Synthesis of Solvent-Mediated Morphology-Controlled PdSn Alloy Nanocatalysts and their Application in Electrocatalysis of Ethylene Glycol and Ethanol.

2D nanodendrites (NDs) and nanosheets (NSs) have been regarded as efficient nanocatalysts for enhancing the electrocatalytic performance due to their low coordinated sites and abundant electrocatalytic centers. Nevertheless, it remains challenging to construct advanced NDs and NSs in a single reaction system. Herein, by tuning the volume ratios of mixed solvents, the reduction and diffusion rate of Sn2+ on Pd NSs template was rationally controlled to prepare PdSn NDs and PdSn NSs. Ascribed to the open 2D nanostructure, high specific surface area, and robust synergistic effect, the as-prepared PdSn NDs and PdSn NSs exhibited distinguished electrocatalytic activities for ethylene glycol oxidation reaction (EGOR) and ethanol oxidation reaction (EOR), as well as commendable electrocatalytic durability, which were far superior to the Pd NSs and commercial Pd/C. In addition, the PdSn NDs exhibited enhanced reaction kinetics because the characteristic branch structure exposed a high density of active sites. This work may provide significant guidance for preparing excellent nanocatalysts with various morphological features by simply optimizing the content of the coexisting solvents.

In Situ Electrodeposition of Ultralow Pt into NiFe-Metal-Organic Framework/Nickel Foam Nanosheet Arrays as a Bifunctional Catalyst for Overall Water Splitting.

Exploring highly effective bifunctional electrocatalysts with surface structural advantages and synergistic optimization effects among multimetals is greatly important for overall water splitting. Herein, we successfully synthesized Pt-loaded NiFe-metal-organic framework nanosheet arrays grown on nickel foam (Pt-NiFe-MOF/NF) via a facile hydrothermal-electrodeposition process. Benefiting from large exposed specific surface, optimal electrical conductivity and efficient metal-support interaction endow Pt-NiFe-MOF/NF with highly catalytic performance, exhibiting small overpotential of 261 mV toward oxygen evolution reaction and 125 mV toward hydrogen evolution reaction at a current density of 100 mA cm-2 in alkaline medium. More significantly, the assembled water electrolyzer comprising the Pt-NiFe-MOF/NF//Pt-NiFe-MOF/NF couple demands a low cell voltage of 1.45 V to reach 10 mA cm-2. This work renders a viable approach to design dual-functional electrocatalysts with exceptional electrocatalytic activity and stability at high current density, showing the great prospect of water electrolysis for commercial application.

Ce-Modified Flowerlike NiFe-MOF Nanostructure Based on Ion Competitive Coordination for Enhancing the Oxygen Evolution Reaction.

Metal-organic framework (MOF) has become a popular electrocatalyst for the oxygen evolution reaction (OER) because of its large specific surface area and adjustable porosity. Nevertheless, the electrochemical performance of MOFs has been greatly limited by poor intrinsic conductivity and catalytic activity. Herein, we report a Ce-doped nanoflower-like MOF material Ce@NiFe-MOF-5 via a facile ion competitive coordination effect and doping method. Benefiting from the nanoflower structure formed by the stacking of nanosheets, a large number of active sites can be exposed, which favors electron/mass transfer during water oxidation. The coordination substitution of Ce ions not only promoted an increase in the number of active sites on the surface of the nanosheets but also optimized the electronic structure of pristine NiFe-MOF. The well-designed Ce@NiFe-MOF-5 catalysts exhibited superior OER performance under basic conditions, which only required an overpotential of 258 mV at a current density of 10 mA cm-2 and a Tafel slope of 54.44 mV dec-1. Moreover, when Ce@NiFe-MOF-5 served as an anode and Pt/C as a cathode, the two-electrode system only needed 1.56 V to drive overall water splitting at 10 mA cm-2.

Ir-Doped Bilayer Heterojunction Hollow Nanoboxes for Electrocatalytic Oxygen Evolution.

The fabrication of hollow nanoelectrocatalysts with multilayered heterogeneous interfaces, derived from metal-organic framework (MOF) materials, represents a highly efficient strategy that promotes the oxygen evolution reaction (OER). Within this research, we successfully synthesized a hollow nanobox of Ir-doped ZIF-67@CoFe PBA with bilayer heterointerfaces. The distinctive structure of Ir-ZIF-67@CoFe PBA provides a substantial number of active sites for reaction intermediates, resulting in improved utilization of precious metals. Furthermore, experimental results indicate the outstanding electrocatalytic performance of the optimized Ir-ZIF-67@CoFe PBA, as indicated by a mere 269 mV overpotential at 10 mA·cm-2, accompanied by a small Tafel slope of 80.1 mV·dec-1. Moreover, the Schottky junction formed between the heterojunction and Ir within Ir-ZIF-67@CoFe PBA accelerates the electron-transfer rate, contributing to its exceptional catalytic performance compared to that of a catalyst derived solely from ZIF-67. This distinctive feature of the catalyst holds tremendous application value.

Simple Synthesis of PdAg Porous Nanowires as Effective Catalysts for Polyol Oxidation Reaction.

The development of efficient and stable Pd-based electrocatalysts is extremely important to facilitate the development of catalysts for polyol oxidation reactions. To synthesize Pd-based catalysts with excellent catalytic performance, a series of PdAg porous nanowires (PdAg PNWs) with different elemental ratios was constructed by facile synthesis using a seed-mediated method. The synthesized PdAg PNWs have a rough surface and a porous one-dimensional structure, which optimize the specific surface area and surface area of catalysts, thereby providing more active sites for catalysts. PdAg PNWs benefited from the geometric effect of porous nanowires and the synergy between Pd and Ag, showing excellent catalysis (8243.0 and 4137.0 mA mgPd-1) for the ethylene glycol oxidation reaction (EGOR) and glycerol oxidation reaction (GOR). Among them, the optimal Pd62Ag38 PNWs show the highest catalytic activity (6.0 times and 3.9 times higher than Pd/C) and stability compared with Pd57Ag43 PNWs, Pd51Ag49 PNWs, and Pd/C for EGOR and GOR. At the same time, this porous one-dimensional structure also endows PdAg PNWs with faster electron transfer capabilities than Pd/C. This work will likely provide an effective strategy for constructing cost-effective catalysts.

Positive remediation on sedimentary P by combination of capping with calcium hydroxide and oxidation with perhydrol.

The capping is called passive remediation because the sedimentary P was released and then immobilized by the capping materials. However, the release depends on the environmental conditions. Therefore, a hypothesis was proposed that the oxidant was used to accelerate sedimentary P release and the capping material was used to capture those released P. It is positive remediation to reduce sedimentary P amount. The results show that soluble reactive phosphorus (SRP) concentration in the overlying water and pore water increased and then decreased gradually under the combination of sodium percarbonate (SPC) and Ca(OH)2, similar as that under the capping with single Ca(OH)2. The sedimentary P amount was reduced considerably and P concentration in the capping layer increased obviously after 60 days, compared with the capping with single Ca(OH)2. All these indicated that oxidation improved the sedimentary P release and the released P was captured and immobilized by the capping material of Ca(OH)2. However, the acceleration of sedimentary P release due to the oxidation is obviously different from the traditional mechanism that the oxic condition in the sediment is favor of the immobilization on sedimentary P. It is attributed to the oxidizability of ·OH from SPC. The reduction of mobile-P and the increase of Ca-P under the combined use are observed. This is similar as traditional mechanism of oxic condition. It is sure that positive remediation reduced sedimentary P amount, resulting in the decrease of P release risk in a long time.

Core@shell PtAuAg@PtAg Hollow Nanodendrites as Effective Electrocatalysts for Methanol and Ethylene Glycol Oxidation.

Pt-based catalysts with core@shell structures are widely used in alcohol oxidations due to their excellent catalytic performance. In this work, we synthesized a series of core@shell PtAuAg@PtAg hollow nanodendrites (HNDs) with different compositions by a simple seed-mediated method. The PtAuAg@PtAg HNDs with a hollow core and dendritic shell exhibit excellent catalytic performance for ethylene glycol oxidation reaction (EGOR) and methanol oxidation reaction (MOR). Among these, Pt38Au29Ag33 HNDs have the highest mass activity (12364.0 mA mgPt-1/3278.0 mA mgPt-1) for EGOR and MOR, which is 4.2 times and 5.3 times higher than that of commercial Pt/C (2941.0 mA mgPt-1/617.6 mA mgPt-1), respectively. More importantly, after successive cyclic voltammetry tests, the retained mass activities of Pt38Au29Ag33 HNDs are 3913.8 mA mgPt-1 and 348.3 mA mgPt-1, which are much higher than that of commercial Pt/C as well. The excellent catalytic performance of PtAuAg@PtAg HNDs can be attributed to the structure of HNDs, which can greatly increase the surface area and active sites, as well as the electronic and synergistic effects among Pt, Au, and Ag. This research may provide new ideas for the development of high-efficiency hollow catalytic materials for EGOR and MOR.

Significant Decrease in Activation Temperature for the Generation of Strong Basicity: A Strategy of Endowing Supports with Reducibility.

Mesoporous solid strong bases are quite attractive due to their good catalytic performance for applications as environmentally friendly catalysts in various reactions. However, pretty harsh conditions are usually compulsory for the fabrication of strong basicity by using traditional thermal activation (e.g., 700 °C for the activation of base precursor KNO3 supported on mesoporous Al2O3). This is energy intensive and harmful to the mesoporous structure. In this study, we report a strategy of endowing supports with reducibility (ESWR) by doping low-valence Cr3+ into mesoporous Al2O3, so that the activation temperature for basicity generation is decreased significantly. Fascinatingly, KNO3 on mesoporous Al2O3 can be motivated to basic sites completely at the temperature of 400 °C via the ESWR strategy, which is much lower than the conventional thermal activation (700 °C). We have demonstrated that the redox reciprocity between KNO3 and Cr3+ is responsible for the low-temperature conversion, and Cr6+ is formed quantitatively as the oxidation product. The obtained solid bases possessing ordered mesostructure and strong basicity provide promising candidates for base-catalyzed synthesis of dimethyl carbonate via transesterification. The catalytic activity is obviously higher than a typical solid base like MgO as well as a series of reported basic catalysts containing alkali metal and alkaline-earth metal oxides.

Exploration of CeO2-CuO Quantum Dots in Situ Grown on Graphene under Hypha Assistance for Highly Efficient Solar-Driven Hydrogen Production.

The development of an artificial model of photoinduced hydrogen production system requires efficient, long-term stability and cost-competitive photocatalysts to store solar energy in chemical bonds. However, the existing photocatalysts still suffer from the high cost, high recombination rate of photoexcited electron-hole pairs, and poor photostability. Herein, we demonstrate the synthesis of a p-type CuO/n-type CeO2 heterojunction in situ grown on graphene via a hypha assistance process. Amazingly, optical and photoelectrochemical measurements show the superiority of this hierarchically biomorphic structure. The observed H2 evolution rate of the CeO2-CuO quantum dots/graphene has reached 2481 µmol·h-1·g-1 and remains unchanged in four hydrogen production cycles. Considering the convenience of microbial culture, this heterostructure system has great potential as a photocatalyst for solar-fuel conversion.

Protein Staining Agents from Cationic and Neutral Luminescent Iridium(III) Complexes.

Seven luminescent iridium(III) complexes were prepared to investigate the relationships between chemical structures and properties of protein staining. For the first time, the effect of the main ligand, the π conjugation effect of the ancillary ligand, and the charge effect of organometallic complexes on protein staining has been revealed. Most importantly, this study gives the first experimental evidence of the potential applications of charge-neutral organometallic complexes in protein staining, which could open an avenue of exploiting novel protein staining agents in the future.

Supramolecular hydrogels for wound repair and hemostasis.

The unique network characteristics and stimuli responsiveness of supramolecular hydrogels have rendered them highly advantageous in the field of wound dressings, showcasing unprecedented potential. However, there are few reports on a comprehensive review of supramolecular hydrogel dressings for wound repair and hemostasis. This review first introduces the major cross-linking methods for supramolecular hydrogels, which includes hydrogen bonding, electrostatic interactions, hydrophobic interactions, host-guest interactions, metal ligand coordination and some other interactions. Then, we review the advanced materials reported in recent years and then summarize the basic principles of each cross-linking method. Next, we classify the network structures of supramolecular hydrogels before outlining their forming process and propose their potential future directions. Furthermore, we also discuss the raw materials, structural design principles, and material characteristics used to achieve the advanced functions of supramolecular hydrogels, such as antibacterial function, tissue adhesion, substance delivery, anti-inflammatory and antioxidant functions, cell behavior regulation, angiogenesis promotion, hemostasis and other innovative functions in recent years. Finally, the existing problems as well as future development directions of the cross-linking strategy, network design, and functions in wound repair and hemostasis of supramolecular hydrogels are discussed. This review is proposed to stimulate further exploration of supramolecular hydrogels on wound repair and hemostasis by researchers in the future.

In situ phosphoselenization induced heterointerface engineering endow NiSe2/Ni2P/FeSe2 hollow nanocages with efficient water oxidation electrocatalysis performance.

Exploiting Earth-abundant and highly effective electrocatalysts toward the oxygen evolution reaction (OER) is critical for boosting water splitting efficiency. Herein, we proposed a novel in situ phosphoselenization strategy to fabricate heterostructured NiSe2/Ni2P/FeSe2 (NiFePSe) nanocages with a modified electronic structure and well-defined nanointerfaces. Owing to the strong interfacial coupling and synergistic effect among the three components, the prepared NiFePSe nanocages exhibit superior OER performance with an ultralow overpotential of 242 mV at 10 mA cm-2 and a small Tafel slope of 55.8 mV dec-1 along with robust stability in 1 M KOH. Remarkably, the highly open 3D porous architecture, delicate internal voids, and numerous surface defects endow the NiFePSe nanocages with abundant active sites and enhanced electron mobility. In addition, the super-hydrophilic surface is conducive to facilitating mass transfer between the electrolyte and electrode and rapidly releasing the bubbles. This work may lead to new breakthroughs in the tuning of multi-component transition metal catalysts and the designing of highly active and durable materials for water splitting.

Synthesis of calcium carbonate-loaded mesoporous SBA-15 nanocomposites for removal of phosphate from solution.

Removal of phosphate from water is very crucial for protecting the ecological environment since massive phosphorus fertilizers have been widely used and caused serious water deterioration. Thus, we fabricated a series of calcium carbonate-loaded mesoporous SBA-15 nanocomposites with different Ca:Si molar ratio (CaAS-x) as phosphorus adsorbents via a simple wet-impregnation method. The multiply approaches including X-ray diffraction (XRD), N2 physisorption, thermogravimetric mass spectrometry (TG-MS), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FT-IR) were used to characterize the structure, morphology, and composition of mesoporous CaAS-x nanocomposites. The phosphate adsorption efficiency of the CaAS-x nanocomposites was studied through adsorption and desorption batch tests. Results showed that the increases of Ca:Si molar ratio (rCa:Si) improved the phosphate removal capacity of CaAS nanocomposites, especially CaAS with the optimum synthesis molar ratio of Ca:Si as 0.55 showed the high adsorption capacity of 92.0 mg·g-1 to high concentration of phosphate (> 200 mg·L-1). Note that the CaAS-0.55 had a fast exponentially increased adsorption capacity with increasing the phosphate concentration and correspondingly showed a much faster phosphate removal rate than pristine CaCO3. Apparently, mesoporous structure of SBA-15 contributed to high disperse of CaCO3 nanoparticles leading to the monolayer chemical adsorption complexation formation of phosphate calcium (i.e., =SPO4Ca, =CaHPO4-, and =CaPO4Ca0). Therefore, mesoporous CaAS-0.55 nanocomposite is an environmental-friendly adsorbent for effective removal of high concentration of phosphate in neutral contaminated wastewater.

One-pot synthesis of PdPtAg porous nanospheres with enhanced electrocatalytic activity toward polyalcohol electrooxidation.

Porous nanospheres (PNSs) have great development prospects in the electrocatalysis field because of their structural characteristics, such as a large specific surface area. However, it is still a challenge to find a simple and energy-saving method for the controllable synthesis of PNS nanocatalysts. In this paper, a one-pot CTAC-assisted strategy was developed for the successful formation of PdPtAg PNSs with high porosity at room temperature. Benefitting from the unique structures, optimized composition, acceleration of charge transfer and enhanced resistance to CO poisoning, the PdPtAg PNSs displayed considerably improved electrocatalytic performance with high mass activity and stability toward the ethylene glycol oxidation reaction (EGOR) and glycerol oxidation reaction (GOR). The EGOR and GOR mass activities of PdPtAg were 5.00 A mgmetal-1 and 3.06 A mgmetal-1, which are 6.22 and 1.91 times that of commercial Pd/C, respectively. This work is expected to offer a new path for improving catalytic performance by simple design and adjustment of morphology.

Synthesis of Cu Nanoparticles Incorporated Mesoporous C/SiO2 for Efficient Tetracycline Degradation.

In this study, a Cu NPs-incorporated carbon-containing mesoporous SiO2 (Cu/C-SiO2) was successfully synthesized through a grinding-assisted self-infiltration method followed by an in situ reduction process. The obtained Cu/C-SiO2 was then employed as a Fenton-like catalyst to remove tetracycline (TC) from aqueous solutions. TEM, EDS, XRD, N2 adsorption-desorption, FTIR, and XPS methods were used to characterize the crystal structure, morphology, porosity, chemical composition, and surface chemical properties of the catalyst. The effects of initial TC concentration, catalyst dosage, H2O2 dosage, solution pH, HA addition, and water media on the TC degradation over Cu/C-SiO2 were investigated. Scavenging and electrochemical experiments were then carried out to analyze the TC degradation mechanism. The results show that the Cu/C-SiO2 can remove 99.9% of the concentrated TC solution (C0 = 500 mg·L-1), and it can be used in a wide pH range (R.E. = 94-99%, pH = 3.0-11.0). Moreover, hydroxyl radicals (•OH) were detected to be the dominant reactive species in this catalytic system. This study provides a simple and promising method for the synthesis of heteroatom-containing mesoporous catalysts for the decomposition of antibiotics in wastewater.

Photoelectrocatalytic oxidation of ethylene glycol on trimetallic PdAgCu nanospheres enhanced by surface plasmon resonance.

The notable surface plasmon resonance (SPR) effect of some metals has been applied to improve the efficiency of alcohol oxidation reactions, whereas the comprehensive investigation of Cu-assisted photoelectrocatalysis remains challenging. We herein successfully prepared trimetallic PdAgCu nanospheres (NSs) with abundant surface bulges for the advanced ethylene glycol oxidation reaction (EGOR) and compared them with bimetallic PdAg NSs to investigate the performance enhancement mechanism. Impressively, the as-optimized PdAgCu NSs exhibited superb mass activity and electrochemical stability. Moreover, under visible light illumination, the mass activity of PdAgCu NSs increased to 1.62 times compared to that in the dark, and in contrast, the mass activity of PdAg NSs only increased to 1.48 times that in the dark. A mechanistic study indicated that the incorporation of Cu not only strengthens the whole SPR effect of PdAgCu NSs but also further modifies the electronic structure of Pd. This work highlighted that the incorporation of Cu into PdAg NSs further enhanced the photoelectrocatalytic performance and increased noble metal atom utilization, which may provide guidance to fabricate novel and promising nanocatalysts in the field of photoelectrocatalysis.

Heterostructure engineering and ultralow Pt-loaded multicomponent nanocage for efficient electrocatalytic oxygen evolution.

Developing highly efficient electrocatalysts based on appropriate heterojunction engineering and electronic structure modification for the oxygen evolution reaction (OER) has been extensively recognized as an effective approach to increase the efficiency of water splitting. Herein, ultralow Pt-loaded (1 %) NiCoFeP@NiCoFe-PBA hollow nanocages with well-defined heterointerfaces and modified electronic environment are successfully fabricated. As expected, the obtained Pt-NiCoFeP@NiCoFe-PBA exhibits outstanding performance with a low overpotential of 255 mV at 10 mA cm-2 and a small Tafel slope of 57.2 mV dec-1. More specifically, the highly open three-dimensional structure, exquisite interior voids and abundant surface defects endow Pt-NiCoFeP@NiCoFe-PBA nanocages with more electrochemical active sites. Meanwhile, experimental results and mechanism studies also reveal that the construction of heterogeneous interfaces as well as incorporation of noble metals could readily induce strong synergistic effects and significantly tailor electronic configurations to optimize the binding energy of the intermediates, thereby achieving prominent OER performance.

Self-driven Ru-modified NiFe MOF nanosheet as multifunctional electrocatalyst for boosting water and urea electrolysis.

Urea electro-oxidation reaction (UOR) has been a promising strategy to replace oxygen evolution reaction (OER) by urea-mediated water splitting for hydrogen production. Naturally, rational design of high-efficiency and multifunctional electrocatalyst towards UOR and hydrogen evolution reaction (HER) is of vital significance, but still a grand challenge. Herein, an innovative 3D Ru-modified NiFe metal-organic framework (MOF) nanoflake array on Ni foam (Ru-NiFe-x/NF) was elaborately designed via spontaneous galvanic replacement reaction (GRR). Notably, the adsorption capability of intermediate species (H*) of catalyst is significantly optimized by Ru modification. Meanwhile, rich high-valence Ni active species can be acquired by self-driven electronic reconstruction in the interface, then dramatically accelerating the electrolysis of water and urea. Remarkably, the optimized Ru-NiFe-③/NF (1.6 at% of Ru) only requires the overpotential of 90 and 310 mV to attain 100 mA cm-2 toward HER and OER in alkaline electrolyte, respectively. Impressively, an ultralow voltage of 1.47 V is required for Ru-NiFe-③/NF to deliver a current density of 100 mA cm-2 in urea-assisted electrolysis cell with superior stability, which is 190 mV lower than that of Pt/C-NF||RuO2/NF couple. This work is desired to explore a facile way to exploit environmentally-friendly energy by coupling hydrogen evolution with urea-rich sewage disposal.

One-pot synthesis of rugged PdRu nanosheets as the efficient catalysts for polyalcohol electrooxidation.

Recently, intensive attention has been attracted to the two-dimensional metal nanosheets, owing to their excellent electrocatalytic performance for direct alcohol fuel cells (DAFCs). Herein, PdRu nanosheets have been synthesized successfully by a facile one-pot method. The rugged nanosheet structure provided plentiful surface active sites to enhance the electrocatalytic activity. Moreover, benefiting from the synergistic effect and improved electronic structure, PdRu NSs exhibited splendid electrocatalytic performance in ethylene glycol oxidation reaction (EGOR) and glycerol oxidation reaction (GOR). Specifically, the mass activity of PdRu NSs was 1.72 and 3.69 times over those of Pd NSs and Pd/C catalysts in EGOR. Moreover, PdRu NSs displayed the largest mass activity in GOR, 1.48 and 2.47 times as large as Pd NSs and Pd/C catalysts. The results of stability tests demonstrated that the durability of PdRu NSs was the highest among the obtained catalysts. This work plays a directive role on the in-depth engineering on Pd-based catalysts with nanosheet architectures.

Synthesis and Properties of Moisture-Cured Reactive Polyurethane Containing Castor Oil and Oxime Compounds.

Reactive polyurethane hot-melt resin (moisture-cured reactive polyurethane, PUR) could successfully be prepared from poly(tetramethylene ether) glycol (PTMG), castor oil and dimethylglyoxime (DMG) by one or two-stage synthesis. Fourier-transform infrared spectroscopy (FTIR) analysis showed that the synthesis resins belonged to NCO-capped castor oil-based polyurethane. The thermal behaviors of the cured PUR were analyzed by differential scanning calorimeter (DSC) and dynamic mechanical analyzer (DMA) instruments. The results showed that the cured resin provided remeltable properties under the dosages of 3 wt% DMG. Furthermore, the phenomenon could be proved by FTIR analysis according to the characteristic absorption peak of NCO groups after the cured resin was heated. Comparing different syntheses, the resin prepared by one-stage synthesis showed random distribution of DMG with PUR structure and that prepared by two-stage synthesis had distribution of DMG with branching structure in the prepolymer. The former obtained lower remeltable temperatures from 90 to 130 °C than the latter temperatures, which had temperatures above 125 °C. The tensile test showed that all of the PUR films exhibited typical tough behavior. Thus, the cured resin with DMG dosages of 3 wt% provided remeltable and mechanical properties at the same time. Overall, the crosslinking density and numbers of dynamic bonds should be kept in balance for preparation of remeltable PUR.