Oxyhydroxide Nanosheets with Highly Efficient Electron–Hole Pair Separation for Hydrogen Evolution

The facile electron–hole pair recombination in earth‐abundant transition‐metal oxides is a major limitation for the development of highly efficient hydrogen evolution photocatalysts. In this work, the thickness of a layered β‐CoOOH semiconductor that contains metal/hydroxy groups was reduced to obtain an atomically thin, two‐dimensional nanostructure. Analysis by ultrafast transient absorption spectroscopy revealed that electron–hole recombination is almost suppressed in the as‐prepared 1.3 nm thick β‐CoOOH nanosheet, which leads to prominent electron–hole separation efficiencies of 60–90 % upon irradiation at 350–450 nm, which are ten times higher than those of the bulk counterpart. X‐ray absorption spectroscopy and first‐principles calculations demonstrate that [HO?CoO_6?x] species on the nanosheet surface promote H⁺ adsorption and H₂ desorption. An aqueous suspension of the β‐CoOOH nanosheets exhibited a high hydrogen production rate of 160 μmol g^?1 h^?1 even when the system was operated for hundreds of hours.     

Facile synthesis of PtSnZn nanosheet thin film at oil–water interface by use of organometallic complexes: An efficient catalyst for methanol oxidation and p‐nitrophenol reduction reactions

PtSnZn nanosheet thin film with stable and high activity towards methanol electro‐oxidation was synthesized via a simple reduction of organometallic precursors including [PtCl₂(cod)] (cod = cis,cis‐1,5‐cyclooctadiene) and [Sn(CH₃)₄] complexes, in the presence of [Zn(acac)₂] (acac = acetylacetonate) complex at toluene–water interface. Catalytic activities of PtSnZn nanosheets were investigated in the p‐nitrophenol (p‐Nip) reduction and methanol oxidation reactions. The obtained results demonstrate that PtSnZn nanosheets exhibit a good electrocatalytic performance for methanol oxidation reaction, the catalytic activity of the PtSnZn nanosheets being at least 3.5 times higher than that of Pt nanoparticle thin film. Also, the apparent rate constant obtained for p‐Nip reduction with the PtSnZn nanosheets is at least 2.3 times higher than that for Pt nanoparticle thin film due to the appropriate interaction between platinum, tin and zinc metals and geometric properties of PtSnZn nanosheet thin film. Nanosheets are highly favourable for superior catalytic performances due to their geometric properties. A facile and efficient route was used to synthesize trimetallic alloy thin film at oil–water interface.     

Cu(II) immobilized on guanidinated epibromohydrin‐functionalized γ‐Fe2O3@TiO2 (γ‐Fe2O3@TiO2‐EG‐Cu(II)): A highly efficient magnetically separable heterogeneous nanocatalyst for one‐pot synthesis of highly substituted imidazoles

A simple, efficient and eco‐friendly procedure has been developed using Cu(II) immobilized on guanidinated epibromohydrin‐functionalized γ‐Fe₂O₃@TiO₂ (γ‐Fe₂O₃@TiO₂‐EG‐Cu(II)) for the synthesis of 2,4,5‐trisubstituted and 1,2,4,5‐tetrasubstituted imidazoles, via the condensation reactions of various aldehydes with benzil and ammonium acetate or ammonium acetate and amines, under solvent‐free conditions. High‐resolution transmission electron microscopy analysis of this catalyst clearly affirmed the formation of a γ‐Fe₂O₃ core and a TiO₂ shell, with mean sizes of about 10–20 and 5–10 nm, respectively. These data were in very good agreement with X‐ray crystallographic measurements (13 and 7 nm). Moreover, magnetization measurements revealed that both γ‐Fe₂O₃@TiO₂ and γ‐Fe₂O₃@TiO₂‐EG‐Cu(II) had superparamagnetic behaviour with saturation magnetization of 23.79 and 22.12 emu g^?1, respectively. γ‐Fe₂O₃@TiO₂‐EG‐Cu(II) was found to be a green and highly efficient nanocatalyst, which could be easily handled, recovered and reused several times without significant loss of its activity. The scope of the presented methodology is quite broad; a variety of aldehydes as well as amines have been shown to be viable substrates. A mechanism for the cyclocondensation reaction has also been proposed.     

Iridium‐Based Cubic Nanocages with 1.1‐nm‐Thick Walls: A Highly Efficient and Durable Electrocatalyst for Water Oxidation in an Acidic Medium

We report a highly active and durable water oxidation electrocatalyst based on cubic nanocages with a composition of Ir₄₄Pd₁₀, together with well‐defined {100} facets and porous walls of roughly 1.1 nm in thickness. Such nanocages substantially outperform all the water oxidation electrocatalysts reported in literature, with an overpotential of only 226 mV for reaching 10 mA cm^?2_geo at a loading of Ir as low as 12.5 μg_Ir cm^?2 on the electrode in acidic media. When benchmarked against a commercial Ir/C electrocatalyst at 250 mV of overpotential, such a nanocage‐based catalyst not only shows enhancements (18.1‐ and 26.2‐fold, respectively) in terms of mass (1.99 A mg^?1_Ir) and specific (3.93 mA cm^?2_Ir) activities, but also greatly enhanced durability. The enhancements can be attributed to a combination of multiple merits, including a high utilization efficiency of Ir atoms and an open structure beneficial to the electrochemical oxidation of Ir to the active form of IrO_x.     

Nano n‐propylsulfonated γ‐Al2O3: a new,efficient and reusable catalyst for synthesis of spiro[indoline‐3,4‐pyrazolo[3,4‐e][1,4]thiazepine]diones in aqueous media

Nano n‐propylsulfonated γ‐Al₂O₃ is easily prepared by the reaction of nano γ‐Al₂O₃ with 1,3‐propanesultone. This reagent can be used as an efficient catalyst for the synthesis of spiro [indoline‐3,4‐pyrazolo[3,4‐e][1,4]thiazepine]diones in aqueous media. This new method consistently has the advantages of excellent yields and short reaction times. Further, the catalyst can be reused and recovered several times. Copyright © 2013 John Wiley & Sons, Ltd.     

Reversely Trapping Isolated Atoms in High Oxidation State for Accelerating the Oxygen Evolution Reaction Kinetics

Developing efficient electrocatalysts for the oxygen evolution reaction (OER) is paramount to the energy conversion and storage devices. However, the structural complexity of heterogeneous electrocatalysts makes it a great challenge to elucidate the dynamic structural evolution and OER mechanisms. Here, we develop a controllable atom-trapping strategy to extract isolated Mo atom from the amorphous MoO_x-decorated CoSe₂ (a-MoO_x@CoSe₂) pre-catalyst into Co-based oxyhydroxide (Mo-CoOOH) through an ultra-fast self-reconstruction process during the OER process. This conceptual advance has been validated by operando characterizations, which reveals that the initially rapid Mo leaching can expedite the dynamic reconstruction of pre-catalyst, and simultaneously trap Mo species in high oxidation state into the lattice of in situ generated CoOOH support. Impressively, the OER kinetics of CoOOH has been greatly accelerated after the reverse decoration of Mo species, in which the Mo-CoOOH affords a markedly decreased overpotential of 297 mV at the current density of 100 mA cm⁻². Density functional theory (DFT) calculations demonstrate that the Co species have been greatly activated via the effective electron coupling with Mo species in high oxidation state. These findings open new avenues toward directly synthesizing atomically dispersed electrocatalysts for high-efficiency water splitting.     

Activating CoOOH Porous Nanosheet Arrays by Partial Iron Substitution for Efficient Oxygen Evolution Reaction

Iron‐substituted CoOOH porous nanosheet arrays grown on carbon fiber cloth (denoted as Fe_xCo_1?xOOH PNSAs/CFC, 0≤x≤0.33) with 3D hierarchical structures are synthesized by in situ anodic oxidation of α‐Co(OH)₂ NSAs/CFC in solution of 0.01 m (NH₄)₂Fe(SO₄)₂. X‐ray absorption fine spectra (XAFS) demonstrate that CoO₆ octahedral structure in CoOOH can be partially substituted by FeO₆ octahedrons during the transformation from α‐Co(OH)₂ to Fe_xCo_1?xOOH, and this is confirmed for the first time in this study. The content of Fe in Fe_xCo_1?xOOH, no more than 1/3 of Co, can be controlled by adjusting the in situ anodic oxidation time. Fe_0.33Co_0.67OOH PNSAs/CFC shows superior OER electrocatalytic performance, with a low overpotential of 266 mV at 10 mA cm^?2, small Tafel slope of 30 mV dec^?1, and high durability.     

Efficient Noble‐Metal‐Free γ‐Fe2O3@NiO Core–Shell Nanostructured Photocatalysts for Water Oxidation

Flowerlike noble‐metal‐free γ‐Fe₂O₃@NiO core–shell hierarchical nanostructures have been fabricated and examined as a catalyst in the photocatalytic oxidation of water with [Ru(bpy)₃](ClO₄)₂ as a photosensitizer and Na₂S₂O₈ as a sacrificial electron acceptor. An apparent TOF of 0.29 μmols^?1 m^?2 and oxygen yield of 51 % were obtained with γ‐Fe₂O₃@NiO. The γ‐Fe₂O₃@NiO core–shell hierarchical nanostructures could be easily separated from the reaction solution whilst maintaining excellent water‐oxidation activity in the fourth and fifth runs. The surface conditions of γ‐Fe₂O₃@NiO also remained unchanged after the photocatalytic reaction, as confirmed by X‐ray photoelectron spectroscopy (XPS).     

Direct Monitoring of γ‐Glutamyl Transpeptidase Activity In Vivo Using a Hyperpolarized 13C‐Labeled Molecular Probe

The γ‐glutamyl transpeptidase (GGT) enzyme plays a central role in glutathione homeostasis. Direct detection of GGT activity could provide critical information for the diagnosis of several pathologies. We propose a new molecular probe, γ‐Glu‐[1‐¹³C]Gly, for monitoring GGT activity in vivo by hyperpolarized (HP) ¹³C magnetic resonance (MR). The properties of γ‐Glu‐[1‐¹³C]Gly are suitable for in vivo HP ¹³C metabolic analysis since the chemical shift between γ‐Glu‐[1‐¹³C]Gly and its metabolic product, [1‐¹³C]Gly, is large (4.3 ppm) and the T₁ of both compounds is relatively long (30 s and 45 s, respectively, in H₂O at 9.4 T). We also demonstrate that γ‐Glu‐[1‐¹³C]Gly is highly sensitive to in vivo modulation of GGT activity induced by the inhibitor acivicin.     

Electrochemical Oxidative Detection of Guanosine‐5′‐triphosphate Based on a New Ionic Liquid Modified Carbon Paste Electrode

An ionic liquid (IL) 1‐(3‐chloro‐2‐hydroxy‐propyl)‐3‐methylimidazolium trifluoroacetate was used as the modifier for the preparation of the modified carbon paste electrode (CPE). The IL‐CPE showed excellent electrocatalytic activity towards the oxidation of guanosine‐5′‐triphosphate (5′‐GTP) in a pH 5.0 Britton‐Robinson buffer solution. Due to the presence of high conductive IL on the electrode surface, the electrooxidation of 5′‐GTP was greatly promoted with a single well‐defined irreversible oxidation peak appeared. The electrode reaction was an adsorption‐controlled process and the electrochemical parameters of 5′‐GTP on IL‐CPE were calculated with the electron transfer coefficient (α) as 0.44, the electron transfer number (n) as 1.99, the apparent heterogeneous electron transfer rate constant (k_s) as 2.21 × 10^?9 s^?1 and the surface coverage (Γ_T) as 1.53 × 10^?10 mol cm^?2. Under the selected conditions a linear calibration curve between the oxidation peak currents and 5′‐GTP concentration was obtained in the range from 2.0 to 1000.0 μmol L^?1 with the detection limit as 0.049 μmol L^?1 (3σ) by differential pulse voltammetry. The proposed method showed good selectivity to the 5‘‐GTP detection without the interferences of coexisting substances and the practical application was checked by measurements of the artificial samples.     

γ‐Fe2O3@Cu3Al‐LDH‐TUD as a new Amphoteric,Highly Efficient and Recyclable Heterogeneous Catalyst for the Solvent‐free Synthesis of Dihydropyrano[3,2‐c]pyrazoles and dihydropyrano[3,2‐c]chromens

Thiourea dioxide was immobilized on γ‐Fe₂O₃@Cu₃Al‐LDH magnetic nanoparticles to prepare the γ‐Fe₂O₃@Cu₃Al‐LDH‐TUD MNPs. The structure and properties of these magnetic nanoparticles were established by FT‐IR, EDX, SEM, XRD, and hystogram of particle size analytical methods. The results obtained from these analytical methods confirmed the successful immobilization of the thiourea dioxide onto the magnetic support. The synthesized magnetic nanoparticles (MNPs) exhibited high catalytic activity in one‐pot three‐component reactions under mild and solvent‐free conditions for the synthesis of diverse ranges of dihydropyrano[3,2‐c]pyrazoles and dihydropyrano[3,2‐c]chromens. All the reactions proceeded smoothly to furnish the respective products in excellent yields. Simple isolation of the products, avoidance of harmful organic solvents, versatility of the catalyst and its easy magnetic separation and reusability with no significant loss of activity are the main advantages of the present method.     

Perylene diimide‐modified magnetic γ‐Fe2O3/CeO2 nanoparticles as peroxidase mimics for highly sensitive colorimetric detection of Vitamin C

Perylene diimide‐modified magnetic γ‐Fe₂O₃/CeO₂ nanoparticles (γ‐Fe₂O₃/CeO₂‐PDI) were prepared and exhibited excellent peroxidase‐like activity. The samples were characterized by HR‐TEM, XRD, Raman, N₂ adsorption, magnetic strength and XPS. The obtained γ‐Fe₂O₃/CeO₂‐PDI had size of 10~20 nm with high specific surface area of 77 m²/g, and could be easily separated from the aqueous solution by using a magnet, which are in favor of its practical application. Due to the decoration of PDI, the γ‐Fe₂O₃/CeO₂‐PDI possessed more surface defects (Ce³⁺) and active oxygen species than that of γ‐Fe₂O₃/CeO₂, resulting in the outstanding catalytic performance. And the composite catalyst also showed highly sensitive and selectivity toward VC with a limit of detection of 0.45 μM. Based on the fluorescent results, a possible hydroxyl radical (?OH) catalytic mechanism was proposed. It is believed that the as‐prepared γ‐Fe₂O₃/CeO₂‐PDI nanoparticles are promising biosensors applied for biomedical and food analysis.     

CoS2 Nanoparticles Embedded in Covalent Organic Polymers as Efficient Electrocatalyst for Oxygen Evolution Reaction with Ultralow Overpotential

Cobalt disulfide (CoS₂) has been explored as attractive electrocatalyst for oxygen evolution reaction (OER). However, bulk CoS₂ sheets have limited catalytic activity due to low exposure of active sites. Herein, through an in-situ vulcanization approach, CoS₂ nanoparticles are embedded into bipyridine-containing covalent organic polymer (BP-COP). The as-prepared nanocomposite CoS₂@BP-COP exhibits high catalytic activity toward OER with an ultra-low overpotential of 270 mV (vs. RHE) at a current density of 10 mA cm⁻², a small Tafel slope of 36 mV dec⁻¹, and an excellent durability for 24 h without decay. The surface of CoS₂ is partially converted into CoOOH to form CoS₂/CoOOH as active sites under OER conditions. CoS₂@BP-COP displays superior OER catalytic activity to CoS₂ nanosheets and commercially available RuO₂ under the same conditions. The outstanding OER performance activity of CoS₂@BP-COP could be attributed to the uniform and small particle sizes of CoS₂/CoOOH distributed in BP-COP.     

Tailoring Oxygen Vacancy on Co3O4 Nanosheets with High Surface Area for Oxygen Evolution Reaction?

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here, we designed an efficient Co₃O₄ electrocatalyst using a pyrolysis strategy for oxygen evolution reaction (OER). Morphological characterization confirmed the ultra-thin structure of nanosheet. Further, the existence of oxygen vacancies was obviously evidenced by the X-ray photoelectron spectroscopy and electron spin resonance spectroscopy. The increased surface area of Co₃O₄ ensures more exposed sites, whereas generated oxygen vacancies on Co₃O₄ surface create more active defects. The two scenarios were beneficial for accelerating the OER across the interface between the anode and electrolyte. As expected, the optimized Co₃O₄ nanosheets can catalyze the OER efficiently with a low overpotential of 310 mV at current density of 10 mA/cm² and remarkable long-term stability in 1.0 mol/L KOH.     

Blending Cr2O3 into a NiO–Ni Electrocatalyst for Sustained Water Splitting

The rising H₂ economy demands active and durable electrocatalysts based on low‐cost, earth‐abundant materials for water electrolysis/photolysis. Here we report nanoscale Ni metal cores over‐coated by a Cr₂O₃‐blended NiO layer synthesized on metallic foam substrates. The Ni@NiO/Cr₂O₃ triphase material exhibits superior activity and stability similar to Pt for the hydrogen‐evolution reaction in basic solutions. The chemically stable Cr₂O₃ is crucial for preventing oxidation of the Ni core, maintaining abundant NiO/Ni interfaces as catalytically active sites in the heterostructure and thus imparting high stability to the hydrogen‐evolution catalyst. The highly active and stable electrocatalyst enables an alkaline electrolyzer operating at 20 mA cm^?2 at a voltage lower than 1.5 V, lasting longer than 3 weeks without decay. The non‐precious metal catalysts afford a high efficiency of about 15 % for light‐driven water splitting using GaAs solar cells.     

Efficient conversion of fructose to 5‐hydroxymethylfurfural by functionalized γ‐Al2O3 beads

Millimeter size γ‐Al₂O₃ beads were prepared by alginate assisted sol–gel method and grafting organic groups with propyl sulfonic acid and alkyl groups as functionalized γ‐Al₂O₃ bead catalysts for fructose dehydration to 5‐hydroxymethylfurfural (5‐HMF). Experiment results showed that the porous structure of γ‐Al₂O₃ beads was favorable to the loading and dispersion of active components, and had an obvious effect on the properties of the catalyst. The lower calcination temperature of γ‐Al₂O₃ beads increased the specific surface area, the hydrophobicity and the activity of catalysts. Competition between the reaction of alkyl groups and ‐SH groups with surface hydroxyl during the preparation process of the catalyst influenced greatly the acid site densities, hydrophobic properties and activity of the catalyst. With an increase in the alkyl group chain, the hydrophobicity of catalysts increased obviously and the activity of the catalyst was enhanced. The most hydrophobic catalyst C₁₆‐SO₃H‐γ‐Al₂O₃–650°C exhibited the highest yield of 5‐HMF (84%) under the following reaction conditions: reaction medium of dimethylsulfoxide/H₂O (V/V, 4:1), catalyst amount of 30 mg, temperature of 110°C and reaction time of 4 hr.     

表面Co2CrO4电化学转化为CoOOH/CrOOH及其增强电催化析氧中的性能

以清洁能源发电为动力的水分解技术是一种很有应用前景的制氢方法,可以缓解日益增长的能源消耗和公众高度关注的环境问题.水分解的氧化过程,即析氧反应(OER),是一个四电子-质子耦合反应,其动力学缓慢,是实现高效电解水的技术难题.以RuO2和IrO2为代表的贵金属氧化物表现出极高的催化活性,但受限于储量低及价格昂贵,很难广泛...     

Understanding the Role of Gold Nanoparticles in Enhancing the Catalytic Activity of Manganese Oxides in Water Oxidation Reactions

The Earth‐abundant and inexpensive manganese oxides (MnO_x) have emerged as an intriguing type of catalysts for the water oxidation reaction. However, the overall turnover frequencies of MnO_x catalysts are still much lower than that of nanostructured IrO₂ and RuO₂ catalysts. Herein, we demonstrate that doping MnO_x polymorphs with gold nanoparticles (AuNPs) can result in a strong enhancement of catalytic activity for the water oxidation reaction. It is observed that, for the first time, the catalytic activity of MnO_x/AuNPs catalysts correlates strongly with the initial valence of the Mn centers. By promoting the formation of Mn³⁺ species, a small amount of AuNPs (<5 %) in α‐MnO₂/AuNP catalysts significantly improved the catalytic activity up to 8.2 times in the photochemical and 6 times in the electrochemical system, compared with the activity of pure α‐MnO₂.     

A Keggin Polyoxometalate Shows Water Oxidation Activity at Neutral pH: POM@ZIF‐8, an Efficient and Robust Electrocatalyst

Keggin‐type polyoxometalate anions [XM₁₂O₄₀]^n? are versatile, as their applications in interdisciplinary areas show. The Keggin anion [CoW₁₂O₄₀]^6? turns into an efficient and robust electrocatalyst upon its confinement in the well‐defined void space of ZIF‐8, a metal–organic framework (MOF). [H₆CoW₁₂O₄₀]@ZIF‐8 is so stable to water oxidation that it retains its initial activity even after 1000 catalytic cycles. The catalyst has a turnover frequency (TOF) of 10.8 mol O₂(mol Co)^?1 s^?1, one of the highest TOFs for electrocatalytic oxygen evolution at neutral pH. Controlled experiments rule out the chances of formation and participation of CoO_x in this electrocatalyic water oxidation.     

Polyethylene Glycol‐(N‐Methylimidazolium) Hydroxide‐Grafted γ‐Fe2O3@HAp: A Novel Nanomagnetic Recyclable Basic Phase‐Transfer Catalyst for the Synthesis of Tetrahydrobenzopyran Derivatives in Aqueous Media

Polyethylene glycol‐(N‐methylimidazolium) hydroxide‐grafted hydroxyapatite encapsulated γ‐Fe₂O₃ nanoparticles, γ‐Fe₂O₃@HAp@PEG(mim)OH, were prepared and characterized by FTIR, SEM, TEM, TGA, and EDAX. This nanocomposite was applied as a novel, green, nanomagnetic, and recyclable basic phase‐transfer catalyst for the synthesis of tetrahydrobenzopyrans in high yields via the three‐component reaction of aromatic aldehydes, malononitrile, and dimedone or 1,3‐cyclohexanedione in aqueous media at ambient temperature.