cerebral cortex of the two groups both showed significant activation (p 0.05), compared with the baseline; In the VGBLUT group, the activation of motor cortex (MC) and prefrontal cortex (PFC) was stronger, and the functional connectivity between PFC and MC was also enhanced. This study showed that VGBULT is potentially more beneficial for the elderly neural activities and cognitive control, and provides a theoretical basis for future research and development of such rehabilitation products. Moreover, fNIRS is a reliable tool for tracking brain activation in the evaluation of retraining regimens.

AuPd bimetallic nanocatalysts exhibit superior catalytic performance in the cleavage of carbon-halogen bonds (C-X) in the hazardous halogenated pollutants. A better understanding of how Au atoms promote the reactivity of Pd sites rather than vaguely interpreting as bimetallic effect and determining which type of Pd sites are necessary for these reactions are crucial factors for the design of atomically precise nanocatalysts that make full use of both the Pd and Au atoms. Herein, we systematically manipulated the coordination number of Pd-Pd, d-orbital occupation state, and the Au-Pd interface of the Pd reactive centers and studied the structure-activity relationship of Au-Pd in the catalyzed cleavage of C-X bonds. It is revealed that Au enhanced the activity of Pd atoms primarily by increasing the occupation state of Pd d-orbitals. Meanwhile, among the Pd sites formed on the Au surface, five to seven contiguous Pd atoms, three or four adjacent Pd atoms, and isolated Pd atoms were found to be the most active in the cleavage of C-Cl, C-Br, and C-I bonds, respectively. Besides, neighboring Au atoms directly contribute to the weakening of the C-Br/C-I bond. This work provides new insight into the rational design of bimetallic metal catalysts with specific catalytic properties.

Capacitive deionization (CDI) is an emerging technology for energy-efficient water desalination, and attracts more and more attention in recent years. It has been concluded that CDI technology shows competitiveness and perspectives on seawater desalination and wastewater treatment. The ionic adsorption mechanism can be clarified by electric double-layer capacitive adsorption and pseudocapacitive adsorption. The performance of CDI depends on both device and materials. The adsorption capacity and energy efficiency was improved significantly with fast growth of researches on material and novel energy storage techniques. This review summarizes researches on CDI technologies with an emphasis on electrode material design and improved adsorption performance.

Precious metal intermetallic nanoclusters (IMNCs) are promising nanocatalysts for practical industrial applications. However, to date, the preparation of these nanoclusters has been restricted to harsh conditions, and only succeeds for a limited number of elements. This study developed a simple and efficient strategy that enables the synthesis of supported IMNCs under ambient conditions via inorganometallic coordination chemistry, specifically, by donating the Cl- ligand, a noble metal chloride (MClab-) forms a heterobimetallic ion (MxFeyClzn-) with the coordination-unsaturated FeCl3. Upon reduction, the ordered heterobimetallic ions are simultaneously transformed into IMNCs and embedded into gamma-Fe2O3 nanosheets, which form from excess FeCl3. In addition to providing convincing spectral evidence for the structure of the heterobimetallic ions, magnetic measurements, atomic-resolution electron microscopy, X-ray absorption spectroscopy, and Fourier transform infrared spectroscopy of chemisorbed CO collectively confirm the successful preparation of the L1(0)-phased Pd3Fe IMNCs. Furthermore, this versatile method can be extended to synthesize other IMNCs, such as AuFe and PtFe, and seems to be applicable to IrFe, RhFe, RuFe, and MCo. When utilized as a heterogeneous catalyst in a Heck coupling reaction, the prepared Pd3Fe IMNCs display satisfactory activity and stability, highlighting their potential applications as advantageous catalysts.