Electronic Engineering of Crystalline/Amorphous CoP/FeCoPx Nanoarrays for Efficient Water Electrolysis.

The development of bifunctional, non-noble metal-based electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) through morphology and electronic engineering is highly attractive for efficient water splitting. Herein, hierarchical nanoarrays consisting of crystalline cobalt phosphide nanorods covered by amorphous Fe-doped cobalt phosphide nanocuboids (CoP/FeCoPx) are constructed as bifunctional catalysts for both HER and OER. Experimental results and theoretical calculations reveal that the catalysts exhibit balanced dual-catalytic properties due to simultaneous introduction of Fe doping and phosphorus vacancies, leading to an optimized electronic structure of the CoP/FeCoPx. Furthermore, the hierarchical nanoarrays made of crystalline/amorphous heterostructures significantly enhance the performance of the electrocatalysts. As a result, the CoP/FeCoPx catalyst demonstrates remarkable performance in both HER and OER, with overpotentials of 74 and 237 mV at 10 mA cm-2 in 1 m KOH, respectively, as well as a low cell voltage of 1.53 V at 10 mA cm-2 for alkaline overall water splitting. This work integrates the morphology engineering involving design of hierarchical crystalline/amorphous nanoarrays and the electronic engineering through Fe doping and phosphorus vacancies for efficient water electrolysis. It may open a new route toward rational design and feasible fabrication of high-performance, multifunctional, non-noble metal-based electrocatalysts for energy conversion.

Tethering Cobalt Ions to BiVO4 Surface via Robust Organic Bifunctional Linker for Efficient Photoelectrochemical Water Splitting.

In the quest for efficient and stable oxygen evolution catalysts (OECs) for photoelectrochemical water splitting, the surface modification of BiVO4 is a crucial step. In this study, a novel and robust OEC, based on 3-(bis(pyridin-2-ylmethyl) amino) propanoic acid bifunctional linker known as dipicolyl alanine acid (DPAA) and cobalt ions, is prepared and fully characterized. The DPAA is anchored to the surface of BiVO4 and utilized to tether cobalt ions. The Co-DPAA/BiVO4 photoanode exhibits remarkable stability and efficiency toward photoelectrochemical water oxidation. Specifically, it showed anodic photocurrent increase of 7.1, 5.0, 3.0, and 1.3-fold at 1.23 VRHE as compared to pristine BiVO4, DPAA/BiVO4, Co-BiVO4, and Co-Pi/BiVO4 photoanodes, respectively. The photoelectrochemical and IMPS studies revealed that the Co-DPAA/BiVO4 photoanode exhibits a longer transient decay time for surface-trapped holes, higher charge transfer kinetics, and charge separation efficiency compared to Co-Pi/BiVO4 and pristine BiVO4 photoelectrodes. This indicates that the Co-DPAA effectively reduces surface recombination and facilitates charge transfer. Moreover, at 1.23 VRHE, the Co-DPAA/BiVO4 photoanode achieved a faradic efficiency of 92% for oxygen evolution reaction and could retain a turnover frequency of 3.65 s-1. The- exhibited effeciency is  higher than most of the efficient molecular oxygen evolution catalyst based on Ru.

Interfacial coupling of Ce-CoSe2 nanoneedle arrays with MXene for efficient overall water splitting.

Designing highly effective, low-cost bifunctional electrocatalysts without noble metals for overall water splitting remains a significant challenge. In this work, interfacial coupling of Ce-doped CoSe2 nanoneedle arrays with MXene (Ce-CoSe2/MXene) is developed via the facile hydrothermal and selenization methods. The extensive specific surface area and favorable hydrophilicity of Ti3AlC2, combined with the optimized electronic structure and abundant active sites from Ce-doping and selenization, contribute to the exceptional bifunctional electrocatalytic performance of the Ce-CoSe2/MXene electrode. Specifically, this heterostructure achieves a low hydrogen evolution reaction (HER) overpotential of 34 mV at 10 mA cm-2, an oxygen evolution reaction (OER) overpotential of 279 mV at 100 mA cm-2, and an overall water splitting (OWS) potential as low as 1.45 V at 10 mA cm-2. In-situ Raman spectroscopy reveals that surface reconstruction would improve catalytic activity and stability. Theoretical calculations indicate that the Ce-CoSe2/MXene can improve the adsorption of intermediates and facilitate HER/OER process by lowering the kinetic barrier, thereby enhancing electrocatalytic activity. This research marks a substantial advancement in the development of low-cost, efficient electrocatalysts for overall water splitting.

Superhydrophilic and Underwater Superaerophobic Dual-Function Peony-Shaped Selenide Micro-nano Array Self-Supported Electrodes for High-Efficiency Overall Water Splitting Driven by Renewable Energy.

With the intensification of global environmental pollution and resource scarcity, hydrogen has garnered significant attention as an ideal alternative to fossil fuels due to its high energy density and nonpolluting nature. Consequently, the urgent development of electrocatalytic water-splitting electrodes for hydrogen production is imperative. In this study, a superwetting selenide catalytic electrode with a peony-flower-shaped micronano array (MoS2/Co0.8Fe0.2Se2/NixSey/nickel foam (NF)) was synthesized on NF via a two-step hydrothermal method. The optimal catalytic activity of cobalt-iron selenide was achieved by adjusting the Co/Fe ratio. The intrinsic catalytic activity of the electrodes was enhanced by incorporating transition metal selenides, which then served as a precursor for the subsequent loading of MoS2 nanoflowers on the surface to fully expose the active sites. Furthermore, the superwetting properties of the electrode accelerated electrolyte penetration and electron/mass transfer, while also facilitating bubble detachment from the electrode surface, thereby preventing "bubble shielding effect". This resulted in superior oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performance, as well as overall water splitting capabilities. In a 1.0 M KOH solution, the electrode required only 166 and 195 mV overpotential to achieve a current density of 10 mA cm-2 for OER and HER, respectively. When functioning as a bifunctional catalytic electrode, only 1.60 V of voltage was necessary to drive the electrolyzer to reach a current density of 10 mA cm-2. Moreover, laboratory simulations of wind and solar energy-driven water splitting validated the feasibility of establishing a sustainable energy-to-hydrogen production chain. This work provides new insights into the preparation of low-overpotential, high-catalytic-activity superhydrophilic and underwater superaerophobic catalytic electrodes by rationally adjusting elemental ratios and exploring changes in electrode surface wettability.

Rapid Synthesis of Ruthenium-Copper Nanocomposites as High-Performance Bifunctional Electrocatalysts for Electrochemical Water Splitting.

Development of high-performance, low-cost catalysts for electrochemical water splitting is key to sustainable hydrogen production. Herein, ultrafast synthesis of carbon-supported ruthenium-copper (RuCu/C) nanocomposites is reported by magnetic induction heating, where the rapid Joule's heating of RuCl3 and CuCl2 at 200 A for 10 s produces Ru-Cl residues-decorated Ru nanocrystals dispersed on a CuClx scaffold, featuring effective Ru to Cu charge transfer. Among the series, the RuCu/C-3 sample exhibits the best activity in 1 m KOH toward both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), with an overpotential of only -23 and +270 mV to reach 10 mA cm-2, respectively. When RuCu/C-3 is used as bifunctional catalysts for electrochemical water splitting, a low cell voltage of 1.53 V is needed to produce 10 mA cm-2, markedly better than that with a mixture of commercial Pt/C+RuO2 (1.59 V). In situ X-ray absorption spectroscopy measurements show that the bifunctional activity is due to reduction of the Ru-Cl residues at low electrode potentials that enriches metallic Ru and oxidation at high electrode potentials that facilitates the formation of amorphous RuOx. These findings highlight the unique potential of MIH in the ultrafast synthesis of high-performance catalysts for electrochemical water splitting.

Green H2 Generation from Seawater Deploying a Bifunctional Hetero-Interfaced CoS2-CoFe-Layered Double Hydroxide in an Electrolyzer.

This work illustrates the practicality and economic benefits of employing a hetero-interfaced electrocatalyst (CoS2@CoFe-LDH), containing cobalt sulphide and iron-cobalt double-layer hydroxide for large-scale hydrogen generation. Here, the rational synthesis and detailed characterization of the CoS2@CoFe-LDH material to unravel its unique heterostructure are essayed. The CoS2@CoFe-LDH operates as a bifunctional electrocatalyst to trigger both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in alkaline seawater (pH 14.0) while showcasing low overpotential requirement for HER (311 mV) and OER (450 mV) at 100 mA cm- 2 current density. The identical CoS2@CoFe-LDH on either electrode in an H-cell setup results in simultaneous H2 and O2 production from seawater with a ≈98% Faradaic efficiency with an applied potential of 1.96V@100 mA cm- 2. Next, this CoS2@CoFe-LDH catalyst is deployed on both sides of a membrane electrode assembly in a one-stack electrolyzer, which retains the intrinsic bifunctional reactivity of the catalyst to generate H2 and O2 in tandem from alkaline seawater with an impeccable energy efficiency (50 kWh kg-1-of-H2). This electrolyzer assembly can be directly linked with a Si-solar cell to produce truly green hydrogen with a solar-to-hydrogen generation efficiency of 15.88%, highlighting the potential of this converting seawater to hydrogen under solar irradiation.

Molybdenum and Vanadium-Codoped Cobalt Carbonate Nanosheets Deposited on Nickel Foam as a High-Efficient Bifunctional Catalyst for Overall Alkaline Water Splitting.

To address issues of global energy sustainability, it is essential to develop highly efficient bifunctional transition metal-based electrocatalysts to accelerate the kinetics of both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Herein, the heterogeneous molybdenum and vanadium codoped cobalt carbonate nanosheets loaded on nickel foam (VMoCoCOx@NF) are fabricated by facile hydrothermal deposition. Firstly, the mole ratio of V/Mo/Co in the composite is optimized by response surface methodology (RSM). When the optimized composite serves as a bifunctional catalyst, the water-splitting current density achieves 10 mA cm-2 and 100 mA cm-2 at cell voltages of 1.54 V and 1.61 V in a 1.0 M KOH electrolyte with robust stability. Furthermore, characterization is carried out using field emission scanning electron microscopy-energy dispersive spectroscopy (FESEM-EDS), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Density functional theory (DFT) calculations reveal that the fabricated VMoCoCOx@NF catalyst synergistically decreases the Gibbs free energy of hydrogen and oxygen-containing intermediates, thus accelerating OER/HER catalytic kinetics. Benefiting from the concerted advantages of porous NF substrates and clustered VMoCoCOx nanosheets, the fabricated catalyst exhibits superior electrocatalytic performance. This work presents a novel approach to developing transition metal catalysts for overall water splitting.

Oxygen-Vacancy-Induced Enhancement of BiVO4 Bifunctional Photoelectrochemical Activity for Overall Water Splitting.

Hydrogen generation via photoelectrochemical (PEC) overall water splitting is an attractive means of renewable energy production so developing and designing the cost-effective and high-activity bifunctional PEC catalysts both for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) has been focused on. Based on first-principles calculations, we propose a feasible strategy to enhance either HER or OER performance in the monoclinic exposed BiVO4 (110) facet by the introduction of oxygen vacancies (Ovacs). Our results show that oxygen vacancies induce charge rearrangements, which enhances charge transfer between active sites and adatoms. Furthermore, the incorporation of oxygen vacancies reduces the work function of the system, which makes charge transfer from the inner to the surface more easily; thus, the charges possess stronger redox capacity. As a result, the Ovac reduces both the hydrogen adsorption-free energy (ΔGH*) for the HER and the overpotential for the OER, facilitating the PEC activity of overall water splitting. The findings provide not only a method to develop bifunctional PEC catalysts based on BiVO4 but also insight into the mechanism of enhanced catalytic performance.

Facilitating charge transfer via a Semi-Coherent Fe(PO3)2-Co2P2O7 heterointerface for highly efficient Zn-Air batteries.

Developing reversible oxygen electrodes for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is crucial for achieving high-performance rechargeable Zn-air batteries (ZABs). This study introduced an nitrogen-doped carbon confined with a semi-coherent Fe(PO3)2-Co2P2O7 heterojunction for bifunctional oxygen electrocatalysis. This nanocomposite yielded an ORR half-wave potential of 0.908 V and an OER overpotential of 291 mV at 10 mA/cm2. ZABs incorporating this catalyst yielded impressive performance, including a peak power density of 203 mW/cm2, a specific capacity of 737 mAh/gZn, and promoted stability. Both experimental and theoretical simulations demonstrated that the unique electric field between Fe(PO3)2 and Co2P2O7 promoted efficient charge transport across the heterointerface. This interaction likely modulated the d-band center of the heterojunction, expedite the desorption of oxygen intermediates, thus improving oxygen catalysis and, consequently, ZAB performance. This work illustrates a significant design principle for creating efficient bifunctional catalysts in energy conversion technologies.

Construction of Molecularly Dispersed Polyoxometalate-Alumina Hybrid Hollow Nanoflowers via Water-Induced Kirkendall Effect.

Hybrid nanomaterials with controllable structures and diverting components have attracted significant interest in the functional materials field. Here, we develop a solvent evaporation-induced self-assembly (EISA) strategy to synthesize nanosheet-assembled phosphomolybdic acid (H3PMo)-alumina hybrid hollow spheres. The resulting nanoflowers display a high surface area (up to 697 m2 g-1), adjustable diameter, high chemical/thermal stability, and especially molecularly dispersed H3PMo species. By employing various microscopic and spectroscopic techniques, the formation mechanism is elucidated, revealing the simultaneous control of the morphology by heteropoly acids and water through the water-induced Kirkendall effect. The versatility of the synthesis method is demonstrated by varying surfactants, heteropoly acids, and metal oxide precursors for the facile synthesis of hybrid metal oxides. Spherical hybrid alumina serves as an attractive support material for constructing metal-acid bifunctional catalysts owing to its advantageous surface area, acidity, and mesoporous microenvironment. Pt-loaded hollow flowers exhibit excellent catalytic performance and exceptional stability in the hydrodeoxygenation of vanillin with recyclability for up to 10 cycles. This research presents an innovative strategy for the controllable synthesis of hybrid metal oxide nanospheres and hollow nanoflowers, providing a multifunctional platform for diverse applications.

Radiosynthesis and preclinical evaluation of a 68Ga-labeled tetrahydroisoquinoline-based ligand for PET imaging of C-X-C chemokine receptor type 4 in an animal model of glioblastoma.

BACKGROUND: This study aimed to develop a novel positron emission tomography (PET) tracer, [68Ga]Ga-TD-01, for CXCR4 imaging. To achieve this goal, the molecular scaffold of TIQ15 was tuned by conjugation with the DOTA chelator to make it suitable for 68Ga radiolabeling. METHODS: A bifunctional chelator was prepared by conjugating the amine group of TIQ15 with p-NCS-Bz-DOTA, yielding TD-01, with a high yield (68.92%). TD-01 was then radiolabeled with 68Ga using 0.1 M ammonium acetate at 60 °C for 10 min. A 1-h dynamic small animal PET/MRI study of the labeled compound in GL261-luc2 tumor-bearing mice was performed, and brain tumor uptake was assessed. Blocking studies involved pre-administration of TIQ15 (10 mg/kg) 10 min before the PET procedure started. RESULTS: [68Ga]Ga-TD-01 exhibited a radiochemical yield (RCY) of 36.33 ± 1.50% (EOS), with a radiochemical purity > 99% and a molar activity of 55.79 ± 1.96 GBq/µmol (EOS). The radiotracer showed in vitro stability in PBS and human plasma for over 4 h. Biodistribution studies in healthy animals revealed favorable kinetics for subsequent PET pharmacokinetic modeling with low uptake in the brain and moderate uptake in lungs, intestines and spleen. Elimination could be assigned to a renal-hepatic pathway as showed by high uptake in kidneys, liver, and urinary bladder. Importantly, [68Ga]Ga-TD-01 uptake in glioblastoma (GBM)-bearing mice significantly decreased upon competition with TIQ15, with a baseline tumor-to-background ratios > 2.5 (20 min p.i.), indicating high specificity. CONCLUSION: The newly developed CXCR4 PET tracer, [68Ga]Ga-TD-01, exhibited a high binding inhibition for CXCR4, excellent in vitro stability, and favorable pharmacokinetics, suggesting that the compound is a promising candidate for full in vivo characterization of CXCR4 expression in GBM, with potential for further development as a tool in cancer diagnosis.

Photoinduced Single Electron Reduction of the 4-O-5 Linkage in Lignin Models for C-P Coupling Catalyzed by Bifunctional N-Heterocyclic Carbenes.

Catalytic activation of Caryl-O bonds is considered as a powerful strategy for the production of aromatics from lignin. However, due to the high reduction potentials of diaryl ether 4-O-5 linkage models, their single electron reduction remains a daunting challenge. This study presents the blue light-induced bifunctional N-heterocyclic carbene (NHC)-catalyzed one-electron reduction of diaryl ether 4-O-5 linkage models for the synthesis of trivalent phosphines. The H-bond between the newly devised bifunctional NHC and diaryl ethers is responsible for the success of the single electron transfer. Furthermore, this approach demonstrates selective one-electron reduction of unsymmetric diaryl ethers, oligomeric phenylene oxide, and lignin model.

Se vacancies and interface engineering modulated bifunctionality prussian blue analogue derivatives for overall water splitting.

It is a challenging task to design and synthesize stable, and high-performance non-precious metals bifunctional catalysts for water-splitting. Herein, the coupling between Se vacancy and interface engineering is highlighted to synthesize a unique CoFeSe hollow nanocubes structure on MXene-modified nickel foam (NF) by in-situ phase transition from bifunctionality prussian blue analogue (PBA) derivatives (VSe-CoFeSe@MXene/NF). DFT theory reveals that the Se vacancy and interface engineering modulate the surface electronic structure and optimize the surface adsorption energy of the intermediates. Experimental data also confirm that the as-prepared CoFeSe@MF catalyst exhibits advanced electrocatalytic properties, 283 mV (OER) and 67 mV (HER) are required to drive the current density of 10 mA cm-2. Notably, it is assembled into a two-electrode system for integral water decomposition, which only requires a low cell potential of 1.57 V at current of 10 mA cm-2, together with excellent durability for 48 h. The strategy is expected to provide a new direction for the design and construction of highly efficient collaborative integrated water decomposition electrocatalysts.

Promoting Electrocatalytic Oxygen Reactions Using Advanced Heterostructures for Rechargeable Zinc-Air Battery Applications.

In order to facilitate electrochemical oxygen reactions in electrically rechargeable zinc-air batteries (ZABs), there is a need to develop innovative approaches for efficient oxygen electrocatalysts. Due to their reliability, high energy density, material abundance, and ecofriendliness, rechargeable ZABs hold promise as next-generation energy storage and conversion devices. However, the large-scale application of ZABs is currently hindered by the slow kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). However, the development of heterostructure-based electrocatalysts has the potential to surpass the limitations imposed by the intrinsic properties of a single material. This Account begins with an explanation of the configurations of ZABs and the fundamentals of the oxygen electrochemistry of the air electrode. Then, we summarize recent progress with respect to the variety of heterostructures that exploit bifunctional electrocatalytic reactions and overview their impact on ZAB performance. The range of heterointerfacial engineering strategies for improving the ORR/OER and ZAB performance includes tailoring the surface chemistry, dimensionality of catalysts, interfacial charge transfer, mass and charge transport, and morphology. We highlight the multicomponent design approaches that take these features into account to create advanced highly active bifunctional catalysts. Finally, we discuss the challenges and future perspectives on this important topic that aim to enhance the bifunctional activity and performance of zinc-air batteries.

Dual excitation channel ratiometric fluorescent probes for visual and fluorescent detection of anthrax spore biomarker and tetracycline hydrochloride.

Long-term and excessive use of tetracycline hydrochloride (TC) can lead to its accumulation in the environment, which can cause water contamination, bacterial resistance, and food safety problems. 2,6-Pyridine dicarboxylic acid (DPA) is a major biomarker of Bacillus anthracis spores, and its rapid and sensitive detection is of great significance for disease prevention and counter-terrorism. A bifunctional ratiometric fluorescent nanoprobe has been fabricated to detect DPA and TC. 3,5-dicarboxyphenylboronic acid (BOP) was intercalated into layered europium hydroxide (LEuH) by the ion-exchange method and exfoliated into nanosheets as a fluorescent nanoprobe (PNP). DPA and TC could significantly enhance the red fluorescence of Eu3+ through the antenna effect under different excitation wavelengths, while the fluorescence of BOP can be used as a reference based on the constant emission intensity, realizing ratiometric detection. A low limit of detection (LOD) for the target (DPA: 9.7 nM, TC: 21.9 nM) can be achieved. In addition, visual detection of DPA and TC was realized using color recognition software based on the obvious color changes. This is the first ratiometric fluorescent nanoprobe based on layered rare-earth hydroxide (LRH) for the detection of DPA and TC simultaneously, which opens new ideas in the design of multifunctional probes.

Bifunctional Role of High-Entropy Selenides in Accelerating Redox Conversion and Modulating Lithium Plating towards Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries, recognized as one of the most promising next-generation energy storage systems, are still limited by the "shuttle effect" of soluble polysulfides (LiPSs) on the cathode and the uncontrolled growth of lithium dendrites on the anode. These issues are critical obstacles to their practical application. Currently, many researchers have addressed these challenges from a unilateral perspective. Herein, we propose bifunctional hosts based on high-entropy selenides (HE-Se) to simultaneously tackle the persistent problems on both the positive and negative electrodes of Li-S batteries. On the one hand, HE-Se interacts with polysulfides to promote their conversion, effectively mitigating the shuttle effect. On the other hand, HE-Se provides multiple lithophilic sites during the initial nucleation of Li+, which reduces overpotential and exhibits excellent lithophilicity and cyclic stability. As a result, Li-S batteries incorporating the HE-Se host demonstrate outstanding performance in terms of rate capability and cycling stability. Additionally, the porous lithophilic HE-Se structure offers sufficient nucleation sites, inhibits the growth of dendritic lithium, and accommodates volume changes during charging and discharging cycles. This study highlights the potential of sulphophilic/lithophilic high-entropy materials in designing advanced Li-S batteries and encourages further exploration in this area.

Synergy of atomic hydrogen reduction and reactive oxygen species oxidation over confined Mn bifunctional site for electrocatalytic deep mineralization.

Traditional reduction or oxidation processes generating one-component free radicals face challenges in deep dechlorination and mineralization of chlorophenols from wastewater. Herein, an efficient electrocatalytic process has been developed, which couples atomic H* reduction with reactive oxidation species (•OH and 1O2) oxidation on a bifunctional cathode for 4 -chlorophenol (4 -CP) removal. The N - doped carbon nanotubes encapsulated manganese nanoparticles was fabricated as cathode, which could generate atomic H* , initiating nucleophilic hydrodechlorination in presence of confined MnO sites. Subsequently, electrophilic oxidation by generating mainly 1O2 on confined Mn7C3 sites and •OH on confined MnO sites, facilitating the oxidative processes. Experimental results and theory calculations demonstrated that reductive dechlorination and oxidative mineralization processes could mutually promote each other, resulting in an enhancement factor of 2.90. At pH 7, this process achieved 100 % removal for 4 -CP, 84 % dechlorination, 76 % total organic carbon (TOC) removal and low energy consumption (0.76 kWh g-1TOC) within 120 min. Notably, TOC for chlorophenols containing Cl substituents at different positions and real lake water containing 4 -CP could be almost completely removed. This research establishes confined non-noble bifunctional active sites that synergistically enhance reductive dechlorination and oxidative degradation processes, holding significant treatment potential for application in deep mineralization of organochlorine from water/wastewater.

Rational Construction of Honeycomb-like Carbon Network-Encapsulated MoSe2 Nanocrystals as Bifunctional Catalysts for Highly Efficient Water Splitting.

The scalable fabrication of cost-efficient bifunctional catalysts with enhanced hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performance plays a significant role in overall water splitting in hydrogen production fields. MoSe2 is considered to be one of the most promising candidates because of its low cost and high catalytic activity. Herein, hierarchical nitrogen-doped carbon networks were constructed to enhance the catalytic activity of the MoSe2-based materials by scalable free-drying combined with an in situ selenization strategy. The rationally designed carbonaceous network-encapsulated MoSe2 composite (MoSe2/NC) endows a continuous honeycomb-like structure. When utilized as a bifunctional electrocatalyst for both HER and OER, the MoSe2/NC electrode exhibits excellent electrochemical performance. Significantly, the MoSe2/NC‖MoSe2/NC cells require a mere 1.5 V to reach a current density of 10 mA cm-2 for overall water splitting in 1 M KOH. Ex situ characterizations and electrochemical kinetic analysis reveal that the superior catalytic performance of the MoSe2/NC composite is mainly attributed to fast electron and ion transportation and good structural stability, which is derived from the abundant active sites and excellent structural flexibility of the honeycomb-like carbon network. This work offers a promising pathway to the scalable fabrication of advanced non-noble bifunctional electrodes for highly efficient hydrogen evolution.

Preparation of Functionalized Ethylene-Vinyl-Alcohol Nanofibrous Membrane Filter for Rapid and Cyclic Removing of Organic Dye from Aqueous Solution.

A functionalized ethylene-vinyl-alcohol (EVOH) nanofibrous membrane (NFM) was fabricated via co-electrospinning H4SiW12O40 (SiW12) and EVOH first, and then grafting citric acid (CCA) on the electrospun SiW12@EVOH NFM. Characterization with FT-IR, EDX, and XPS confirmed that CCA was introduced to the surface of SiW12@EVOH NFM and the Keggin structure of SiW12 was maintained well in the composite fibers. Due to a number of carboxyl groups introduced by CCA, the as-prepared SiW12@EVOH-CCA NFM can form a high number of hydrogen bonds with CR, and thus can be used to selectively absorb congo red (CR) in aqueous solutions. More importantly, the CR enriched in the NFM can be rapidly degraded via photocatalysis. SiW12 in the NFM acted as a photocatalyst, and the hydroxyl groups in the NFM acted as an electron donor to accelerate the photodegradation rate of CR. Meanwhile, the SiW12@EVOH-CCA NFM was regenerated and then exhibited a relatively stable adsorption capacity in five cycles of filtration-regeneration. The bifunctional nanofibrous membrane filter showed potential for use in the thorough purification of dye wastewater.

Development of 52Mn Labeled Trastuzumab for Extended Time Point PET Imaging of HER2.

PURPOSE: Due to their long circulation time in the blood, monoclonal antibodies (mAbs) such as trastuzumab, are usually radiolabeled with long-lived positron emitters for the development of agents for Positron Emission Tomography (PET) imaging. Manganese-52 (52Mn, t1/2 = 5.6 d, ß+ = 29.6%, E(ßave) = 242 keV) is suitable for imaging at longer time points providing a complementary technique to Zirconium-89 (89Zr, t1/2 = 3.3 d, ß+ = 22.7%, E(ßave) = 396 keV)) because of its long half-life and low positron energy. To exploit these properties, we aimed to investigate suitable bifunctional chelators that could be readily conjugated to antibodies and labeled with 52Mn under mild conditions using trastuzumab as a proof-of-concept. PROCEDURES: Trastuzumab was incubated with S-2-(4-isothiocyanatobenzyl)-1,4,7,10-tetraazacyclododecane tetraacetic acid (p-SCN-Bn-DOTA), 1-Oxa-4,7,10-tetraazacyclododecane-5-S-(4-isothiocyantobenzyl)-4,7,10-triacetic acid (p-SCN-Bn-Oxo-DO3A), and 3,6,9,15-tetraazabicyclo[9.3.1] pentadeca-1(15),11,13-triene-4-S-(4-isothiocyanatobenzyl)-3,6,9-triacetic acid (p-SCN-Bn-PCTA) at a tenfold molar excess. The immunoconjugates were purified, combined with [52Mn]MnCl2 at different ratios, and the labeling efficiency was assessed by iTLC. The immunoreactive fraction of the radiocomplex was determined through a Lindmo assay. Cell studies were conducted in HER2 + (BT474) and HER2- (MDA-MB-468) cell lines followed by in vivo studies. RESULTS: Trastuzumab-Oxo-DO3A was labeled within 30 min at 37 °C with a radiochemical yield (RCY) of 90 ± 1.5% and with the highest specific activity of the chelators investigated of 16.64 MBq/nmol. The labeled compound was purified with a resulting radiochemical purity of > 98% and retained a 67 ± 1.2% immunoreactivity. DOTA and PCTA immunoconjugates resulted in < 50 ± 2.5% (RCY) with similar specific activity. Mouse serum stability studies of [52Mn]Mn-Oxo-DO3A-trastuzumab showed 95% intact complex for over 5 days. Cell uptake studies showed higher uptake in HER2 + (12.51 ± 0.83% /mg) cells compared to HER2- (0.85 ± 0.10%/mg) cells. PET images of mice bearing BT474 tumors showed high tumor uptake that was consistent with the biodistribution (42.02 ± 2.16%ID/g, 14 d) compared to MDA-MB-468 tumors (2.20 ± 0.80%ID/g, 14 d). Additionally, both models exhibited low bone uptake of < 1% ID/g. CONCLUSION: The bifunctional chelator p-SCN-Bn-Oxo-DO3A is promising for the development of 52Mn radiopharmaceuticals as it was easily conjugated, radiolabeled at mild conditions, and illustrated stability for a prolonged duration both in vitro and in vivo. High-quality PET/CT images of [52Mn]Mn-Oxo-DO3A-trastuzumab were obtained 14 d post-injection. This study illustrates the potential of [52Mn]Mn-Oxo-DO3A for the evaluation of antibodies using PET imaging.