Bi/CeO2-Decorated CuS Electrocatalysts for CO2-to-Formate Conversion.

The electrocatalytic carbon dioxide (CO2) reduction reaction (CO2RR) is extensively regarded as a promising strategy to reach carbon neutralization. Copper sulfide (CuS) has been widely studied for its ability to produce C1 products with high selectivity. However, challenges still remain owing to the poor selectivity of formate. Here, a Bi/CeO2/CuS composite was synthesized using a simple solvothermal method. Bi/CeO2-decorated CuS possessed high formate selectivity, with the Faraday efficiency and current density reaching 88% and 17 mA cm-2, respectively, in an H-cell. The Bi/CeO2/CuS structure significantly reduces the energy barrier formed by OCHO*, resulting in the high activity and selectivity of the CO2 conversion to formate. Ce4+ readily undergoes reduction to Ce3+, allowing the formation of a conductive network of Ce4+/Ce3+. This network facilitates electron transfer, stabilizes the Cu+ species, and enhances the adsorption and activation of CO2. Furthermore, sulfur catalyzes the OCHO* transformation to formate. This work describes a highly efficient catalyst for CO2 to formate, which will aid in catalyst design for CO2RR to target products.

Scalable Production of 2D Non-Layered Metal Oxides through Metal-Organic Gel Rapid Redox Transformation.

Two-dimensional (2D) nonlayered metal compounds with porous structure show broad application prospects in electrochemistry-related fields due to their abundant active sites, open ions/electrons diffusion channels, and faradaic reactions. However, scalable and universal synthesis of 2D porous compounds still remains challenging. Here, inspired by blowing gum, a metal-organic gel (MOG) rapid redox transformation (MRRT) strategy is proposed for the mass production of a wide variety of 2D porous metal oxides. Adequate crosslinking degree of MOG precursor and its rapid redox with NO3- are critical for generating gas pressure from interior to exterior, thus blowing the MOG into 2D carbon nanosheets, which further act as self-sacrifice template for formation of oxides with porous and ultrathin structure. The versatility of this strategy is demonstrated by the fabrication of 39 metal oxides, including 10 transition metal oxides, one II-main group oxide, two III-main group oxides, 22 perovskite oxides, four high-entropy oxides. As an illustrative verification, the 2D transition metal oxides exhibit excellent capacitive deionization (CDI) performance. Moreover, the assembled CDI cell could act as desalting battery to supply electrical energy during electrode regeneration. This MRRT strategy offers opportunities for achieving universal synthesis of 2D porous oxides with nonlayered structures and studying their electrochemistry-related applications.

Fe-Decorated Nitrogen-Doped Carbon Nanospheres as an Electrochemical Sensing Platform for the Detection of Acetaminophen.

In this work, Fe-decorated nitrogen-doped carbon nanospheres are prepared for electrochemical monitoring of acetaminophen. Via a direct pyrolysis of the melamine-formaldehyde resin spheres, the well-distributed Fe-NC spheres were obtained. The as-prepared Fe-NC possesses enhanced catalysis towards the redox of acetaminophen for abundant active sites and high-speed charge transfer. The effect of loading Fe species on the electrochemical sensing of acetaminophen is investigated in detail. The synergistic effect of nitrogen doping along with the above-mentioned properties is taken advantage of in the fabrication of electrochemical sensors for the acetaminophen determination. Based on the calibration plot, the limits of detection (LOD) were calculated to be 0.026 µM with a linear range from 0-100 µM. Additionally satisfactory repeatability, stability, and selectivity are obtained.

Biomass-derived N,S co-doped 3D multichannel carbon supported Au@Pd@Pt catalysts for oxygen reduction.

A beancurd-derived mesoporous carbon (NSC) was prepared by an environmentally friendly procedure, and then it was investigated as Au@Pd@Pt core-shell catalysts support (Au@Pd@Pt-NSC) for oxygen reduction reaction (ORR). The Au@Pd@Pt-NSC (E1/2 = 0.91 V) has a marginally negative ORR half-wave potential compared with other materials, in particular Pt/C (E1/2 = 0.87 V) and Au@Pd@Pt-C (E1/2 = 0.81 V). The specific and mass activities of the Au@Pd@Pt-NSC were 5 and 13 times higher than the commercial a Pt/C catalyst. After 20000 cycles of rapid durability test, the Au@Pd@Pt-NSC sample showed a loss of just 4.9% compared with the initial ECSA area, which can be attributed to the favorable interaction between Au@Pd@Pt and NSC. These results can be considered of environmental relevance and high potential applicability.

Highly active iron-nitrogen-boron-carbon bifunctional electrocatalytic platform for hydrogen peroxide sensing and oxygen reduction.

An iron-nitrogen-boron-carbon (Fe-N-B-C) bifunctional electrocatalyst was prepared by means of a facile one-step hydrothermal reduction of graphene oxide using dimethylamine borane as doping agent. In addition, hemins were efficiently anchored during doping/reducing process on this modified graphene. The as-prepared Fe-N-B-C electro-catalyst showed enhanced response as regards its potential for reduction of H2O2 and O2. In view of its catalytic activity, this Fe-N-B-C material was tested for the determination of H2O2 with a chronoamperometry method, obtaining a detection limit as low as 0.055 µM, which is better than that of some Hemin-N-C materials. Regarding O2 reduction reaction, a study performed using a rotating disk electrode indicated that this material exhibits a positive onset potential (0.90V vs. RHE), high selectivity (4e- process), high limiting-current density (4.75 mA cm-2) and strong resistance against the crossover-effect from methanol in alkaline medium, making it to be the promising candidate as alternative for commercial Pt/C catalysts. These results could have commercial and environmental relevance and would deserve further complementary investigation.

1000-Fold Preconcentration of Per- and Polyfluorinated Alkyl Substances within 10 Minutes via Electrochemical Aerosol Formation.

We present a simple and efficient method for preconcentrating per- and polyfluorinated alkyl substances (PFAS) in water. Our method was inspired by the sea-spray aerosol enrichment in nature. Gas bubbles in the ocean serve to scavenge surface active material, carrying it to the air-ocean interface, where the bubbles burst and form a sea-spray aerosol. These aerosol particles are enriched in surface-active organic compounds such as free fatty acids and anionic surfactants. In our method, we in situ generate H2 microbubbles by electrochemical water reduction using a porous Ni foam electrode. These H2 bubbles pick up PFAS as they rise through the water column that contains low concentration PFAS. When these bubbles reach the water surface, they burst and produce aerosol droplets that are enriched in PFAS. Using this method, we demonstrated ∼1000-fold preconcentration for ten common PFAS in the concentration range from 1 pM to 1 nM (or ∼0.5 ng/L to 500 ng/L) in 10 min. We also developed a diffusion-limited adsorption model that is in quantitative agreement with the experimental data. In addition, we demonstrated using this method to preconcentrate PFAS in tap water, indicating its potential use for quantitative analysis of PFAS in real-world water samples.

Redox-Responsive Pickering Emulsions Based on Silica Nanoparticles and Electrochemical Active Fluorescent Molecules.

In this paper, we report a novel redox-responsive water-in-oil Pickering emulsion stabilized by negatively charged silica nanoparticles in combination with a trace amount of redox switchable fluorescent molecule ferrocene azine (FcA), in which ferrocene serves as a redox-sensitive group and anthryl unit serves as a fluorescence emission center. By alternately adding oxidants and reducing agents at a moderate condition, the amphiphilicity of silica nanoparticles changes because of the adsorption of Fc+A and the desorption of FcA on the silica surface. On the one hand, the stability of emulsions can be transformed between stable and unstable at ambient temperature via redox trigger and the regulation process can be cycled at least three times. On the other hand, the fluorescent intensity of the FcA molecule can be regulated by redox stimuli; thus, the change in fluorescent behavior of the emulsion droplets is observed upon redox cycles, which makes it useful in the fluorescent label of stimuli-responsive Pickering emulsions. This work provides a deep understanding of the regulation mechanism of Pickering emulsions upon redox stimuli and opens the new way for in situ fluorescent label of stimulus-responsive Pickering emulsions without introducing additional fluorescent molecules.

Fundamental understanding of nitrogen in biomass electrocatalysts for oxygen reduction and zinc-air batteries.

Exploring high-efficiency catalysts for oxygen reduction reactions (ORRs) is essential for the development of large-scale applications of fuel cell and metal-air batteries technology. The as-prepared Fe-NC-800 via polymerization-pyrolysis strategy exhibited superior ORR activity with onset potential of 1.030 V vs. reversible hydrogen electrode (RHE) and half-wave potential of 0.908 V vs. RHE, which is higher than that of the Pt/C catalyst and most of other Fe-based catalysts. The different d-band center values can be attributed to the influence of different N-doped carbon, leading to the adjustment in the ORR activity. In addition, Fe-NC-800-based Zn-air battery showed better electrochemical performance with a high discharge specific capacity of 806 mA h g-1 and a high-power density of 220 mW cm-2 than that of the Pt/C-based battery. Therefore, the biomass Fe-NC-800 catalyst may become a promising substitute for Pt/C catalysts in energy storage and conversion devices.

Ultrasensitive Chemodynamic Therapy: Bimetallic Peroxide Triggers High pH-Activated, Synergistic Effect/H2 O2 Self-Supply-Mediated Cascade Fenton Chemistry.

Recently, nanoparticle-triggered in situ catalytic Fenton/Fenton-like reaction is widely explored for tumor-specific chemodynamic therapy (CDT). However, despite the great potential of CDT in tumor treatment, insensitive response to the relatively high pH of the tumor sites and the insufficient intratumoral H2 O2 level leads to limited efficiency of most Fenton/Fenton-like reactions, which greatly imped its clinical conversion. This paper reports the fabrication of Fenton-type bimetallic peroxides for ultrasensitive chemodynamic therapy with high pH-activated, synergistic effect/H2 O2 self-supply-mediated cascade Fenton chemistry for the first time. The observations reveal that these bimetallic peroxides exhibit an ultrasensitive acid-activated decomposition-mediated Fenton-like reaction at the relatively high pH of 6.5-7.0, accompanied with highly increased •OH generation efficiency (especially, 40-60-fold increase at pH 7.0) by the metal-mediated synergistic effect-enhanced Fenton chemistry as well as in situ self-generated H2 O2 supplement. Moreover, the bimetallic peroxides exhibit high tumor accumulation which along with a high-efficiency tumor catalytic-therapeutic with negligible side effects in vivo. Developing these novel bimetallic peroxides, together with the already demonstrated capacity of the key metals (Fe, Mn, Cu, etc.) for magnetic resonance imaging or photodynamic/immune-enhanced therapy, will propel interest in development of smart high-efficiency nanoplatform for cancer theranostics.

In Situ 3D-to-2D Transformation of Manganese-Based Layered Silicates for Tumor-Specific T1-Weighted Magnetic Resonance Imaging with High Signal-to-Noise and Excretability.

Recently, Mn(II)-based T1-weighted magnetic resonance imaging (MRI) contrast agents (CAs) have been explored widely for cancer diagnosis. However, the "always-on" properties and poor excretability of the conventional Mn(II)-based CAs leads to high background signals and unsatisfactory clearance from the body. Here, we report an "in situ three-dimensional to two-dimensional (3D-to-2D) transformation" method to prepare novel excretable 2D manganese-based layered silicates (Mn-LSNs) with extremely high signal-to-noise for tumor-specific MR imaging for the first time. Our observations combined with density functional theory (DFT) calculations reveal that 3D metal (Mn, Fe, Co) oxide nanoparticles are initially formed from the molecular precursor solution and then in situ transform into 2D metal (Mn, Fe, Co)-based layered silicates triggered by the addition of tetraethyl orthosilicate, which provides a time-saving and versatile way to prepare novel 2D silicate nanomaterials. The unique ion-exchangeable capacity and high host layer charge density endow Mn-LSNs with an "ON/OFF" pH/GSH stimuli-activatable T1 relaxivity with superb high signal-to-noise (640-, 1200-fold for slightly acidic and reductive changes, respectively). Further in vivo MR imaging reveals that Mn-LSNs exhibit a continuously rapid T1-MRI signal enhancement in tumor tissue and no visible signal enhancement in normal tissue, indicating an excellent tumor-specific imaging. In addition, Mn-LSNs exhibit a rapid excretion from the mouse body in 24 h and invisible organ toxicity, which could help to solve the critical intractable degradation issue of conventional inorganic CAs. Moreover, the tumor microenvironment (pH/GSH/H2O2) specific degradability of Mn-LSNs could help to improve the penetration depth of particles into the tumor parenchyma. Developing this novel Mn-LSNs contrast agent, together with the already demonstrated capacity of layered silicates for drug and gene delivery, provides opportunities for future cancer theranostics.

Studies on the interaction between 9-fluorenylmethyl chloroformate and Fe3+ and Cu2+ ions: spectroscopic and theoretical calculation approach.

The interaction between 9-fluorenylmethyl chloroformate (FMOC-Cl) and Fe3+ and Cu2+ ions was investigated using fluorescence, UV/Vis absorption spectroscopies and theoretical calculation. The optical property of FMOC-Cl was studied in detail in absence and presence of various transition metal ions with particular affinity to Fe3+ and Cu2+ ions. With the fluorescence characteristic band centered at 307 and 315 nm for FMOC-Cl, the introduction of Fe3+ or Cu2+ ions leads to the fluorescence quenching of FMOC-Cl with different shift and intensities of two fluorescent bands. It allows us to differentiate between FMOC-Cl and Fe3+ and Cu2+ ions interaction behavior. The study on fluorescent kinetics confirms that the fluorescence quenching of FMOC-Cl with Fe3+ and Cu2+ ions is based on the formation of non-fluorescent material, that is, static quenching. Further analyses of bond lengths, Mulliken atomic charges and the frontier orbital compositions for FMOC-Cl and its complexes with Fe3+ and Cu2+ ions were carried out. The theoretical calculations prove the fluorescence quenching originates from the formation of coordination bonds between the oxygen atom of the carbonyl group of FMOC-Cl and Fe3+ and Cu2+ ions. The commercially available FMOC-Cl can be used as excellent fluorescent probe toward Fe3+ and Cu2+ ions with high sensitivity.