Preparation of mesoporous biogas residue biochar via a self-template strategy for efficient removal of ciprofloxacin: Effect of pyrolysis temperature.

Biochar preparation and application is an anticipated pathway for the resource utilization of biogas residue. In this study, biochars were prepared by the pyrolysis of biogas residue from food waste anaerobic digestion (named as BRBCs) under various pyrolysis temperatures (300, 500, 700, and 900 °C), and the effect of pyrolysis temperatures on the physicochemical characteristics of BRBCs was examined. The adsorption performance toward ciprofloxacin (CIP), a typical antibiotic in waterbodies, was also investigated. The results showed that pyrolysis temperature significantly changed the physicochemical properties of BRBCs. In addition, the minerals in the biogas residue, especially SiO2, were rearranged to form a mesoporous structure in biochar through a self-template strategy (without activator). BRBC prepared at 900 °C exhibited a high specific surface area and pore volume, well-developed mesopore structure, and more carbon structure defects, and exhibited the largest CIP adsorption capacity with 70.29 mg g-1, which was ascribed to the combined interaction of pore diffusion, π-π interactions, hydrogen bonding, complexation, and electrostatic forces. Furthermore, the adsorption of CIP by BRBC900 was well described by two-compartment kinetic and Langmuir isotherm models. BRBC900 showed good adsorption performance toward CIP at pH 7-9. The adsorption of CIP by BRBC is a spontaneous, exothermic, entropy-increasing process. Moreover, BRBC also presented a good recycling potential. Therefore, the preparation of mesoporous biochar based on a self-template strategy not only provides an option for the resource utilization of biogas residue but also offers a new option for the treatment of antibiotic wastewater.

N-Containing Porous Carbon-Based MnO Composites as Anode with High Capacity and Stability for Lithium-Ion Batteries.

MnO has attracted much attention as the anode for Li-ion batteries (LIBs) owing to its high specific capacity. However, the low conductivity limited its large application. An effective solution to solve this problem is carbon coating. Biomass carbon materials have aroused much interest for being low-cost and rich in functional groups and hetero atoms. This work designs porous N-containing MnO composites based on the chemical-activated tremella using a self-templated method. The tremella, after activation, could offer more active sites for carbon to coordinate with the Mn ions. And the as-prepared composites could also inherit the special porous nanostructures of the tremella, which is beneficial for Li+ transfer. Moreover, the pyrrolic/pyridinic N from the tremella can further improve the conductivity and the electrolyte wettability of the composites. Finally, the composites show a high reversible specific capacity of 1000 mAh g-1 with 98% capacity retention after 200 cycles at 100 mA g-1. They also displayed excellent long-cycle performance with 99% capacity retention (relative to the capacity second cycle) after long 1000 cycles under high current density, which is higher than in most reported transition metal oxide anodes. Above all, this study put forward an efficient and convenient strategy based on the low-cost biomass to construct N-containing porous composite anodes with a fast Li+ diffusion rate, high electronic conductivity, and outstanding structure stability.

A Hexagonal Nut-Like Metal-Organic Framework and Its Conformal Transformation.

Hollow structured metal-organic frameworks (MOFs) and their derivatives are desired in catalysis, energy storage, etc. However, fabrication of novel hollow MOFs and revelation of their formation mechanisms remain challenging. Herein, open hollow 2D MOFs in the form of hexagonal nut are prepared through self-template method, which can be readily scaled up at gram scale in a one-pot preparation. The evolution from the initial superstructure to the final stable MOFs is tracked by wide-angle X-ray scattering, transforming from solid hexagon to open hollow hexagon. More importantly, this protocol can be extended to synthesizing a series of open hollow structured MOFs with sizes ranging from ≈120 to ≈1200 nm. Further, open hollow structured cobalt/N-doped porous carbon composites are realized through conformal transformation of the as-prepared MOFs, which demonstrates promising applications in sustainable energy conversion technologies. This study sheds light on the kinetically controlled synthesis of novel 2D MOFs for their extended utilizations.

One-dimensional cobalt oxide nanotubes with rich defect for oxygen evolution reaction.

For the electrochemcial hydrogen production, the oxygen evolution reaction (OER) is a pivotal half-reaction in water splitting. However, OER suffers sluggish kinetics and high overpotential, leading to the increase of overall energy consumption and decrease of the energy efficiency. In this work, high-quality cobalt oxide porous nanotubes (Co3O4-PNTs) are easily obtained by simple self-template approach. One-dimensional (1D) porous structure provides the large specific surface area, enough abundant active atoms and effective mass transfer. In addition, Co3O4-PNTs also own self-stability of 1D architecture, benefitting the their durability for electrocatalytic reaction. Thus, Co3O4-PNTs with optimal annealing temperature and time reveal the attractive alkaline OER performance (Tafel slope of 56 mV dec-1and 323 mV overpotential at 10 mA cm-2), which outperform the Co3O4nanoparticles and benchmark commercial RuO2nanoparticles. Furthermore, Co3O4-PNTs also exhibit excellent OER durability for least 10 h at the 10 mA cm-2. Overall, Co3O4-PNTs with low cost can be serve as a highly reactive and economical catalyst for OER.

Self-template synthesis of flower-like hierarchical graphene/copper oxide@copper(II) metal-organic framework composite for the voltammetric determination of caffeic acid.

Flower-like graphene/CuO@Cu-BTC (GR/CuO@Cu-BTC) composite was employed as electrode material for the voltammetric determination of caffeic acid (CA) in the wine. The composite material was prepared via the self-template method. In this synthetic process, budlike CuO not only acts as the template, but also provides Cu2+ ions for in situ growth of the Cu-BTC shell. The utilization of GR as petal greatly boosts the stability and electronic conductivity of CuO@Cu-BTC. The GR/CuO@Cu-BTC composite possesses unique structural features with high specific surface area and good conductivity, exhibiting excellent electrocatalytic activity towards the oxidation of CA. Under optimized conditions, the sensor shows a good linear response to CA concentration over the range 0.020-10.0 µM, together with a low limit of detection (LOD) of 7.0 nM. Selectivity, reproducibility, and stability were investigated, and the method has been applied for the determination of CA in wine samples. Graphical abstract Schematic representation of electrochemical sensor for the detection of caffeic acid was designed based on flower-like graphene/copper oxide@copper(II) metal-organic framework (GR/CuO@Cu-BTC) composite electrode material.

Self-Template-Directed Metal-Organic Frameworks Network and the Derived Honeycomb-Like Carbon Flakes via Confinement Pyrolysis.

Metal-organic frameworks (MOFs) have become a research hotspot since they have been explored as convenient precursors for preparing various multifunctional nanomaterials. However, the preparation of MOF networks with controllable flake morphology in large scale is not realized yet. Herein, a self-template strategy is developed to prepare MOF networks. In this work, layered double-metal hydroxide (LDH) and other layered metal hydroxides are used not only as a scaffold but also as a self-sacrificed metal source. After capturing the abundant metal cations identically from the LDH by the organic linkers, MOF networks are in situ formed. It is interesting that the MOF network-derived carbon materials retain the flake morphology and exhibit a unique honeycomb-like macroporous structure due to the confined shrinkage of the polyhedral facets. The overall properties of the carbon networks are adjustable according to the tailored metal compositions in LDH and the derived MOFs, which are desirable for target-oriented applications as exemplified by the electrochemical application in supercapacitors.

Self-Templated Synthesis of Co- and N-Doped Carbon Microtubes Composed of Hollow Nanospheres and Nanotubes for Efficient Oxygen Reduction Reaction.

A facile, self-templated strategy for the synthesis of Co- and N-doped carbon microtubular structures composed of nanoscale hollow spheres and nanotubes is proposed. Cobalt oxalate microtubes serve simultaneously as the solid cobalt precursor for the in situ conversion reaction to metal-organic framework and self-templates for the 1D tubular structure.

Self-template-directed synthesis of porous perovskite nanowires at room temperature for high-performance visible-light photodetectors.

The unique optoelectronic properties and promising photovoltaic applications of organolead halide perovskites have driven the exploration of facile strategies to synthesize organometal halide perovskites and corresponding hybrid materials and devices. Currently, the preparation of CH3 NH3 PbBr3 perovskite nanowires, especially those with porous features, is still a great challenge. An efficient self-template-directed synthesis of high-quality porous CH3 NH3 PbBr3 perovskite nanowires in solution at room temperature using the Pb-containing precursor nanowires as both the sacrificial template and the Pb(2+) source in the presence of CH3 NH3 Br and HBr is now presented. The initial formation of CH3 NH3 PbBr3 perovskite layers on the surface of the precursor nanowires and the following dissolution of the organic component of the latter led to the formation of mesopores and the preservation of the 1D morphology. Furthermore, the perovskite nanowires are potential materials for visible-light photodetectors with high sensitivity and stability.

Ultrathin Carbon Sheet Obtained by Self-Template Method toward Highly Effective Charge Transfer for Si-Based Anodes.

A dynamic and stable charge transfer process is the key to exerting lithium storage characteristics of the silicon anode with a large volume change. In this work, the composite with an ultrathin carbon sheet skeleton is prepared by freeze-drying and a copyrolysis process after uniformly mixing citric acid and hydroxylated Si NPs, which is different from traditional conformal carbon coating derived from citric acid. A flexible carbon sheet reduces internal particle (Si-OH@NC) slip and cooperates with interfacial Si-O-C bonding to buffer machinal stress in the electrode during cycling. More importantly, the carbon sheet network increases the point-to-surface contact area between the active material and the conductive agent, ensures continuous electrical connection from the current collector to the active material, and promotes a rapid and stable electron transfer process. Besides, the N-doped C structure with remarkable nucleophilicity guarantees fast ion transport, which is confirmed by theoretical calculation. In this way, the reaction reversibility of the Si-based electrode is further realized during cycles. As a result, the electrode delivers excellent cycle performance (reversible capacity of 1001.9 mAh g-1 at 1 A g-1 after 500 cycles) and rate performance (capacity retention of 86.8 and 65.8% at 1 and 3 A g-1, respectively, compared to 0.2 A g-1). The idea of constructing a highly efficient electrode conductive network through a doped-carbon sheet network is also applicable to other active materials with huge volume changes during lithium storage.

Reducing Carbonaceous Salts for Facile Fabrication of Monolayer Graphene.

Novel methods and mechanisms for graphene fabrication are of great importance in the development of materials science. Herein, a facile method to directly convert carbonaceous salts into high-quality freestanding graphene via a simple one-step redox reaction, is reported. The redox couple can be a combination of sodium borohydride (reductant) and sodium carbonate (oxidant), which can readily react with each other when evenly mixed/calcined and yield gram-scale, high-quality, contamination-free, micron-sized, freestanding graphene. More importantly, this method is applicable to a variety of input reductants and oxidants that are low cost and easily accessible. An in-depth investigation reveals that the carbonaceous oxidants can not only provide reduced carbon mass for graphene formation but also act as a self-template to guide the polymerization of carbon atoms following the pattern of the monolayer, six-carbon rings. In addition, the direct formation of graphene exhibits theoretically lower energy barriers than that of other allotropes such as fullerene and carbon nanotube. This facile, low-cost, scalable, and applicable method for mass production of high-quality graphene is expected to revolutionize graphene fabrication technology and boost its practical application to the industry level.

Hierarchical porous biochar from kelp: Insight into self-template effect and highly efficient removal of methylene blue from water.

Biochar is known to efficiently remove dyes especially for biochar with hierarchical pores and partial N-species. Here, a facile pyrolysis is used to yield N-doped biochar from kelp without additives, showing surface areas of 771 m2/g as temperature up to 1000 °C and hierarchical small-sized mesopores (2-4 nm) and wide meso-macropores (8-60 nm). A possible self-template mechanism from inorganics is proposed to form hierarchical pore architecture in biochar and used for methylene blue (MB) removal. Biochar pyrolyzed at 1000 °C is found to be efficient for MB removal with uptake of 379.8 mg/g under ambient conditions, one of the largest ever recorded uptakes for other biochar without activation, owing to synergistic effects of high surface areas, mesopores, and graphitized N-species. These results confirm that a facile pyrolysis for transformation of kelp into efficient dyes adsorbent is a cost-effective process for economic and environmental protection.

Novel Bilayer-Shelled N, O-Doped Hollow Porous Carbon Microspheres as High Performance Anode for Potassium-Ion Hybrid Capacitors.

With the advantages of high energy/power density, long cycling life and low cost, dual-carbon potassium ion hybrid capacitors (PIHCs) have great potential in the field of energy storage. Here, a novel bilayer-shelled N, O-doped hollow porous carbon microspheres (NOHPC) anode has been prepared by a self-template method, which is consisted of a dense thin shell and a hollow porous spherical core. Excitingly, the NOHPC anode possesses a high K-storage capacity of 325.9 mA h g-1 at 0.1 A g-1 and a capacity of 201.1 mAh g-1 at 5 A g-1 after 6000 cycles. In combination with ex situ characterizations and density functional theory calculations, the high reversible capacity has been demonstrated to be attributed to the co-doping of N/O heteroatoms and porous structure improved K+ adsorption and intercalation capabilities, and the stable long-cycling performance originating from the bilayer-shelled hollow porous carbon sphere structure. Meanwhile, the hollow porous activated carbon microspheres (HPAC) cathode with a high specific surface area (1472.65 m2 g-1) deriving from etching NOHPC with KOH, contributing to a high electrochemical adsorption capacity of 71.2 mAh g-1 at 1 A g-1. Notably, the NOHPC//HPAC PIHC delivers a high energy density of 90.1 Wh kg-1 at a power density of 939.6 W kg-1 after 6000 consecutive charge-discharge cycles.

A porous carbon based on the surface and structural regulation of wasted lignin for long-cycle lithium-ion battery.

Lignin, as the second most abundant source in nature, is considered as a good precursor for hard carbon. However, direct carbonization of pure lignin leads to low surface area and porosity. Herein we develop a method to prepare lignin-based porous carbon by a self-template method assisted with surface modification. The oxygen-containing functional groups are introduced to regulate the surface chemistry of lignin. And the metal ions are chosen to coordinate with the oxygen-containing group in the lignin, which can form the carbonates to act as the self template to regulate the pores structure. The aromatic skeleton of lignin can also disperse the metal ions to bring uniform pore-forming sites. The results show that the carbonized lignin modified by chloroacetic acid (CCL) shows mesopores with surface area of 233.4384 m2 g-1. As anode for lithium-ion batteries (LIBs), the CCL shows a specific capacity of 500 mAh g-1 at 50 mA g-1. The capacity retention was 99 % after 1000 cycles at 1000 mA g-1, which are superior to most reported carbon anode. This work proposes a low-cost anode for LIBs and put forward a regulation strategy for bio-mass carbon. Besides, it would reduce the discard of lignin and alleviate the pollution.

Self-template synthesis of mesoporous vanadium oxide nanospheres with intrinsic peroxidase-like activity and high antibacterial performance.

Mesoporous vanadium oxide nanospheres are a very promising nanozyme for antibacterial and chemical sensing. However, controllable synthesis of mesoporous vanadium oxide nanospheres with uniform structure and small diameter (<200 nm) remains challenging. Herein, mesoporous vanadium oxide nanospheres (MVONs) with a small, uniform and adjustable particle size (52-105 nm), large mesopore size (5.1-5.8 nm), and high specific surface area (up to 63.7 m2 g-1) are constructed via a self-template strategy using tannic acid, formaldehyde and vanadium compounds as a polymerizable ligand, cross-linking agent and metal source, respectively. The relationships between synthesis conditions and material nanostructure are systematically investigated. The particle size and peroxidase-like activity of MVONs can be easily changed by adding different amounts of Pluronic block copolymer F127. Owing to the mesoporous structure, high specific surface area and small particle size, MVONs can effectively convert H2O2 into extremely toxic reactive oxygen species, and further kill Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). This research establishes a universal, reliable method for synthesizing mesoporous vanadium oxide nanospheres, which might be used in catalysis, biosensors, and antibacterial treatment.

Synthesis of Mesoporous Ag2O/SnO2 Nanospheres for Selective Sensing of Formaldehyde at a Low Working Temperature.

Formaldehyde (HCHO) is a prevalent indoor gas pollutant that has been seriously endangering human health. Developing semiconductor metal oxide (SMO) gas sensors for selective measurement of formaldehyde at low working temperatures remains a great challenge. In this work, silver/tin-polyphenol hybrid spheres are applied as a sacrificial template for the fabrication of spherical mesoporous Ag2O/SnO2 sensing materials. The obtained mesoporous Ag2O/SnO2 spheres have a uniform particle size (∼80 nm), large pore size (5.8 nm), and high specific surface area (71.3 m2 g-1). The response is 140 toward formaldehyde (10 ppm) at a low working temperature (75 °C). The detection limit reaches a low level of 23.6 ppb. Most importantly, it has excellent selectivity toward interfering gases. When the concentration of the interfering gas (e.g., ethanol) is 5 times as high as that of formaldehyde, the response is little affected. Theoretical calculations suggest that the addition of Ag2O can significantly enhance the adsorption energy toward formaldehyde, thus improving formaldehyde sensing performance. This work demonstrates an efficient self-template synthesis strategy for noble metal catalyst-decorated mesoporous metal oxide spheres, which could boost gas sensing performance at a lower working temperature.

Sodium alginate-derived porous carbon: Self-template carbonization mechanism and application in capacitive energy storage.

Sodium alginate (SA) is an environment-friendly and low-cost polysaccharide carbohydrate extracted from seaweed. As a carbon precursor, sodium alginate has the advantages of clear molecular structure, small molecular weight, and easy controls of the structure and composition of the product, but there have been few studies for the mechanism for SA carbonization. In this work, the carbon skeleton cross-linking mode, heteroatom doping and defect generation mechanism in the process of SA pyrolysis are clarified. Subsequently, based on the understanding of the carbonization mechanism of SA-derived carbon, we have prepared a stable SA-derived interconnected porous carbon by self-template method. The materials prepared by this method possess high oxygen content (17.6 at%) and high specific surface area (384.4 m2 g-1). Zn-ion hybrid capacitors (ZICs) device assembled with SA-derived porous carbon performs superior energy densities (based on cathode mass) of 78.35 and 35.56 Wh kg-1 at the power densities of 160 and 5120 W kg-1, respectively. This work deeply explained the carbonization mechanism of sodium alginate and evaluated the application prospects of SA-based carbon in ZICs comprehensively.

Molten Salt Self-Template Synthesis Strategy of Oxygen-Rich Porous Carbon Cathodes for Zinc Ion Hybrid Capacitors.

Porous carbon materials are widely used in capacitive energy storage devices because of their chemical stability, low cost, and controllable textures. Molten salt self-template methods are powerful and sustainable synthesis strategies for preparing porous carbons with tunable pore textures and surface chemistries. Herein, we propose a self-template synthesis strategy for preparing oxygen-rich porous carbons (ORC) by directly carbonizing potassium chloroacetate (ClCH2COOK) as the single carbon source. The potassium chloride salts generated in the carbonization play the roles of the template and etchant agent in the pore formation process. The as-prepared ORC samples feature abundant mesopores (average pore sizes of 1.95-2.19 nm and mesopore ratio of 36.4%), high specific surface areas (1410-1886 m2 g-1), and high oxygen doping levels (4.3-8.2 atom %). The zinc ion hybrid capacitors with an ORC cathode exhibited an ultrahigh capacitance of 308 F g-1 at 0.5 A g-1 and a high energy density of 136.5 Wh kg-1 at a power density of 570 W kg-1. Density functional theory demonstrates that oxygen-containing functional groups are conducive to the adsorption of Zn ions. Our work proposes a general synthesis methodology for the synthesis of oxygen-rich porous carbons for a variety of electrochemical energy storage devices.

Boosting lithium-ion storage performance by ultrafine bimetal carbides nanoparticles coupled with Hollow-like carbon composites.

Metallic carbides demonstrated tremendous application potential in energy conversion field deriving from their distinctive electrochemical activity and chemical stability. Herein, a molybdenum-based hybrid self-template strategy was adopted to confine ultrafine molybdenum carbides and tungsten carbides nanoparticles in N, P-codoped carbon nanotubes (MoC/WC@N, P-CNTs) for enhanced lithium-ion storage. Specifically, hierarchical MoW-polydopamine nanotubes were prepared via a self-template strategy, which employed Mo3O10(C6H8N)2·2H2O nanowires as the template. Ultrafine MoC and WC nanoparticles embedded in ultrathin carbon nanosheets could be obtained rationally after carbonization treatment, which could not only prevent carbides nanoparticles from agglomeration and oxidation, but also endow the rapid electron transfer rate. Thus, MoC/WC@N, P-CNTs displayed outstanding lithium storage abilities with great rate property and long-term cycling durability. The stable specific capacity of 475.0 mAh g-1 could be preserved at high current intensity of 5.0 A g-1 after 1000 cycles, which was one of the best performances for metal carbides anodes. Furthermore, the successful fabrication of lithium-ion hybrid capacitors (LIHCs) delivered the maximum energy density of 117 Wh kg-1 and power density of 6571 W kg-1. Moreover, the superior capacity retention of 89.7 % after 2000 cycles also indicated the excellent cycling stability. The present work highlights a self-template strategy for designing nanostructures toward efficient energy storage and conversion fields.

Self-Template Synthesis of Nitrogen-Doped Hollow Carbon Nanospheres with Rational Mesoporosity for Efficient Supercapacitors.

Rational design and economic fabrication are essential to develop carbonic electrode materials with optimized porosity for high-performance supercapacitors. Herein, nitrogen-doped hollow carbon nanospheres (NHCSs) derived from resorcinol and formaldehyde resin are successfully prepared via a self-template strategy. The porosity and heteroatoms in the carbon shell can be adjusted by purposefully introducing various dosages of ammonium ferric citrate (AFC). Under the optimum AFC dosage (30 mg), the as-prepared NHCS-30 possesses hierarchical architecture, high specific surface area up to 1987 m2·g-1, an ultrahigh mesopore proportion of 98%, and moderate contents of heteroatoms, and these features endow it with a high specific capacitance of 206.5 F·g-1 at 0.2 A·g-1, with a good rate capability of 125 F·g-1 at 20 A·g-1 as well as outstanding electrochemical stability after 5000 cycles in a 6 M KOH electrolyte. Furthermore, the assembled NHCS-30 based symmetric supercapacitor delivers an energy density of 14.1 W·h·kg-1 at a power density of 200 W·kg-1 in a 6 M KOH electrolyte. This work provides not only an appealing model to study the effect of structural and component change on capacitance, but also general guidance to expand functionality electrode materials by the self-template method.

Self-Template Synthesis of Prussian Blue Analogue Hollow Polyhedrons as Superior Sodium Storage Cathodes.

Prussian blue and its analogues with three-dimensional frame structures have been shown to be of great importance in the research and development of sodium-ion batteries (SIBs). Herein, we develop a simple and convenient self-template method to prepare a hollow-structured Prussian blue analogue (CoFe-PBA). This structure is conducive to buffer the volume changes during ion extraction and insertion processes and shorten the ion diffusion path. When further building a thin polydopamine (PDA) coating, the synthesized CoFe-PBA@PDA exhibits a high discharge capacity of 123.1 mAh g-1 at 0.1 A g-1 with a capacity retention of 71.5% after 500 cycles. Moreover, the capacity retention of CoFe-PBA@PDA after 100 cycles is 14.3% higher than that of the two comparison samples. In addition, the reversible structure of CoFe-PBA@PDA without forming a new phase was verified by in situ X-ray diffraction. This work may provide another design idea or strategy for improving the stability of the PBA cathodes used in SIBs.