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Phosphorus is widely present in living organisms and nature and exists in a variety of isomers with variable crystal structures. There are several common phosphorus monomers in biomedicine, including red phosphorus (RP), black phosphorus (BLK-P), violet phosphorus (VP), and blue phosphorus (BLU-P). Phosphorus-based semiconductor materials (PSCM) have adjustable band gaps, high photogenerated carrier mobility, and efficient photothermal conversion as well as good biocompatibility and degradability. In addition, phosphorus, an essential element for life-sustaining activities, is present in all cells of the human body, accounting for approximately 1% of the body's total weight. Therefore, phosphorus-based nanomaterials have extensive applications in the biomedical field. This review will clarify the classification, preparation methods, physicochemical properties, mechanisms of action, and applications in biomedicine of phosphorus-based nanomaterials while also offering new ideas for their development in biomedicine. [ABSTRACT FROM AUTHOR]

Core–shell layered double hydroxide microsphereswith tunable interior architecturehave been synthesized by a facile and cost-effective in situgrowth method. The SEM and TEM images revealed that the obtainedmicrospheres display a three-dimensional architecture with core–shell,yolk–shell, and hollow interior structure respectively, withcontinuous changes in specific surface area and pore-size distribution.Moreover, the hollow NiAl-LDH microspheres exhibit excellent pseudocapacitanceperformance, including high specific capacitance and rate capability,good charge/discharge stability and long-term cycling life, owingto the greatly improved faradaic redox reaction and mass transfer.Therefore, this work provides a promising approach for the designand synthesis of structure tunable materials with largely enhancedsupercapacitor behavior, which can be potentially applied in energystorage/conversion devices. [ABSTRACT FROM AUTHOR]

Electrocatalytic oxidation of glycerol (GLY; from a biodiesel byproduct) to lactic acid (LA; the key monomers for polylactic acid; PLA) is considered a sustainable approach for biomass waste upcycling and is coupled with cathodic hydrogen (H 2 ) production. However, current research still suffer from issues of low current density and low LA selectivity. Herein, we reported a photoassisted electrocatalytic strategy to achieve the selective oxidation of GLY to LA over a gold nanowire (Au NW) catalyst, attaining a high current density of 387 mA cm -2 at 0.95 V vs RHE, together with a high LA selectivity of 80%, outperforming most of the reported works in the literature. We reveal that the light-assistance strategy plays a dual role, which can both accelerate the reaction rate through the photothermal effect and also promote the adsorption of the middle hydroxyl of GLY over Au NWs to realize the selective oxidation of GLY to LA. As a proof-of-concept, we realized the direct conversion of crude GLY that was extracted from cooking oil to attain LA and coupled it with H 2 production using the developed photoassisted electrooxidation process, revealing the potential of this strategy in practical applications.

Electrocatalytic hydrogenation (ECH) of oxalic acid (OX) to produce glycolic acid (GA), an important building block of biodegradable polymers as well as application in various branches of chemistry, has attracted extensive attention in the industry, while it still encounters challenges of low reaction rate and selectivity. Herein, we reported a cation adsorption strategy to realize the efficient ECH of OX to GA by adsorbing Al 3+ ions on an anatase titanium dioxide (TiO 2 ) nanosheet array, achieving 2-fold enhanced GA productivity (1.3 vs 0.65 mmol cm -2 h -1 ) with higher Faradaic efficiency (FE) (85 vs 69%) at -0.74 V vs RHE. We reveal that the Al 3+ adatoms on TiO 2 both act as electrophilic adsorption sites to enhance the carbonyl (C═O) adsorption of OX and glyoxylic acid (intermediate) and also promote the generation of reactive hydrogen (H*) on TiO 2 , thus promoting the reaction rate. This strategy is demonstrated effective for different carboxylic acids. Furthermore, we realized the coproduction of GA at the bipolar of a H-type cell by pairing ECH of OX (at cathode) and electrooxidation of ethylene glycol (at anode), demonstrating an economical manner with maximum electron economy.

Photoelectrocatalytic (PEC) glycerol oxidation offers a sustainable approach to produce dihydroxyacetone (DHA) as a valuable chemical, which can find use in cosmetic, pharmaceutical industries, etc. However, it still suffers from the low selectivity (≤60%) that substantially limits the application. Here, we report the PEC oxidation of glycerol to DHA with a selectivity of 75.4% over a heterogeneous photoanode of Bi 2 O 3 nanoparticles on TiO 2 nanorod arrays (Bi 2 O 3 /TiO 2 ). The selectivity of DHA can be maintained at ∼65% under a relatively high conversion of glycerol (∼50%). The existing p-n junction between Bi 2 O 3 and TiO 2 promotes charge transfer and thus guarantees high photocurrent density. Experimental combined with theoretical studies reveal that Bi 2 O 3 prefers to interact with the middle hydroxyl of glycerol that facilitates the selective oxidation of glycerol to DHA. Comprehensive reaction mechanism studies suggest that the reaction follows two parallel pathways, including electrophilic OH* (major) and lattice oxygen (minor) oxidations. Finally, we designed a self-powered PEC system, achieving a DHA productivity of 1.04 mg cm -2 h -1 with >70% selectivity and a H 2 productivity of 0.32 mL cm -2 h -1 . This work may shed light on the potential of PEC strategy for biomass valorization toward value-added products via PEC anode surface engineering.

An efficient and controllable method to synthesize continuous metal-organic framework (MOF) films is highly desired. Herein, we demonstrate a facile and universal electrochemical method to synthesize homogeneous and uniform zeolitic imidazolate framework (ZIF, a typical class of MOF family) films on various macroconductive substrates (e.g., conductive glass, Ni foam and carbon cloth) as well as nanostructured substrates (one-dimensional nanorod array, two-dimensional nanowall array, and three-dimensional nanoframework). Particularly, the MOF film can be easily transformed into hierarchical ordered carbon nanotube networks, which display multifunctional electrocatalytic performances, such as excellent activity and good long-term stability in overall water splitting and oxygen reduction. It is worth mentioning that this is the first reported work for electrosynthesis of ZIF films on various conductive substrates, illustrating the great potential of the fast and economical method for constructing functional and integrated films or electrodes toward energy-related applications.

Transition metal oxides, such as Co 3 O 4 , have attracted great attention for lithium-ion batteries (LIBs) due to their high theoretical capacity and satisfactory chemical stability. However, the slow kinetics of Li-ion and electron transport as well as poor cycling stability still largely restrains their applications. Here, we report the rational design of well-defined mesoporous ultrathin Co 3 O 4 nanosheet arrays (NSAs) by topological transformation of layered double hydroxides nanosheet arrays (NSAs), which demonstrate significantly enhanced performance as anode for LIBs. The as-obtained Co 3 O 4 NSAs with suitable thickness and abundant mesopores show excellent electrochemistry performance for LIBs, giving a high specific charge capacity of 2019.6 mAh g -1 at 0.1 A g -1 , a good rate capability, and a remarkable cycling stability (1576.9 mAh g -1 after the 80th cycle), which is much superior to that of Co 3 O 4 with thicker or thinner nanosheets as well as to that of the reported results. This facile strategy may be extended to the synthesis of other transition metal oxide NSAs, which can be potentially used in energy storage and conversion devices., Competing Interests: The authors declare no competing financial interest.

The exploitation of highly efficiency and low-cost electrocatalysts toward oxygen evolution reaction (OER) is a meaningful route in renewable energy technologies including solar fuel and water splitting. Herein, NiFe-layered double hydroxide (NiFe-LDH) hollow microsphere (HMS) was designed and synthesized via a one-step in situ growth method by using SiO 2 as a sacrificial template. Benefiting from the unique architecture, NiFe-LDH HMS shows highly efficient OER electrocatalytic activity with a preferable current density (71.69 mA cm -2 at η = 300 mV) and a small onset overpotential (239 mV at 10 mA cm -2 ), which outperforms the 20 wt % commercial Ir/C catalyst. Moreover, it exhibits a remarkably low Tafel slope (53 mV dec -1 ) as well as a satisfactory long-time stability. Electrochemical studies reveal that this hierarchical structure facilitates a full exposure of active sites and facile ion transport kinetics, accounting for the excellent performance. It is expected that the NiFe-LDH microsphere material can serve as a promising non-noble-metal-based electrocatalyst toward water oxidation reaction.

Three-component microspheres containing an SiO(2)-coated Fe(3)O(4) magnetite core and a layered double hydroxide (LDH) nanoplatelet shell have been synthesized via an in situ growth method. The resulting Fe(3)O(4)@SiO(2)@NiAl-LDH microspheres display three-dimensional core-shell architecture with flowerlike morphology, large surface area (83 m(2)/g), and uniform mesochannels (4.3 nm). The Ni(2+) cations in the NiAl-LDH shell provide docking sites for histidine and the materials exhibit excellent performance in the separation of a histidine (His)-tagged green fluorescent protein, with a binding capacity as high as 239 μg/mg. The microspheres show highly selective adsorption of the His-tagged protein from Escherichia coli lysate, demonstrating their practical applicability. Moreover, the microspheres possess superparamagnetism and high saturation magnetization (36.8 emu/g), which allows them to be easily separated from solution by means of an external magnetic field and subsequently reused. The high stability and selectivity of the Fe(3)O(4)@SiO(2)@NiAl-LDH microspheres for the His-tagged protein were retained over several separation cycles. Therefore, this work provides a promising approach for the design and synthesis of multifunctional LDH microspheres, which can be used for the practical purification of recombinant proteins, as well as having other potential applications in a variety of biomedical fields including drug delivery and biosensors., (© 2011 American Chemical Society)

The ordered ultrathin films (UTFs) based on CoFe-LDH (layered double hydroxide) nanoplatelets and manganese porphyrin (Mn-TPPS) have been fabricated on ITO substrates via a magnetic-field-assisted (MFA) layer-by-layer (LBL) method and were demonstrated as an electrochemical sensor for glucose. The XRD pattern for the film indicates a long-range stacking order in the normal direction of the substrate. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) images of the MFA LDH/Mn-TPPS UTFs reveal a continuous and uniform surface morphology. Cyclic voltammetry, impedance spectroscopy, and chronoamperometry were used to evaluate the electrochemical performance of the film, and the results show that the MFA-0.5 (0.5 T magnetic field) CoFe-LDH/Mn-TPPS-modified electrode displays the strongest redox current peaks and fastest electron transfer process compared with those of MFA-0 (without magnetic-field) and MFA-0.15 (0.15 T magnetic field). Furthermore, the MFA-0.5 CoFe-LDH/Mn-TPPS exhibits remarkable electrocatalytic activity toward the oxidation of glucose with a linear response range (0.1-15 mM; R(2) = 0.999), low detection limit (0.79 μM) and high sensitivity (66.3 μA mM(-1) cm(-2)). In addition, the glucose sensor prepared by the MFA LBL method also shows good selectivity and reproducibility as well as resistance to poisoning in a chloride ion solution. Therefore, the novel strategy in this work creates new opportunities for the fabrication of nonenzyme sensors with prospective applications in practical detection., (© 2011 American Chemical Society)