Salts-assistant synthesis of g-C3N4/Prussian-blue analogue/nickel foam with hierarchical structures as binder-free electrodes for supercapacitors.

The exploitation of high-performance electrode materials is significant to develop supercapacitors with satisfied energy and power output properties. In this study, a g-C3N4/Prussian-blue analogue (PBA)/Nickel foam (NF) with hierarchical micro/nano structures was developed by a simple salts-directed self-assembly approach. In this synthetic strategy, NF acted as both 3D macroporous conductive substrate and Ni source for PBA formation. Moreover, the incidental salt in molten salt-synthesized g-C3N4 nanosheets could regulate the combination mode between g-C3N4 and PBA to generate interactive networks of g-C3N4 nanosheets-covered PBA nano-protuberances on NF surfaces, which further expended the electrode/electrolyte interfaces. Based on the merits from this unique hierarchical structure and the synergy effect of PBA and g-C3N4, the optimized g-C3N4/PBA/NF electrode exhibited a maximum areal capacitance of 3366 mF cm-2 at current of 2 mA cm-2, as well as 2118 mF cm-2 even under large current of 20 mA cm-2. The solid-state asymmetric supercapacitor using g-C3N4/PBA/NF electrode possessed an extended working potential window of 1.8 V, prominent energy density of 0.195 mWh cm-2 and power density of 27.06 mW cm-2. Compared to the device with pure NiFe-PBA electrode, a better cyclic stability with capacitance retention rate of 80% after 5000 cycles was also achieved due to the protective effect of g-C3N4 shells on the etching of PBA nano-protuberances in electrolyte. This work not only builds a promising electrode material for supercapacitors, but also provide an effective way to apply molten salt-synthesized g-C3N4 nanosheet without purification.

Construction of organic-inorganic "chelate" adsorption sites on metal oxide semiconductor for room temperature NO2 sensing.

Metal oxide semiconductors (MOS) have been extensively studied for gas sensing due to their excellent chemical stability and adjustable electronic properties. However, there is still a lack of ingenious design strategies to achieve customizable gas detection in complex environments. Herein, a novel and scalable strategy of constructing organic-inorganic "chelate" adsorption sites is proposed to promote the affinity of MOS sensing materials to target molecules. Specifically, 3-aminopropyltriethoxysilane (APTES)-functionalized reduced graphene oxide (rGO) was decorated on In2O3 tubes (AG/Inx), and its NO2 sensing performance was studied. As a result, the optimal AG/Inx shows boosted room-temperature NO2 response, and its response to 1 ppm NO2 is 4.8 times that of In2O3. More attractively, the optimal AG/Inx exhibits good selectivity, as well as outstanding detection ability (Rg/Ra = 1.6) for low concentration NO2 (20 ppb). Experimental results suggest that APTES-rGO not only acts as the electron acceptor to accelerate charge transfer, but also enhances NO2 adsorption. Further theoretical calculations reveal that NO2 is simultaneously adsorbed at rGO and APTES via a flexible "chelate" mechanism. The multidentate adsorption configuration remarkably strengthens the NO2-host interaction, which is conducive to improving sensing performance. This work may inspire the material design of a new generation high-performance gas sensors.

Three-dimensional carbon dots/Prussian blue analogues nanocubes /nickel foams as self-standing electrodes for high-performance hybrid electrochemical capacitors.

Developing the high-performance supercapacitors is overwhelmingly dependent on the composition design and structure tailoring of electrode materials. By a one-step solution method, the composite of carbon dots/Prussian blue analogues nanocubes-incorporated three-dimensional Ni foams was prepared and used as a self-standing positive electrode for hybrid electrochemical capacitors (HEC). Aside from the role of Ni source for Prussian blue analogues (PBA), Ni foams acts as 3D conductive supports, making electrolytes more accessible to the internal surface of electrode. Meanwhile, carbon dots can be absorbed for the formation of carbon dots/PBA nanocubes on Ni foams surfaces, offering optimized interfaces for the interactions between electrodes and electrolytes and relieving the decomposition of PBA in alkaline electrolyte. With these merits, the carbon dots/Prussian blue analogues nanocubes-Ni foams electrode in the hybrid electrolyte of 0.5 M KOH and 1.3 M Na2SO4 exhibits a maximum specific capacity of 659 C g-1 at current density of 0.5 A g-1 and 344 C g-1 even under large current density of 5 A g-1. An extended working potential window of 1.8 V, high energy density of 65 Wh kg-1 and high power density of 4.052 kW kg-1 as well as improved cyclic stability are also achieved in the assembled HEC. This study builds a boulevard to improve the application potential of PBA in HEC, which will be beneficial for the development of supercapacitors.

Au25 Nanoclusters Incorporating Three-Dimensionally Ordered Macroporous In2O3 for Highly Sensitive and Selective Formaldehyde Sensing.

Detection of formaldehyde (FA) in the atmosphere is of significant importance because exposure to FA may cause serious health problems such as sick-house syndrome, leukemia, and cancer. Modifying metal oxide semiconductors (MOSs) with noble metal nanoparticles (NPs) is an efficient method to enhance FA-sensing properties. Herein, a series of Au25 nanocluster (NC)-decorated three-dimensionally ordered macroporous In2O3 materials (Au25/3DOM In2O3) is created, and the loading amount of Au25 NCs was optimized based on FA responses. To reveal the effect of gold size on FA responses, we constructed Au144 NC-loaded 3DOM In2O3 and Au NP (2.9 nm)-modified 3DOM In2O3 and compared their gas-sensing properties with the optimal Au25/3DOM In2O3. The results show that in comparison with its counterparts, the optimal Au25/3DOM In2O3 presents higher sensitivity, shorter response/recovery times, better selectivity, and excellent reproducibility. More attractively, the responses to FA are dependent on the size of Au particles loaded on In2O3. We suggest that the enhanced FA responses for the optimal material are mainly attributed to the electronic and chemical-sensitization effects of Au25 NCs, and the size-dependent effect of FA responses is ascribed to the size of Au NPs affecting the formation of oxygen-adsorbing species. This work provides an efficient way for fabricating noble metal NP-loaded MOSs with tunable gas-sensing properties.

Selective Photocatalytic Reduction of CO2 to CH4 Modulated by Chloride Modification on Bi2WO6 Nanosheets.

Solar-driven photocatalytic CO2 reduction into CH4 with H2O is considered to be a promising way to alleviate the energy crisis and greenhouse effect. However, current CO2 photoreduction technologies tend to overlook the role of photooxidation half reaction as well as the effect of the protons produced by water oxidation on CH4 generation, resulting in low CO2 conversion efficiency and poor CH4 selectivity. In the present study, a series of chloride-modified Bi2WO6 nanosheets were constructed in view of chloride-assisted photocatalytic water oxidation. The results show that the CH4 yield of the synthesized sample can be enhanced up to about 10 times compared to that with no Cl- modification. Besides, the selectivity of CH4 can be regulated by the loading amount of chloride, varying from 51.29% for Bi2WO6 to 94.98% for the maximum. The increase of product yield is attributed to chloride modification, which not only changed the morphology of the catalyst, but also modified the pathway of water oxidation. Further studies on intermediate products and the density functional theory calculation confirm that the Cl- ions on Bi2WO6 nanosheets not only promote H2O oxidation, but also lower the energy barrier for intermediate *CHO generation, thus facilitating CH4 production. The results gained herein may provide some illuminating insights into the design of a highly selective photocatalyst for efficient CO2 reduction.

N-Doped Graphene Quantum Dot-Decorated Three-Dimensional Ordered Macroporous In2O3 for NO2 Sensing at Low Temperatures.

Nitrogen dioxide (NO2) detection is of great importance because the emission of NO2 gas profoundly endangers the natural environment and human health. However, a few challenges, including lowering detection limit, improving response/recovery kinetics, and reducing working temperature, should be further addressed before practical applications. Herein, a series of N-doped graphene quantum dot (N-GQD)-modified three-dimensional ordered macroporous (3DOM) In2O3 composites are constructed and their NO2 response properties are studied. The results show that compared to pure 3DOM In2O3, reduced graphene oxide (rGO)/3DOM In2O3, and N-doped graphene sheets (NS)/3DOM In2O3, the N-GQDs/3DOM In2O3 sensing materials exhibit higher NO2 responses with fast response and recovery speed and low working temperature (100 °C). In addition, the detection limit of NO2 response for the optimal N-GQDs/In2O3 sensor is as low as 100 ppb. Upon exposure to CO, CH4, NH3, acetone, ethanol, toluene, and formaldehyde, only very weak responses could be observed, indicating good selectivity for the synthesized material. More attractively, the responses of the optimized N-GQDs/In2O3 sensor exhibit no obviously big fluctuation over 60 days, implying good long-term stability. We suggest that the formation of heterojunctions between 3DOM In2O3 and N-GQDs and the doping N atoms in N-GQDs play crucial roles in improving the NO2 sensing properties.

Co nanoparticles supported on three-dimensionally N-doped holey graphene aerogels for electrocatalytic oxygen reduction.

The reactive and stable catalysts for the oxygen reduction reaction are highly desirable for low temperature fuel cells. The commercial oxygen reduction reaction electrocatalysts generally reply on noble metal based nanomaterials, which suffer from inherent cost and selectivity issues. At present, it still remains challenge for designing efficient non-noble metal-based oxygen reduction reaction electrocatalysts. Herein, we successfully synthesize Co nanoparticles supported on three-dimensionally N-doped holey graphene aerogels hybrids by the high-temperature calcination of the graphene aerogels-polyallylamine-CoII hybrids. The component optimized hybrids show the excellent electrocatalytic activity for oxygen reduction reaction in alkaline media, which is comparable to commercial Pt/C electrocatalyst. Meanwhile, the hybrids also show eminent tolerance for CO and methanol, attributing to their excellent oxygen reduction reaction selectivity. The three-dimensionally interconnected structure of graphene aerogels, N-doping, uniform dispersion and high crystallinity of Co nanoparticles, and holey structure of graphene contribute to the striking oxygen reduction reaction activity of hybrids.

Self-template synthesis of defect-rich NiO nanotubes as efficient electrocatalysts for methanol oxidation reaction.

Developing robust and inexpensive non-noble metal based anode electrocatalysts is highly desirable for alkaline direct methanol fuel cells (ADMFCs). Herein, we successfully develop a facile self-template synthetic strategy for gram-grade porous NiO nanotubes (NTs) by pyrolyzing a nanorod-like Ni-dimethylglyoxime complex. The pyrolysis temperature highly correlates with the morphology and crystallinity of NiO NTs. The optimal NiO NTs exhibit a large electrochemically active surface area, a fast catalytic kinetics, and a small charge transfer resistance, which induce an outstanding electrocatalytic activity for the methanol oxidation reaction (MOR). Compared with conventional NiO nanoparticles, NiO NTs achieve a 11.5-fold increase in mass activity at 1.5 V for the MOR due to nanotubal morphology and abundant non-vacancy defects on the NiO NT surface. Moreover, NiO NTs have a higher electrocatalytic activity for the intermediates of the MOR (such as formaldehyde and formate) than conventional NiO nanoparticles, which also contribute to MOR activity enhancement. Given the facile synthesis and enhanced electrocatalytic performance, NiO NTs may be promising anode electrocatalysts for ADMFCs.

Carbonate doped Bi2MoO6 hierarchical nanostructure with enhanced transformation of active radicals for efficient photocatalytic removal of NO.

Doping heteroatoms in photocatalyst is an effective strategy to signally enhance the photocatalytic activity. Herein, we have favorably fabricated the carbonate doped Bi2MoO6 via a facile one-pot solvothermal method, which was verified by structure and constituent characterization analysis. In addition, the NO removal efficiency of carbonate-intercalated Bi2MoO6 is ~34%, far-exceeding that of the pure Bi2MoO6 (~13%), whilst exhibits a good stability and durability, owing to that the dopants could modulate the electron states of the Bi2MoO6, thus stimulating charge separation and migration, incenting transformation of reactive oxygen species and facilitating reactants activation, which are synthetically investigated by experimental characterization coupled with DFT calculation. Significantly, the in situ DRIFTS measurement was employed to dynamic monitor the NO oxidation process and clarify the photocatalytic mechanism under visible light irradiation. This work provides an efficient strategy to design photocatalysts with tunable motivating charge conversion and reactants activation towards NO photooxidation.

Rapid oxidation-etching synthesis of low-crystalline δ-MnO2 tubular nanostructures under ambient with high capacitance.

The 1D low-crystalline and ultrathin MnO2-RT nanotubes consisted of tiny nanoflakes are rapid synthesized at ambient temperature through a facile oxidation-etching method, where Cu nanowires are served as sacrificial templates. Meanwhile, the MnO2-RT nanotubes can be undergone further nucleation and growth to generate 3D porous MnO2 nanotubes by calcination treatment and hydrothermal reaction, respectively. Importantly, the high specific capacitance of 384.6 F g-1 is obtained at the current density of 0.25 A g-1 for the low-crystalline MnO2-RT nanotubes, owing to its ultra-thin wall thickness, high surface area and highly disordered structure. Furthermore, the cycle stability of the low-crystalline MnO2 nanotubes can be improved by hydrothermal treatment, owing to the enhanced crystallinity.

One-step hydrothermal synthesis of Cu-doped MnO2 coated diatomite for degradation of methylene blue in Fenton-like system.

In this work, we have synthesized Cu-doped MnO2@diatomite successfully though a one-step hydrothermal approach. Meanwhile, application for degradation of methylene blue in Fenton-like system was investigated. The compounds were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscope (XPS), Inductively Coupled Plasma analysis (ICP) and UV-vis spectroscopy measurements, beam scanning electron microscope (FIB/SEM), energy dispersive X-ray spectrometer (EDS). The observations revealed that copper was indeed intercalated into layered structure of MnO2 and Density functional theory (DFT) calculations predicted that Cu2+ intercalated MnO2@diatomite brought about the narrowing of band gap and the enhancing of charge mobility during catalysis. Electron Density Difference of CuMnD demonstrated excellent oxidation ability to dissociate H2O2 and generate hydroxyl radical (OH) to degrade the MB. Moreover, the proper copper doping of sample is more easily to form oxygen defect, which generate more surface hydroxyl groups as reaction sites for surface adsorption. In addition, the degradation efficiency of CuMnD was tremendously influenced by the initial pH, H2O2 dosage and copper content of catalyst. Ultimately, 0.02-25-CuMnD along with molar ration of Cu/Mn with 0.4402 showed the best degradation efficiency which was about 96.2% within 4 h with 16.5 mM of H2O2 and pH 2.06.

Cyanogel auto-reduction induced synthesis of PdCo nanocubes on carbon nanobowls: a highly active electrocatalyst for ethanol electrooxidation.

Direct ethanol fuel cells (DEFCs) with a high conversion efficiency are quite promising candidates for energy conversion devices. Herein, we have successfully synthesized PdCo alloy nanocubes supported on carbon nanobowl (denoted as Pd2Co1/CNB) nanohybrids by using the cyanogel auto-reduction method at high temperature. The morphology, composition and structure of Pd2Co1/CNB nanohybrids are characterized in detail, revealing that PdCo nanocubes have a high alloying degree and special {110} facets. In cyclic voltammetry measurements, Pd2Co1/CNB nanohybrids show a mass activity of 1089.0 A g Pd-1 and a specific activity of 40.03 mA cm-2 for ethanol electrooxidation at peak potential, which are much higher than that of the commercial Pd/C electrocatalyst (278.2 A gPd-1 and 8.22 mA cm-2). Additionally, chronoamperometry measurements show that Pd2Co1/CNB nanohybrids have excellent durability for ethanol electrooxidation. A high alloying degree, special {110} facets and the CNB supporting material contribute to the high activity and durability of Pd2Co1/CNB nanohybrids, making them a highly promising Pt-alternative electrocatalyst for ethanol electrooxidation in DEFCs.

Anion exchange of a cationic Cd(ii)-based metal-organic framework with potassium ferricyanide towards highly active Fe3C-containing Fe/N/C catalysts for oxygen reduction.

A highly active and stable Fe3C-containing Fe/N/C catalyst, derived from a cationic Cd(ii)-based metal-organic framework involving accurate control over Fe-doping via anion-exchange with potassium ferricyanide, shows superior oxygen reduction performance over the benchmark Pt/C catalyst in an alkaline electrolyte.

Tailoring the components and morphology of discharge products towards highly rechargeable Li-CO/CO2 batteries.

A new non-aqueous Li-CO/CO2 battery with the main discharge products being Li2CO3 and carbon is introduced for the first time. Our findings demonstrate that with the addition of CO, the components and morphology of the discharge products are skillfully tailored, becoming more uniform, with poorer crystallinity and better conductivity. Thanks to these features, the utilization of a cathode in the Li-CO/CO2 battery system is increased and the discharge products are more easily decomposed. These positive effects caused by CO endow the Li-CO/CO2 battery with enhanced electrochemical performances.

Synergistic photocatalysis of Cr(VI) reduction and 4-Chlorophenol degradation over hydroxylated α-Fe2O3 under visible light irradiation.

A series of Fe2O3 materials with hydroxyl are synthesized in different monohydric alcohol (C2-C5) solvents by solvothermal method and characterized by XRD, BET, XPS, TG and EA. The amount of hydroxyl is demonstrated to be emerged on the surface of the as-synthesized Fe2O3 particles and their contents are determined to be from 7.99 to 3.74 wt%. The Cr(VI) reduction experiments show that the hydroxyl content of Fe2O3 samples exacts great influence on the photocatalytic activity under visible light irradiation (λ>400 nm) and that the Fe2O3 sample synthesized in n-butyl alcohol exhibits the optimal photocatalytic activity. The synergistic photocatalysis for 4-Chlorophenol (4-CP) degradation and Cr(VI) reduction over above Fe2O3 sample is further investigated. The photocatalytic ratio of Cr(VI) reduction are enhanced from 24.8% to 70.2% while that of 4-CP oxidation are increased from 13.5% to 47.8% after 1 h visible light irradiation. The Fe2O3 sample keeps good degradation rates of mixed pollutants after 9 runs. The active oxygen intermediates O2(-)˙, ˙OH and H2O2 formed in the photoreaction process are discovered by ESR measurement and UV-vis test. The photocatalytic degradation mechanism is proposed accordingly.

Indirect Z-Scheme BiOI/g-C3N4 Photocatalysts with Enhanced Photoreduction CO2 Activity under Visible Light Irradiation.

Rational design and construction of Z-scheme photocatalysts has received much attention in the field of CO2 reduction because of its great potential to solve the current energy and environmental crises. In this study, a series of Z-scheme BiOI/g-C3N4 photocatalysts are synthesized and their photocatalytic performance for CO2 reduction to produce CO, H2 and/or CH4 is evaluated under visible light irradiation (λ > 400 nm). The results show that the as-synthesized composites exhibit more highly efficient photocatalytic activity than pure g-C3N4 and BiOI and that the product yields change remarkably depending on the reaction conditions such as irradiation light wavelength. Emphasis is placed on identifying how the charge transfers across the heterojunctions and an indirect Z-scheme charge transfer mechanism is verified by detecting the intermediate I3(-) ions. The reaction mechanism is further proposed based on the detection of the intermediate (•)OH and H2O2. This work may be useful for rationally designing of new types of Z-scheme photocatalyst and provide some illuminating insights into the Z-scheme transfer mechanism.

Greener synthesis of electrospun collagen/hydroxyapatite composite fibers with an excellent microstructure for bone tissue engineering.

In bone tissue engineering, collagen/hydroxyapatite (HAP) fibrous composite obtained via electrospinning method has been demonstrated to support the cells' adhesion and bone regeneration. However, electrospinning of natural collagen often requires the use of cytotoxic organic solvents, and the HAP crystals were usually aggregated and randomly distributed within a fibrous matrix of collagen, limiting their clinical potential. Here, an effective and greener method for the preparation of collagen/HAP composite fibers was developed for the first time, and this green product not only had 40 times higher mechanical properties than that previously reported, but also had an excellent microstructure similar to that of natural bone. By dissolving type I collagen in environmentally friendly phosphate buffered saline/ethanol solution instead of the frequently-used cytotoxic organic solvents, followed with the key step of desalination, co-electrospinning the collagen solution with the HAP sol, generates a collagen/HAP composite with a uniform and continuous fibrous morphology. Interestingly, the nano-HAP needles were found to preferentially orient along the longitudinal direction of the collagen fibers, which mimicked the nanostructure of natural bones. Based on the characterization of the related products, the formation mechanism for this novel phenomenon was proposed. After cross-linking with 1-ethyl-3-(3-dimethyl-aminopropyl)-1-carbodiimide hydrochloride/N-hydroxysuccinimide, the obtained composite exhibited a significant enhancement in mechanical properties. In addition, the biocompatibility of the obtained composite fibers was evaluated by in vitro culture of the human myeloma cells (U2-OS). Taken together, the process outlined herein provides an effective, non-toxic approach for the fabrication of collagen/HAP composite nanofibers that could be good candidates for bone tissue engineering.

Enhanced Photoreduction CO2 Activity over Direct Z-Scheme α-Fe2O3/Cu2O Heterostructures under Visible Light Irradiation.

Hematite-cuprous oxide (α-Fe2O3/Cu2O) nanocomposites are synthesized based on the design of Z-scheme photocatalyst for CO2 reduction. The band structure for the typical Fe2O3/Cu2O (with 1:1 mole ratio) is characterized by UV-vis reflectance spectroscopy and X-ray/ultraviolet photoelectron spectroscopy, and its heterojunction is determined to be Type II band alignment. The photoreduction CO2 activities of the heterostructures are investigated in the presence of water vapor. The CO yields are changed with Fe/Cu mole ratio, and the maximal CO yield attains 5.0 µmol·g cat(-1) after 3 h of visible-light irradiation. Besides the effect of light wavelength, H2O/CO2 molar ratio and temperature on the products is studied. The selectivity of the prepared catalysts is tunable by modulating the light wavelength. The reaction mechanism is proposed and further confirmed experimentally. The results gained herein may provide some insights into the design of Z-scheme photocatalysts for CO2 reduction.

Alkaline earth metal (Mg, Sr, Ba)-organic frameworks based on 2,2',6,6'-tetracarboxybiphenyl for proton conduction.

Three new alkaline earth metal based metal-organic frameworks (MOFs), namely M-BPTC (M = Mg, Sr, Ba), have been synthesized by using BPTC (2,2',6,6'-tetracarboxybiphenyl) as ligand under hydrothermal conditions. These MOFs exhibit interesting structural diversity, variable chemical and thermal stability, as well as proton conductivity. Mg-BPTC with the formula {[Mg(BPTC)0.5(H2O)3]·5H2O}n consists of BPTC(4-) extended metal layers, and novel highly ordered infinite tape-like structures of cyclic water octamers reside interlayer. Three-dimensional porous {[Sr2(BPTC)(H2O)6]·H2O}n (Sr-BPTC) features inorganic Sr-O chains (I(1)O(2)) and open hydrophilic channels where water heptamers and carboxyl oxygen atoms conspire to form H-bond networks, whereas 3D {[Ba6(BPTC)3(H2O)6]·11H2O}n (Ba-BPTC) shows Ba-O inorganic layer (I(2)O(1)) and 1D channels incorporating large water 14-mers and 18-mers. M-BPTC (M = Mg, Sr) species exhibit excellent water stability and proton conductivity due to their respective appropriate pathways for proton transporting. M-BPTC (M = Sr, Ba) structures are highly thermally stable due to the presence of the inorganic connectivity. The present results suggest that M-BPTC (M = Mg, Sr) are promising materials for proton conduction and provide insight into the hydrogen bonding motif.

Self-assembly of an imidazolate-bridged Fe(III)/Cu(II) heterometallic cage.

A rare, discrete, mixed-valent, heterometallic Fe(III)/Cu(II) cage, [Cu6Fe8L8](ClO4)12·χsolvent (H3L = tris{[2-{(imidazole-4-yl)methylidene}amino]ethyl}amine), was designed and synthesized via metal-ion-directed self-assembly with neutral tripodal metalloligands. The formation of this coordination cage was demonstrated by X-ray crystallography, ESI mass spectrometry, FT-IR, and UV-vis-NIR spectroscopy.