The Pathway of Sulfide Oxidation to Octasulfur Globules in the Cytoplasm of Aerobic Bacteria.

Sulfur-oxidizing bacteria can oxidize hydrogen sulfide (H2S) to produce sulfur globules. Although the process is common, the pathway is unclear. In recombinant Escherichia coli and wild-type Corynebacterium vitaeruminis DSM 20294 with sulfide:quinone oxidoreductase (SQR) but no enzymes to oxidize zero valence sulfur, SQR oxidized H2S into short-chain inorganic polysulfide (H2Sn, n ≥ 2) and organic polysulfide (RSnH, n ≥ 2), which reacted with each other to form long-chain GSnH (n ≥ 2) and H2Sn before producing octasulfur (S8), the main component of elemental sulfur. GSnH also reacted with glutathione (GSH) to form GSnG (n ≥ 2) and H2S; H2S was again oxidized by SQR. After GSH was depleted, SQR simply oxidized H2S to H2Sn, which spontaneously generated S8. S8 aggregated into sulfur globules in the cytoplasm. The results highlight the process of sulfide oxidation to S8 globules in the bacterial cytoplasm and demonstrate the potential of using heterotrophic bacteria with SQR to convert toxic H2S into relatively benign S8 globules. IMPORTANCE Our results provide evidence of H2S oxidation producing octasulfur globules via sulfide:quinone oxidoreductase (SQR) catalysis and spontaneous reactions in the bacterial cytoplasm. Since the process is an important event in geochemical cycling, a better understanding facilitates further studies and provides theoretical support for using heterotrophic bacteria with SQR to oxidize toxic H2S into sulfur globules for recovery.

Synthesis of cationic carbon dots and their effects on human serum proteins and in vitro blood coagulation.

Cationic carbon dots (CCDs) are a promising alternative to gene-delivery systems, and good biosafety levels are crucial for their in vivo use. In this study, spherical and monodispersed CCDs with an average surface potential of +28.7 mV were prepared using sucrose and glutamate (denoted SG-CCDs) using a one-pot autoclave-assisted method. Molecular interactions between the SG-CCDs and four major human serum proteins (albumin, immunoglobulin G, fibrinogen, and transferrin) were investigated. The results were further verified on human serum, and the effect of the SG-CCDs on in vitro blood coagulation was examined. The results showed that the fluorescence of human serum was clearly quenched by the SG-CCDs through a dynamic collision mechanism. Moreover, SG-CCDs at a concentration of 20 µM exhibited minor effects on the secondary structure of human serum. The activated partial thromboplastin and prothrombin time as well as the fibrinogen concentration were not changed, indicating that the SG-CCDs did not interfere with the coagulation process. This study provided an understandable background on the behaviour of CCDs in clinical applications.

Encapsulation of Homogeneous Catalysts in Mesoporous Materials Using Diffusion-Limited Atomic Layer Deposition.

The heterogenization of homogeneous metal complex catalysts has attracted great attention. The encapsulation of metal complexes into nanochannels of mesoporous materials is achieved by coating metal oxides at/near the pore entrance by diffusion-limited atomic layer deposition (ALD) to produce a hollow plug. The pore size of the hollow plug is precisely controlled on the sub-nanometer scale by the number of ALD cycles to fit various metal complexes with different molecular sizes. Typically, Co or Ti complexes are successfully encapsulated into the nanochannels of SBA-15, SBA-16, and MCM-41. The encapsulated Co and Ti catalysts show excellent catalytic activity and reusability in the hydrolytic kinetic resolution of epoxides and asymmetric cyanosilylation of carbonyl compounds, respectively. This ALD-assisted encapsulation method can be extended to the encapsulation of other homogeneous catalysts into different mesoporous materials for various heterogeneous reactions.

Superconductor-insulator transition in quasi-one-dimensional single-crystal Nb2PdS5 nanowires.

Superconductor-insulator transition (SIT) in one-dimensional (1D) nanowires attracts great attention in the past decade and remains an open question since contrasting results were reported in nanowires with different morphologies (i.e., granular, polycrystalline, or amorphous) or environments. Nb2PdS5 is a recently discovered low-dimensional superconductor with typical quasi-1D chain structure. By decreasing the wire diameter in the range of 100-300 nm, we observed a clear SIT with a 1D transport character driven by both the cross-sectional area and external magnetic field. We also found that the upper critical magnetic field (Hc2) decreases with the reduction of nanowire cross-sectional area. The temperature dependence of the resistance below Tc can be described by the thermally activated phase slip (TAPS) theory without any signature of quantum phase slips (QPS). These findings demonstrated that the enhanced Coulomb interactions with the shrinkage of the wire diameter competes with the interchain Josephson-like coupling may play a crucial role on the SIT in quasi-1D system.

Single-atom Mo-tailored high-entropy-alloy ultrathin nanosheets with intrinsic tensile strain enhance electrocatalysis.

The precise structural integration of single-atom and high-entropy-alloy features for energy electrocatalysis is highly appealing for energy conversion, yet remains a grand challenge. Herein, we report a class of single-atom Mo-tailored PdPtNiCuZn high-entropy-alloy nanosheets with dilute Pt-Pt ensembles and intrinsic tensile strain (Mo1-PdPtNiCuZn) as efficient electrocatalysts for enhancing the methanol oxidation reaction catalysis. The as-made Mo1-PdPtNiCuZn delivers an extraordinary mass activity of 24.55 A mgPt-1 and 11.62 A mgPd+Pt-1, along with impressive long-term durability. The planted oxophilic Mo single atoms as promoters modify the electronic structure of isolated Pt sites in the high-entropy-alloy host, suppressing the formation of CO adsorbates and steering the reaction towards the formate pathway. Meanwhile, Mo promoters and tensile strain synergistically optimize the adsorption behaviour of intermediates to achieve a more energetically favourable pathway and minimize the methanol oxidation reaction barrier. This work advances the design of atomically precise catalytic sites by creating a new paradigm of single atom-tailored high-entropy alloys, opening an encouraging pathway to the design of CO-tolerance electrocatalysts.

In situ annealing achieves an ultrafast synthesis of high coercive strontium ferrite foams and beyond.

Strontium ferrite nanostructures have attracted intensive interest recently due to the increasing demand for cost-effective features and good chemical corrosion resistance of magnetic materials, yet the ultrafast synthesis of strontium ferrite with desired coercivity is still experiencing a severe challenge. Herein, porous strontium ferrite foams with a coercivity up to 23.35 kOe were prepared by ultrafast in situ annealing for 1 min based on an auto-combustion strategy. The high coercivity of strontium ferrite benefits from the increasing magnetocrystalline anisotropy caused by the ion substitution and the appropriate grain size close to the critical single-domain size of strontium ferrite. In addition, this ultrafast synthesis can be extended to prepare a series of porous spinel, lanthanide-based perovskites, and their high-entropy counterpart foams. We also demonstrate that this strategy is feasible for preparing biphasic composite oxide foams. Furthermore, this work provides important guidance for the design of porous permanent magnet materials and the efficient preparation of porous oxide foam materials.

N-hexane-assisted synthesis of plasmonic Au-mediated polymeric carbon nitride photocatalyst for remarkable H2 evolution under visible-light irradiation.

Plasmonic Au-mediated polymeric carbon nitride (PCN) has been recognized as one of the promising materials for photocatalytic applications due to its excellent properties in wide visible light spectrum, however it is still hindered by low catalytic efficiency. In this work, it was established that strong metal-support interactions (MSI) at the interface between plasmonic Au nanoparticles (NPs) and PCN nanosheets (PCNS) improves its photocatalytic efficiency. The resulting Au/PCNS2.5 exhibits excellent photocatalytic activity with H2 evolution rate up to 4.84 mmol g-1h-1 under visible light, 12.4 times higher than that of bulk PCN. Such strong MSI significantly strengthens the localized surface plasmon resonance (LSPR) effect of Au NPs and the charge "pump" role of Schottky junctions at Au-PCNS interface, resulting in broad light absorption range as well as effective separation and transfer of charge carrier. This work provides a new way to design the plasmonic photocatalysts for splitting water as well as other plasmon-driven chemical reactions.

MnIn2S4 nanosheets growing on rods-like ß-MnO2 via covalent bonds as high-performance photocatalyst for boosting Cr(VI) photocatalytic reduction under visible light irradiation: Behavior and mechanism study.

It is an urgent and onerous task to develop catalysts for photocatalytic reduction of Cr(VI) in wastewater under wide pH range. In this work, a novel hierarchical Z-scheme MnO2/MnIn2S4 (MISO) heterojunction photocatalyst with MnIn2S4 nanosheets growing on the surface of ß-MnO2 nanorods is constructed for efficient photocatalytic reduction of Cr(VI). The optimized 2.0-MISO photocatalyst exhibits the almost 100% reduction efficiency in the pH range of 2.1-5.6 under visible light irradiation, and the apparent rate constant is 0.05814 min-1, which is 29.96 and 3.27 times higher than the pure ß-MnO2 and MnIn2S4, respectively. A efficient photocatalytic reduction of Cr(VI) to Cr(III) species on 2.0-MISO photocatalyst in actual industry wastewater (286.7 mg/L) up to 99.8% is achieved. Under natural light, the 2.0-MISO photocatalyst also shows rapid reduction of Cr(VI) species. The photocorrosion of MnIn2S4 was significantly hindered by the construction of heterojunction. And the O2- and e- species are the main active species during the Cr(VI) photoreduction process. The connection mode between MnIn2S4 and ß-MnO2 is verified by DFT calculations and a possible photocatalytic mechanism is also proposed.

Short-Range Diffusion Enables General Synthesis of Medium-Entropy Alloy Aerogels.

Medium-entropy alloy aerogels (MEAAs) with the advantages of both multimetallic alloys and aerogels are promising new materials in catalytic applications. However, limited by the immiscible behavior of different metals, achieving single-phase MEAAs is still a grand challenge. Herein, a general strategy for preparing ultralight 3D porous MEAAs with the lowest density of 39.3 mg cm-3 among the metal materials is reported, through combining auto-combustion and subsequent low-temperature reduction procedures. The homogenous mixing of precursors at the ionic level makes the short-range diffusion of metal atoms possible to drive the formation of single-phase MEAAs. As a proof of concept in catalysis, as-synthesized Ni50 Co15 Fe30 Cu5 MEAAs exhibit a high mass activity of 1.62 A mg-1 and specific activity of 132.24 mA cm-2 toward methanol oxidation reactions, much higher than those of the low-entropy counterparts. In situ Fourier transform infrared and NMR spectroscopies reveal that MEAAs can enable highly selective conversion of methanol to formate. Most importantly, a methanol-oxidation-assisted MEAAs-based water electrolyzer can achieve a low cell voltage of 1.476 V at 10 mA cm-2 for making value-added formate at the anode and H2 at the cathode, 173 mV lower than that of traditional alkaline water electrolyzers.

In-situ synthesis of dual Z-scheme heterojunctions of cuprous oxide/layered double hydroxides/nitrogen-rich graphitic carbon nitride for photocatalytic sterilization.

Two-dimensional (2D) layered double hydroxides (LDHs) and graphitic carbon nitride (g-C3N4) with sufficiently positive valence bands and negative conduction bands are promising materials for producing superoxide radicals (·O2-) and hydroxyl radicals (·OH) for photocatalytic sterilization; however, their relatively wide bandgaps limit the utilization of light in photocatalysis. Herein, the electronegative N-CN nanosheets were used to adsorb Cu2+, Zn2+ and Al3+ cations in situ to form uniformly distributed LDHs nanosheets. Then, the LDHs on LDHs/N-CN composites were partially reduced in situ into ultrafine Cu2O to harvest sufficient solar energy. Zeta potential measurements revealed that the constructed Cu2O/LDHs/N-CN composites and bacterial solution exhibited opposite charges, which induced strong electrostatic adsorption in photocatalytic sterilization. Under visible light, the highly hydrophilic 0D/2D/2D Cu2O/LDHs/N-CN heterojunctions exhibited the highest sterilization rate of 98.96% toward Escherichia coli without an obvious decrease after 4 cycles. It was experimentally and theoretically confirmed that a dual Z-scheme charge migration path in the Cu2O/LDHs/N-CN heterojunction was achieved, harnessing the full synergetic potential of the combined system. This work provides an effective method for synthesizing a robust, hydrophilic and positively charged heterojunction to further improve photocatalytic sterilization activity.

Mesoporous cobalt ferrite phosphides/reduced graphene oxide as highly effective electrocatalyst for overall water splitting.

Although the electrochemical production of hydrogen has been considered as a promising strategy to obtain the sustainable resources, the sluggish kinetics of anodic oxygen evolution reaction (OER) hindered the sustainable energy development. Herein, we design mesoporous cobalt ferrite phosphides hybridized on reduced graphene oxide (rGO) as a highly efficient bifunctional catalyst through a simple nanocasting method. The hybrid catalyst possesses the abundant interface, which provides the large active sites, as well as the hybrid rGO accelerates the electron exchange and ion diffusion. Moreover, the mesoporous structure not only prevents the aggregation of actives sites, but also benefits for the rapid escape of bubbles during catalytical process, which can significantly improve the catalytic performance. Consequently, the resulting mCo0.5Fe0.5P/rGO shows superior catalytic performance with a low overpotential of 250 mV at a current density of 10 mA cm-2 for OER and outstanding long-term stability. More importantly, an electrolyzer with mCo0.5Fe0.5P/rGO as both anode and cathode catalysts shows a low voltage of 1.66 V to afford a current density of 10 mA cm-2. This work offers a new route for designing the highly efficient OER and overall water splitting electrocatalysts.

Fe3O4 nanoparticles coated with ultra-thin carbon layer for polarization-controlled microwave absorption performance.

The sufficient interface contact in the composite absorbing material is beneficial to increase the dielectric loss and promote the microwave absorption performance. In this paper, the composite nanoparticles (NPs), Fe3O4 covered with ultra-thin carbon layer (Fe3O4/C), were synthesized by simple high temperature solution-phase and subsequent high-temperature steam carbonization methods. Small size Fe3O4/C composite NPs have large heterogeneous interfaces, which can control the polarization loss of composite NPs through the method of interface regulation and achieve high microwave absorption performance. The strongest reflection loss of the composite NPs with an average particle size of 52 nm can reach -58.5 dB at 14.88 GHz with a thickness of 2 mm, and the corresponding effective absorption (RL ≤ -10 dB) bandwidth (EAB) is 5.63 GHz (12.37-18 GHz). In particular, the high-efficiency absorption (RL ≤ -20 dB) bandwidth of Fe3O4/C can reach 15.44 GHz (2-17.44 GHz) with a thickness of 1.7-10 mm. The current method for controlling polarization loss provide a meaningful reference for future microwave absorption research.

Rational construction of porous N-doped Fe2O3 films on porous graphene foams by molecular layer deposition for tunable microwave absorption.

Graphene-based materials with porous microstructure have attracted immense attentions due to their wide application in microwave absorption. However, constructing magnetic film with both porous microstructure and uniform pore size by using traditional methods still remains a challenge. To overcome this problem, we reported a facile strategy of molecular layer deposition (MLD) for successfully fabrication of the hybrid-architecture of porous graphene foams and nitrogen-doped porous Fe2O3 films. The surfaces of porous graphene foams are uniformly covered by porous Fe2O3 films without aggregation and the pore structures are widely distributed. The porous graphene-based composites exhibit remarkably enhanced microwave absorption performance compared to the pristine graphene foams. The minimum reflection loss value is increased by approximately 8 times, reaching -64.36 dB with a thickness of only 2.18 mm. More importantly, the absorption property can be precisely modulated by tuning the MLD cycle numbers and effective absorption bandwidth covers 3.04-18.0 GHz by adjusting the thickness from 1.0 to 5.0 mm. This work provides new insights for exploring novel and high-performance graphene-based microwave absorbents and offers a new idea to rationally design three-dimensional composites with porous magnetic films.

Defining the Qualities of High-Quality Palladium on Carbon Catalysts for Hydrogenolysis.

Palladium-catalyzed hydrogenolysis is often the final step in challenging natural product total syntheses and a key step in industrial processes producing fine chemicals. Here, we demonstrate that there is wide variability in the efficiency of commercial sources of palladium on carbon (Pd/C) resulting in significant differences in selectivity, reaction times, and yields. We identified the physicochemical properties of efficient catalysts for hydrogenolysis: (1) small Pd/PdO particle size (2) homogeneous distribution of Pd/PdO on the carbon support, and (3) palladium oxidation state are good predictors of catalytic efficiency. Now chemists can identify and predict a catalyst's efficiency prior to the use of valuable synthetic material and time.

Hierarchical core-shell electrode with NiWO4 nanoparticles wrapped MnCo2O4 nanowire arrays on Ni foam for high-performance asymmetric supercapacitors.

Rational construction of MnCo2O4-based core-shell nanomaterials with distinctive and desirable architectures possesses great potential in the advanced electrode material of high-performance supercapacitors. Here, a new class of hierarchical core-shell nanowire arrays (NWAs) with a shell of NiWO4 nanoparticles and a core of MnCo2O4 nanowires is reported, which can significantly improve the electrochemical energy storage properties of supercapacitors. The unique core-shell structure endows the MnCo2O4@NiWO4 NWAs electrode with a high areal specific capacitance of 5.09 F cm-2 at a current density of 1 mA cm-2 and a superior cyclic retention of 96% after 5000 charge-discharge cycles, which are more preferable than those of MnCo2O4 NWAs electrode. More importantly, an aqueous electrochemical energy storage device (core-shell MnCo2O4@NiWO4 NWAs as the positive electrode and active carbon as the negative electrode, MnCo2O4@NiWO4//AC ASC) was assembled and shows a high energy density of 0.23 mWh cm-2 at a power density of 2.66 mW cm-2, and 0.09 mWh cm-2 at 16.00 mW cm-2, indicating hopeful potential for practical applications. This work highlights the significance of NiWO4 as a shell for hierarchical core-shell nanostructures, which can further improve the electron transport characteristic of the electrode material, thereby achieving performance breakthroughs in energy storage devices.

Amino-functionalized graphene oxide-supported networked Pd-Ag nanowires as highly efficient catalyst for reducing Cr(VI) in industrial effluent by formic acid.

Cr(VI) pollution in wastewater has increasingly become a global environmental problem owing to its acute toxicity. Herein, we present the one-pot procedure for preparing the amino-functionalized (-NH2) graphene oxide (GO-) supported networked Pd-Ag nanowires by co-reduction growth in polyol solution, which show the highly efficient catalytic performance with the excellent cycling stability for the catalytic Cr(VI) reduction by formic acid as an in-situ source of hydrogen at room temperature. The electron transfer from Ag and amino to Pd increases the electron density of Pd, which enhances the catalytic formic acid decomposition and subsequent the catalytic Cr(VI) reduction. The catalytic reduction rate constant of Pd3Ag1/GO-NH2 is determined to be 0.0768 min-1, which is much superior to the monometallic Pd/GO-NH2 and Pd3Ag1/GO. This study provides a novel strategy to develop catalysts for the catalytic reduction of Cr(VI) to Cr(III) in the industrial effluent using formic acid as an in-situ source of hydrogen.

Novel single excitation dual-emission carbon dots for colorimetric and ratiometric fluorescent dual mode detection of Cu2+ and Al3+ ions.

In this study, dual-emission carbon dots (D-CDs) are synthesized via a simple one-step solvothermal treatment of red tea. The obtained D-CDs are characterized by XPS, IR, TEM, XRD, fluorescence and UV-vis spectroscopy techniques. It is found that D-CDs present a strong red fluorescence emission peak at 671 nm and weak blue fluorescence emission peak at 478 nm under the excitation wavelength of 410 nm. The unique dual-emission properties of D-CDs provide great opportunities in ratiometric fluorescence sensing applications. The results show that Cu2+ ions can quench the fluorescence of the red emission band of D-CDs effectively, resulting in the disappearance of red fluorescence ultimately. Upon the addition of Al3+ ions, the fluorescence of blue emission band at 478 nm grows apparently, and the fluorescence color transforms gradually from red to orange, then to yellow-green. Based on these findings, a novel ratiometric fluorescence and colorimetric dual mode nanosensor is developed for simultaneous detection of Cu2+ and Al3+ ions. Regarding Cu2+ ions, the fluorescent detection linear range is 0.1-50 µM with detection limit of 0.1 µM, and the colorimetric detection limit is estimated as 25 µM. With regard to Al3+ ions, the fluorescent detection linear range is 0-20 µM and 25-100 µM with detection limit of 0.5 µM, and the colorimetric detection limit is 20 µM. Furthermore, the fluorescence response mechanisms of Cu2+ and Al3+ ions were discussed detailed. To the best of our current knowledge, this will be the first research work on the simultaneous determination of Cu2+ and Al3+ using D-CDs as fluorescent probes.

Fabrication, characterization, and magnetic properties of exchange-coupled porous BaFe8Al4O19/Co0.6Zn0.4Fe2O4 nanocomposite magnets.

Fabrication of exchange-coupled nanocomposite magnets has been considered to be the most effective method to achieve the high energy product for advanced permanent magnet applications. In this work, we report a facile auto-combustion synthesis to prepare porous exchange-coupled hard-soft ferrite-based magnetic BaFe8Al4O19-x wt% Co0.6Zn0.4Fe2O4 nanocomposites (where x = 10, 20, 30 and 40), which realize an effective exchange-coupled interaction when the x value is less than 30. Compared with BaFe8Al4O19, the optimized nanocomposite with 20% Co0.6Zn0.4Fe2O4 shows a 70.3% increase in Ms and a 60.4% enhancement in Mr and maintains a high Hc value of 8.8 kOe. The work demonstrates that the auto-combustion synthesis is a promising approach for the fabrication of high-performance ferrite-based permanent magnets.