Ultralow RuO2 Doped NiS2 Heterojunction as a Multifunctional Electrocatalyst for Hydrogen Evolution linking to Biomass Organics Oxidation.

Hydrogen energy and biomass energy are green and sustainable forms that can solve the energy crisis all over the world. Electrocatalytic water splitting is a marvelous way to produce hydrogen and biomass platform molecules can be added into the electrolyte to reduce the overpotential and meanwhile are converted into some useful organics, but the key point is the design of electrocatalyst. Herein, ultralow noble metal Ru is doped into NiS2 to form RuO2@NiS2 heterojunction. Amongst them, the 0.06 RuO2@NiS2 has low overpotentials of 363 mV for OER and 71 mV for HER in 1 m KOH, which are superior to the RuO2 and Pt/C. Besides, the 0.06 RuO2@NiS2 shows a low overpotential of 173 mV in 1 m KOH+0.1 m glycerol, and the glycerol is oxidized to glyceraldehyde and formic acid via the high Faraday efficiency GlyOR process, and the splitting voltage is only 1.17 V. In addition, the 0.06 RuO2@NiS2 has a low overpotential of 206 mV in 1 m KOH+0.1 m glucose, and the glucose is converted to glucaric acid, lactic acid, and formic acid. This work has a "one stone three birds" effect for the production of hydrogen, low splitting voltage, and high-value-added biomass chemicals.

Ag Nanoparticles and Rod-Shaped AgCl Decorated Porous PEDOT as a Bifunctional Material for Hydrogen Evolution Catalyst and Supercapacitor Electrode.

PEDOT-Ag/AgCl is a highly promising material with dual functions of hydrogen evolution reaction (HER) and supercapacitors. In this study, a simple low-temperature stirring and light irradiation method was used to synthesize PEDOT-Ag/AgCl on the surface. Then, PEDOT-Ag/AgCl was analyzed using X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy. PEDOT-Ag/AgCl reacted in 1 M KOH alkaline electrolyte with an overpotential of 157 mV at 20 mA·cm-2 and a Tafel slope of 66.95 mv·dec-1. Owing to the synergistic effect of PEDOT and Ag/AgCl, this material had a small resistance (1.7 Ω) and a large specific capacitance (978 F·g-1 at current density of 0.5 A·g-1). The synthesis method can prepare nanostructured PEDOT with uniformly-distributed Ag nanoparticles and rod-shaped AgCl on the surface, which can be used as both HER electrocatalysts and supercapacitor electrodes.

Preparation and properties of lignin-based dual network hydrogel and its application in sensing.

Ionic conductive hydrogels prepared from various biological macromolecules are ideal materials for the manufacture of human motion sensors from the perspective of resource regeneration and environmental sustainability. However, it is now difficult to develop conductive hydrogels including excellent self-healing and mechanical properties, mainly due to their inherent trade-off between dynamic cross-linked healing and stable cross-linked mechanical strength. In this work, alkali lignin-Polyvinyl alcohol-polyacrylic acid double network conductive hydrogels with high mechanical strength and good self-healing properties were prepared. We formed the primary network structure by hydrogen bonding interaction between polyvinyl alcohol, alkali lignin and polyacrylic acid, and the secondary network structure by coordination interaction with polyacrylic acid through the addition of Fe3+. The added lignin acts as a dynamic linkage bridge in a porous network mediated by multiple ligand bonds, imparting superior mechanical properties to the hydrogels. The relationships between the alkali lignin and iron ion dosage and the comprehensive properties of hydrogels (adhesion, antibacterial, self-healing, electrical conductivity and mechanical properties) were studied in detail. On this basis, the hydrogels explored the role of lignin in the regulation of hydrogels properties and revealed the self-healing and conductive mechanism.

Iron clusters regulate local charge distribution in Fe-N4 sites to boost oxygen electroreduction.

The atomically-dispersed and nitrogen-coordinated iron (FeNC) on a carbon catalyst is a potential non-noble metal catalyst that can replace precious metal electrocatalysts. However, its activity is often unsatisfactory owing to the symmetric charge distribution around the iron matrix. In this study, atomically- dispersed Fe-N4 and Fe nanoclusters loaded with N-doped porous carbon (FeNCs/FeSAs-NC-Z8@34) were rationally fabricated by introducing homologous metal clusters and increasing the N content of the support. FeNCs/FeSAs-NC-Z8@34 exhibited a half-wave potential of 0.918 V, which exceeded that of the commercial benchmark Pt/C catalyst. Theoretical calculations verified that introducing Fe nanoclusters can break the symmetric electronic structure of Fe-N4, thus inducing charge redistribution. Furthermore, it can optimize a part of Fe 3d occupancy orbitals and accelerate OO fracture in OOH* (rate-determining step), thus significantly improving oxygen reduction reaction activity. This work provides a reasonably advanced pathway to modulate the electronic structure of the single-atom center and optimize the catalytic activity of single-atom catalysts.

Interface engineering Ni/Ni12P5@CNx Mott-Schottky heterojunction tailoring electrocatalytic pathways for zinc-air battery.

Due to the poor bifunctional electrocatalytic performances of electrocatalysts in zinc-air battery, herein, we first synthesized Ni/Ni12P5@CNx Mott-Schottky heterojunction to ameliorate the high-cost and instability of precious metals. We modulated the different contents of Ni and Ni12P5 in the Ni/Ni12P5@CNx Mott-Schottky heterojunction, and found that 0.6 Ni/Ni12P5@CNx has outstanding electrocatalytic performances, with half-wave potential of 0.83 V, and OER potential of 1.49 V at 10 mA cm-2. Also, the ΔE value is only 0.66 V. Moreover, 0.6 Ni/Ni12P5@CNx is assembled into ZAB, which has a high power density of 181 mW cm-2 and a high specific capacity of 710 mAh g-1. This indicates it has a good cycle stability. The density functional theory (DFT) calculations reveal that electrons spontaneously flow from Ni to Ni12P5 through the formed buffer layer in the Ni/Ni12P5@CNx Mott-Schottky heterojunction. The Schottky barrier formed modulates the electrocatalytic pathway to have good bifunctional electrocatalytic activity for ORR and OER.

A Scientometric Review: Biomass Gasification Study from 2006 to 2020.

Biomass gasification represents a significant way to produce energy from biomass. It features renewable properties and offers great potential for utilization. The application of biomass gasification products, design of the gasifier, type of biomass feedstock, gasification agents, and gasification parameters are key for the biomass gasification process. This work applies bibliometric approaches to provide a comprehensive and objective analysis of worldwide biomass gasification study trends over the period from 2006 to 2020 according to the Web Of Science core collection data. A total of 3222 articles associated with biomass gasification was retrieved, and its number grew annually. The subjects of study are diversified, primarily classified into "Energy & Fuels", "Engineering Chemical", and "Green Sustainable Science Technology". Moreover, Energy was a top published journal in the field of biomass gasification. Austrian contributors had the majority of publications, next to China and the USA. Liejin Luo from Xi'an Jiaotong University possessed the greatest H-index. Keyword evaluation showed that biomass gasification is a current hotspot, among which life-cycle assessment, sustainability, and deep processing of gasification products are future research directions. This work is predicted to offer further research interest in biomass gasification.

Fabrication of lignin reinforced hybrid hydrogels with antimicrobial and self-adhesion for strain sensors.

Ionic conductive hydrogels prepared from various biological macromolecules are ideal materials for the manufacture of human motion sensors from the perspective of resource regeneration and environmental sustainability. However, it is still challenging to prepare hydrogels with both high toughness and self-healing ability. In this study, lignin-based ß-CD-PVA (LCP) self-healing conductive hydrogels with high tensile properties were prepared by one-step method using alkali lignin as a plasticizer. Compared with PVA hydrogel, the maximum storage modulus and elongation were increased by 2.5 and 20.0 times, respectively. Uniform distribution of lignin can increase the fluidity and distance of polymer molecular chains, thus improving the viscoelastic and tensile properties of the LCP self-healing hydrogel. LCP hydrogels can maintain self-healing ability in both high (45 °C) and low temperature (0 °C) environments, and the self-healing ability is not affected by pH. Moreover, it also has good conductivity, anti-bacterial, thermostability, and anti-UV property, which has a good application prospect in the field of 3D printing and wearable electronic devices, which expands the efficient utilization of lignin in biorefinery.

An Efficient Catalyst Derived from Carboxylated Lignin-Anchored Iron Nanoparticle Compounds for Carbon Monoxide Hydrogenation Application.

Catalytic activity and target product selectivity are strongly correlated to the size, crystallographic phase, and morphology of nanoparticles. In this study, waste lignin from paper pulp industry is employed as the carbon source, which is modified with carboxyl groups at the molecular level to facilitate anchoring of metals, and a new type of carbon-based catalyst was obtained after carbonization. As a result, the size of the metal particles is effectively controlled by the chelation between -COO- and Fe3+. Furthermore, Fe/CM-CL with a particle size of 1.5-2.5 nm shows excellent catalytic performance, the conversion of carbon monoxide reaches 82.3%, and the selectivity of methane reaches 73.2%.

Biochar Nanocomposite Derived from Watermelon Peels for Electrocatalytic Hydrogen Production.

Water splitting is the most potential method to produce hydrogen energy, however, the conventional electrocatalysts encounter the hindrances of high overpotential and low hydrogen production efficiency. Herein, we report a carbon-based nanocomposite (denoted as CCW-x, x stands for the calcination temperature) derived from watermelon peels and CoCl2, and the as-synthesized CCW-x is used as the electrocatalyst. The overpotential and the Tafel slope of CCW-700 for oxygen evolution reaction (OER) is 237 mV at 10 mA cm-2 and 69.8 mV dec-1, respectively, both of which are lower than those of commercial RuO2. For hydrogen evolution reaction (HER), the overpotential of CCW-700 (111 mV) is higher than that of the widely studied Pt/C (73 mV) but still lower than those of lots of carbon-based nanomaterials (122-177 mV). In the light of CCW-700 is highly active for both OER and HER, we assembled a water-splitting electrocatalyst by employing nickel foam loaded with CCW-700 as the anode and cathode in 1 M KOH. The water-splitting voltage is only 1.54 V for the CCW-700//CCW-700 electrodes and 1.62 V for the RuO2//Pt/C ones. Therefore, the so-denoted CCW-x powder possesses good electrocatalytic hydrogen production efficiency.

Metal Organic Framework (MOF)/Wood Derived Multi-cylinders High-Power 3D Reactor.

3D monolithic reactor has shown great promise for varied heterogeneous catalysis reactions including water treatment, energy generation and storage, and clean fuel production. As a natural porous material, macroporous wood is regarded as an excellent support for inorganic catalyst due to its abundant polar functional groups and channels. On the other hand, a metal organic framework (MOF) has been widely used as heterogeneous catalyst due to its high specific surface area and large amount of microporosities. Combining macroporous wood and a microporous MOF is expected to produce a high-performance 3D reactor and is demonstrated here for Fischer-Tropsch synthesis. The carbonized MOF/wood reactor retains the original cellular structure with over 180 000 channels/cm2. When being decorated with hexagonal-shaped core-shell Co@C nanoparticles aggregates derived from Co-MOF, the MOF/wood reactor resembles a multi-cylinders reactor for Fischer-Tropsch synthesis. Because of the unique combination of macro- and microporous hierarchical structure, the 3D MOF/wood reactor demonstrates exceptional performance under high gas hourly space velocity (81.2% CO conversion and 48.5% C5+ selectivity at 50 L·h-1·gcat-1 GHSV). This validates that MOF/wood can serve as a multi-cylinders and high-power reactor for catalytic reactions, which is expected to be applicable for environmental and energy applications.

Flexible and Super Thermal Insulating Cellulose Nanofibril/Emulsion Composite Aerogel with Quasi-Closed Pores.

Because of the prevailing environment and energy challenges, there has been a growing interest in biobased materials for thermal insulation application. Although cellulose aerogel has been considered as an excellent thermal insulating material, its thermal conductivity is generally negatively affected by the interconnected internal pores. Herein, it is demonstrated that a cellulose nanofibril (CNF)/emulsion composite aerogel with quasi-closed internal pores can be facilely fabricated by Pickering emulsion templating and solvent exchange methods. The CNF-stabilized oil-in-water Pickering emulsion (with an average diameter of 1.3 µm) can be converted into quasi-closed pores by sequential solvent exchange to acetone and tert-butanol (TBA), followed by freeze-drying from TBA to suppress the formation of large ice crystals. The presence of quasi-closed pores from emulsion templating is verified by both confocal microscopy and scanning electron microscopy images and is confirmed to reduce thermal conductivity to as low as 15.5 mW/(m K). Compared to the CNF aerogel, increasing emulsion content can lead to better volume retention with significantly reduced density (11.4 mg/cm3), increased mesoporosity, and enhanced specific modulus (18.2 kPa/(mg/cm3)) and specific yield strength (1.6 kPa/(mg/cm3)). In addition, the CNF/emulsion composite aerogel also demonstrates superb flexibility and infrared shielding performance.

Lignin-Derived Graphene-Like Carbon Nanosheets as an Efficient Catalyst Support for Fischer-Tropsch Synthesis.

Bio-renewable lignin has been used as a precursor for the preparation of various carbon materials, such as carbon fibers, ordered mesoporous carbon and graphite carbon cages. Nevertheless, up to now, there are few studies about prepare graphene-like carbon nanosheets derived from lignin. In this study, we synthesized graphene-like carbon nanosheets, using lignin as the precursor, via one-step pyrolysis route. Fortunately, physical and chemical characterization results indicate that it has high pore volume and hierarchical pore with wrinkled sheet graphene structure. Furthermore, the capability of graphene-like carbon nanosheets was investigated as a catalyst support in Fischer-Tropsch synthesis. The results of catalytic evaluation show that Fe2O3/GCNs has excellent catalytic activity and the selectivity of lower olefins, compared with Fe2O3/AC.

Facile Synthesis of Z-Scheme Ag3PO4/Sulfur-Doped g-C3N4 Heterojunction Hybrids with Enhanced Visible Light Photocatalytic Performance.

Ag3PO4/sulfur-doped g-C3N4 heterojunctions were fabricated by the means of a facile calcination and co-precipitation method. Structural characterization suggested that Ag3PO4 was successfully loaded onto sulfur-doped g-C3N4. The absorption band edges of sulfur-doped g-C3N4 were shifted to the longer wavelength in comparison with bulk g-C3N4. The Ag3PO4/sulfur-doped g-C3N4 heterojunctions manifested substantially higher visible-light photocatalytic performance as compared with Ag3PO4/bulk g-C3N4. Photoluminescence spectra suggested that the stable Ag3PO4/SGCN heterojunctions could effectively address the electron-hole recombination rate, together with remarkably enhancing the photocatalytic activity. The enhancement of light absorption and better dispersion in Ag3PO4/sulfur-doped g-C3N4 provide more migration channels, together with posing crucial responsibility for the enhanced photocatalytic performance.

ZnO nanorod arrays grown on g-C3N4 micro-sheets for enhanced visible light photocatalytic H2 evolution.

The designed synthesis of noble-metal-free photocatalysts with hierarchical heteroassemblies in a facile, mild and eco-friendly way becomes more and more important, because we can explore the novel properties and applications of novel heterostructures via this method. Herein we report a two-step aqueous strategy for novel hierarchical heterostructures of ZnO nanorod (NR) arrays grown on graphitic carbon nitride (g-C3N4). The novel g-C3N4/ZnO NR heterostructures that integrate g-C3N4 and ZnO NR via high-quality g-C3N4-ZnO heterojunctions have beneficial properties such as high specific surface area (SSA), open spatial architecture, good electronic conductivity, and effective charge transfer interfaces, and are promising in many related areas such as water splitting, solar cells, etc. As a noble-metal-free and visible-light-responsive photocatalytic material, a typical g-C3N4/ZnO NR photocatalytic system exhibits enhanced photocatalytic activity toward H2 evolution, almost 3.5 times higher than that of pure g-C3N4. The superior photocatalytic property can be ascribed to the synergistic effect of the unique g-C3N4/ZnO NR heterostructures.

Carbon quantum dots as a fluorophore for "inner filter effect" detection of metronidazole in pharmaceutical preparations.

With houttuynia cordata as carbon source, photoluminescent carbon quantum dots (CDs) were obtained via a one-step hydrothermal procedure. The absorption band of metronidazole (MNZ, maximum absorption wavelength at 319 nm) can well overlap with the excitation bands of CDs (maximum excitation wavelength at 320 nm). A fluorescent approach has been developed for detection of MNZ based on the inner filter effect (IFE), in which as-prepared CDs act as an IFE fluorophore and the MNZ as an IFE absorber. We have investigated the mechanism of quenching the fluorescence of CDs and found that the IFE leads to an exponential decay in fluorescence intensity of CDs with increasing concentration of MNZ, but showed a good linear relationship (R 2 = 0.9930) between ln(F 0/F) with the concentration of MNZ in the range of 3.3 × 10-6 to 2.4 × 10-4 mol L-1. Due to the absence of surface modification of the CDs or establishing any covalent linking between the absorber (MNZ) and the fluorophore (CDs), the developed method is simple, rapid, low-cost and less time-consuming. Meanwhile, it possesses a higher sensitivity, wider linear range, and satisfactory selectivity and has potential application for detection of MNZ in pharmaceutical preparations.

2D molybdenum nitride nanosheets as anode materials for improved lithium storage.

Two-dimensional (2D) molybdenum nitride (MoN) nanosheets are promising anode materials for improved lithium-ion batteries. However, the reported synthesis methods of MoN generally rely on high-temperature and complex procedures with low cost efficiency. Herein, we report a facile one-pot synthesis of 2D MoN nanosheets at a low temperature of 400 °C via a solid-state reaction of molybdenum disulfide, sulfur and sodium amide in an autoclave. When employed as the anode material for lithium ion batteries, the as-developed MoN electrode exhibits outstanding cyclability with a high capacity retention of 898 mA h g-1 over 400 cycles at a current rate of 200 mA g-1 as well as a superb rate capability with a capacity of 505 mA h g-1 at a high rate up to 2 A g-1. The excellent lithium storage performance of the MoN electrode is attributed to its advantageously high conductivity and unique 2D nanostructure.

Effect of graphitic carbon modification on the catalytic performance of Fe@SiO2-GC catalysts for forming lower olefins via Fischer-Tropsch synthesis.

Mesoporous silica-encapsulated iron materials contribute to the suppression of self-aggregation and thereby enhances the Fischer-Tropsch synthesis activity. However, constructing Fe-based supported catalysts with high activity and selectivity in the Fischer-Tropsch synthesis to lower olefins (FTO) by a conventional mesoporous silica support has been proven challenging due to its low hydrothermal stability and low reducibility. Herein, we developed a core-shell Fe@SiO2-GC structure with an optimized interface of the catalyst by introducing graphitic carbon (GC) that weakened the Fe-SiO2 interaction. Transmission electron microscopy and nitrogen adsorption-desorption characterization proved GC-modified catalysts had well-defined core-shell structures. The Fe@SiO2-GC-2 containing the optimal GC content had the largest surface area and pore volume, and outperformed Fe2O3@SiO2 in terms of CO conversion (60.1%) and C2-C4 olefin selectivity (40.7%) within 100 h. The significant improvement of FTO performance was attributed to the rigid porous framework of GC, which allowed free access of syngas and inhibited mesoporous channel collapse during FTO, so the catalytic activity and stability were improved by the synergism between higher Fe dispersion and reducibility. Moreover, the narrow well-defined mesoporous channel also exerted a modest spatial restriction effect, which inhibited the formation of long-chain hydrocarbon and tailored the product distribution toward lower distillate, thus improving the selectivity toward C2-C4.

Influence of Molecular Weight on Structure and Catalytic Characteristics of Ordered Mesoporous Carbon Derived from Lignin.

Bio-renewable lignin has been used as a carbon source for the preparation of porous carbon materials. Nevertheless, up to now, there are few studies about the influence of molecular weight of lignin on the structure and morphology of the ordered mesoporous carbon. Here, we synthesized the ordered mesoporous carbon derived from different molecular weights of lignin and Pluronic F127. Fortunately, we found that molecular weight is an important factor for obtaining highly ordered channels, high specific surface area, and ordered mesoporous carbon. More importantly, the narrow well-defined mesoporous channel could exert a spatial restriction effect to some extent, which can serve as nanoreactors for efficient reactions and enhance catalytic performance. The highly ordered mesoporous carbon from lignin is a good candidate for Fischer-Tropsch synthesis catalyst supports.

Development of a Novel Terpolymer as a Green and Efficient Decalcifying Agent for Crude Petroleum.

A novel environmental decalcifying agent was prepared with allylpolyethoxy amino carboxylate (APEAA), hydroxyethyl acrylate (HEA), and maleic anhydride (MA) by means of free-radical polymerization in an aqueous solution. The morphology and structure of the samples were characterized through scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectrometry, and 1H nuclear magnetic resonance (1H NMR) spectra. The molecular-weight distribution of APEAA-HEA-MA was determined by the gel permeation chromatography method. APEAA-HEA-MA was used as a green decalcifying agent to remove calcium from crude petroleum, and the impact of factors such as monomer ratio, copolymerization time, dosages, and desalination temperature was analyzed. It is found that the decalcification rate of APEAA-HEA-MA could reach to its maximum, and the calcium removal efficiency was approximately 97.88% when the monomer molar ratio of APEAA-HEA-MA was 1:2:5, the reaction time of copolymerization was 2 h, the dosage was 100 ppm, and the desalination temperature was 100 °C. This research work can promote the exploration on facile synthesis of a novel terpolymer and its potential application in refinery desalting processes.

Uniformity dispersive, anti-coking core@double-shell-structured Co@SiO2@C: Effect of graphitic carbon modified interior pore-walls on C5+ selectivity in Fischer-Tropsch synthesis.

Highly dispersed Co nanoparticles with proper interaction with mesoporous support are benefit for the suppression of self-aggregation, which enhances its Fischer-Tropsch synthesis (FTs) activity. However, construct such Co based supported catalysts with high activity and stability in FTs by conventional mesoporous support, especially the common used mesoporous SiO2, has proven challenging due to their undesirable hydrothermal stability and poor reducibility. Herein, we developed a unique core@double-shell Co@SiO2@C structure with optimized interface of the mesoporous catalyst by introducing graphitic carbon layer which can weaken the interaction between metallic Co and silica. Transmission electron microscopy (TEM) images, together with Nitrogen adsorption-desorption characterization result, proved the well-defined core@double-shell structure of graphitic carbon modified catalyst. The Co@SiO2@C-2 material produced after optimizing the calcination temperature to 600°C process large surface area and pore volume, and show higher CO conversion (62.2%) and C5+ selectivity (62.2%) than Co3O4@SiO2 in a period of 100h. The significant improvement in the FTS performance of Co@SiO2@C is not only attributed to a good synergistic effect by a combination of the Co dispersion and reducibility. The unique core@double-shell structure with graphitic carbon modified interior pore-walls also contributes to the formation of heavy hydrocarbon, as well as the protecting with the metallic Co particles away from oxidation and aggregation.