Lab-on-Device Synthesis of Hierarchical Macro/Mesoporous WO3 Semiconducting Films for High-Performance H2S Sensing.

The performance consistency of the gas sensor is strongly dependent on the interface binding between the sensitive materials and the electrodes. Traditional powder coating methods can inevitably lead to differences in terms of substrate-film interface interaction and device performance, affecting the stability and lifetime. Thus, efficient growth of sensitive materials on device substrates is crucial and essential to enhance the sensing performance, especially for stability. Herein, hierarchically ordered macro/mesoporous WO3 films are in situ synthesized on the electrode via a facile soft/hard dual-template strategy. Orderly arrayed uniform polystyrene (PS) microspheres with tailored size (ca. 1.2 µm) are used as a hard template, and surfactant Pluronic F127 as a soft template can co-assemble with tungsten precursor into ordered mesostructure in the interstitials of PS colloidal crystal induced by solvent evaporation. Benefiting from its rich porosity and high stability, the macro/mesoporous WO3-based sensor shows high sensitivity (Rair/Rgas = 307), fast response/recovery speed (5/9 s), and excellent selectivity (SH2S/Smax > 7) toward 50 ppm H2S gas (a biomarker for halitosis). Significantly, the sensors exhibit an extended service life with a negligible change in sensing performance within 60 days. This lab-on-device synthesis provides a platform method for constructing stable nanodevices with good consistency and high stability, which are highly desired for developing high-performance sensors.

Facile and scalable synthesis of functionalized hierarchical porous polymers for efficient uranium adsorption.

Efficient uranium capture from wastewater holds great importance for the environmental remediation and sustainable development of nuclear energy, but it is a tremendous challenge. Herein, a facile and scalable approach is reported to fabricate functionalized hierarchical porous polymers (PPN-3) decorated with high density of phosphate groups for uranium adsorption. The as-constructed hierarchical porous structure could allow rapid diffusion of uranyl ions, while abundant phosphate groups that serve as adsorption sites could provide the high affinity for uranyl. Consequently, PPN-3 shows a high uranium adsorption uptake of 923.06 mg g-1 and reaches adsorption equilibrium within simply 10 min in uranium-spiked aqueous solution. Moreover, PPN-3 affords selective adsorption of uranyl over multiple metal ions and possesses a rapid and high removal rate of U(VI) in real water systems. Furthermore, this study offers direct polymerization strategy for the cost-effective fabrication of phosphate-functionalized porous organic polymers, which may provide promising application potential for uranium extraction.

Construction of a highly efficient adsorbent for one-step purification of recombinant proteins: Functionalized cellulose-based monolith fabricated via phase separation method.

Currently, purification step in the recombinant protein manufacture is still a great challenge and its cost far outweighs those of the upstream process. In this study, a functionalized cellulose-based monolith was constructed as an efficient affinity adsorbent for one-step purification of recombinant proteins. Firstly, the fundamental cellulose monolith (CE monolith) was fabricated based on thermally induced phase separation, followed by being modified with nitrilotriacetic acid anhydride through esterification to give NCE monolith. After chelating with Ni2+, the affinity adsorbent NCE-Ni2+ monolith was obtained, which was demonstrated to possess a hierarchically porous morphology with a relatively high surface area, porosity and compressive strength. The adsorption behavior of NCE-Ni2+ monolith towards ß2-microglobulin with 6 N-terminus His-tag (His-ß2M) was evaluated through batch and fixed-bed column experiments. The results revealed that NCE-Ni2+ monolith exhibited a relatively fast His-ß2M adsorption rate with a maximum adsorption capacity of 329.2 mg/g. The fixed-bed column adsorption implied that NCE-Ni2+ monolith showed high efficiency for His-ß2M adsorption. Finally, NCE-Ni2+ monolith was demonstrated to have an excellent His-ß2M purification ability from E. coli lysate with exceptional reusability. Therefore, the resultant NCE-Ni2+ monolith had large potential to be used as an efficient adsorbent for recombinant protein purification in practical applications.

Confined growth of Ultrathin, nanometer-sized FeOOH/CoP heterojunction nanosheet arrays as efficient self-supported electrode for oxygen evolution reaction.

Self-supported electrodes, featuring abundant active species and rapid mass transfer, are promising for practical applications in water electrolysis. However, constructing efficient self-supported electrodes with a strong affinity between the catalytic components and the substrate is of great challenge. In this study, by combining the ideas of in-situ construction and space-confined growth, we designed a novel self-supported FeOOH/cobalt phosphide (CoP) heterojunctions grown on a carefully modified commercial Ni foam (NF) with three-dimensional (3D) hierarchically porous Ni skeleton (FeOOH/CoP/3D NF). The specific porous structure of 3D NF directs the confined growth of FeOOH/CoP catalyst into ultra-thin and small-sized nanosheet arrays with abundant edge active sites. The active FeOOH/CoP component is stably anchored on the rough pore wall of 3D NF support, leading to superior stability and improved conductivity. These structural advantages contributed to a highly facilitated oxygen evolution reaction (OER) activity and enhanced durability of the FeOOH/CoP/3D NF electrode. Herein, the FeOOH/CoP/3D NF electrode afforded a low overpotential of 234 mV at 10 mA cm-2 (41 mV smaller than FeOOH/CoP grown on unmodified Ni foam) and high stability for over 90 h, which is among the top reported OER catalysts. Our study provides an effective idea and technique for the construction of active and robust self-supported electrodes for water electrolysis.

Hierarchically porous cellulose-based carbon aerogels with N-doped skeletons and encapsulated iron-based catalysts for efficient tetracycline catalytic degradation.

Three-dimensional interpenetrating and hierarchically porous carbon material is an efficient catalyst support in water remediation and it is still a daunting challenge to establish the relationship between hierarchically porous structure and catalytic degradation performance. Herein, a highly porous silica (SiO2)/cellulose-based carbon aerogel with iron-based catalyst (FexOy) was fabricated by in-situ synthesis, freeze-drying and pyrolysis, where the addition of SiO2 induced the hierarchically porous morphology and three-dimensional interpenetrating sheet-like network with nitrogen doping. The destruction of cellulose crystalline structure by SiO2 and the iron-catalyzed breakdown of glycosidic bonds synergistically facilitated the formation of electron-rich graphite-like carbon skeleton. The unique microstructure is confirmed to be favorable for the diffusion of reactants and electron transport during catalytic process, thus boosting the catalytic degradation performance of carbon aerogels. As a result, the catalytic degradation efficiency of tetracycline under light irradiation by adding only 5 mg of FexOy/SiO2 cellulose carbon aerogels was as high as 90 % within 60 min, demonstrating the synergistic effect of photocatalysis and Fenton reaction. This ingenious structure design provides new insight into the relationship between hierarchically porous structure of carbon aerogels and their catalytic degradation performance, and opens a new avenue to develop cellulose-based carbon aerogel catalysts with efficient catalytic performance.

Biomineralization-Inspired Confined-Space Fabrication of Polyimide Aerogels.

The biomineralization process endows biominerals with unique hierarchically porous structures and physical-chemical properties by filling the restricted microreaction space with amorphous phases before the growth of inorganic crystals. In this paper, a confined-space fabrication method inspired by biomineralization for preparing hierarchically porous polyimide (PI) aerogels and PI-derived carbon aerogels is introduced. The confined structure is established through a self-assembly method of vacuum impregnation and ultrasound-assisted freeze-drying. The hierarchically porous structure is controlled by adjusting the structure characteristics of the confined space and secondary aerogels. Subsequently, a variety of performance demonstrations are conducted to demonstrate the mechanical properties and application prospects in the fields of thermal insulation and electromagnetic shielding of the prepared aerogel.

Facile Synthesis of Hierarchically Porous Ni-N-C for Efficient CO2 Electroreduction to CO.

The reasonable design of atomically dispersed Ni-Nx sites in porous carbon nanostructures is an efficient strategy to enhance the electrochemical CO2 reduction reaction (CO2RR) catalytic activity. In this work, atomically dispersed Ni-Nx sites on hierarchically porous carbon catalysts (HP-Ni-NC) were fabricated by a facile NaCl template-assisted pyrolysis method. The catalysts exhibit a large specific surface area and a hierarchical porous structure, facilitating the exposure of numerous active sites and the mass/electron transport during the CO2RR. Consequently, the CO Faradaic efficiency maintained over 90% in a wide potential window on the optimized HP-Ni-NC-2 catalyst. The CO partial current achieved 15.2 mA cm-2 at -0.9 V (vs reversible hydrogen electrode) in a H-cell. Furthermore, the current density can achieve 250 mA cm-2 at a cell voltage of 3.11 V in a membrane electrode assembly electrolyzer, demonstrating great promise for commercial-scale application. This study presents a facile approach to synthesizing hierarchically porous structure single-atom catalysts with superior catalytic performance toward CO2RR.

Synthesis of Hierarchically Porous Bioactive Glass and Its Mineralization Activity.

Mesoporous bioactive glass is a promising biomaterial for bone tissue engineering due to its good biocompatibility and bioactivity. In this work, we synthesized a hierarchically porous bioactive glass (HPBG) using polyelectrolyte-surfactant mesomorphous complex as template. Through the interaction with silicate oligomers, calcium and phosphorus sources were successfully introduced into the synthesis of hierarchically porous silica, and HPBG with ordered mesoporous and nanoporous structures was obtained. The morphology, pore structure and particle size of HPBG can be controlled by adding block copolymer as co-template or adjusting the synthesis parameters. The ability to induce hydroxyapatite deposition in simulated body fluids (SBF) demonstrated the good in vitro bioactivity of HPBG. Overall, this work provides a general method for the synthesis of hierarchically porous bioactive glasses.

3D ordered amorphous and porous TiO2 framework anode with low insertion barrier and fast kinetics for K-ion hybrid capacitors.

TiO2 is considered as a low cost, long-term stable, and safe anode for high power K-ion hybrid capacitors (KICs) due to its abundant reserve, small volume expansion rate, and sloping voltage plateau that avoids K-ion plating at high voltage polarization. However, the enhancement of its low capacity and sluggish kinetics caused by poor electroconductivity and high insertion barrier is still challenging to further develop high-performance KICs. Herein, the reduced graphene oxide (rGO) is embedded in the walls of 3D ordered macro-/mesoporous TiO2 (termed as TiO2@rGO framework) to create intimate TiO2/rGO interfaces, ensuring the effectively electron transportation during potassiation/depotassiation of TiO2 while maintaining rapid ions/electrolyte diffusion. Furthermore, the controlled amorphous TiO2 framework can further lower the lattice insertion energies, contributing to a fast accommodation of K-ion. As expected, the amorphous TiO2@rGO framework (TiO2@rGO-1) exhibits a superior rate capability (148.8 mAh g-1 at 5 A g-1) and cycling stability (171.2 mAh g-1 at 1 A g-1 after 800 cycles). The assembled KICs can reach a high energy/power density of 125.2 Wh kg-1/4267.4 W kg-1 as well as a long-term lifespan. This tactic provides a reliable and general way to design a TiO2-based anode with fast kinetics toward high-performance KICs.

Green-Manufactured and Recyclable Coatings for Subambient Daytime Radiative Cooling.

Passive daytime radiative cooling, which reflects sunlight and simultaneously emits heat into space to cool surfaces without energy input, is a promising strategy for energy conservation. Integrating radiative cooling with building systems can tremendously alleviate electrical cooling, but manufacturing high-efficient and eco-friendly coatings remains an urgent and challenging task. Here, we present a simple and scale-up strategy for fabricating ultrawhite coatings consisting of porous ethyl cellulose matrix-random BaSO4 nanoparticles utilizing green solvents. With the synergistic effect of the ideal intrinsic properties of the materials and the strong Mie scattering of the porous structure, the ultrawhite coating possesses a record solar reflectance of 98.6% and a thermal emittance of 98.1%, resulting in a subambient temperature drop of over 2.5 °C under a solar intensity of ∼920 W m-2. Better yet, our coatings can be conveniently brushed, rolled, or sprayed onto various types of substrates, with excellent durability, self-cleaning, and cost-effectiveness, paving an attractive and viable pathway for large-scale applications in practical buildings.

A Single-Atom Fe-N-C Catalyst with Ultrahigh Utilization of Active Sites for Efficient Oxygen Reduction.

Fe-N-C single-atom catalysts (SACs) are emerging as a promising class of electrocatalysts for the oxygen reduction reaction (ORR) to replace Pt-based catalysts. However, due to the limited loading of Fe for SACs and the inaccessibility of internal active sites, only a small portion of the sites near the external surface are able to contribute to the ORR activity. Here, this work reports a metal-organic framework-derived Fe-N-C SAC with a hierarchically porous and concave nanoarchitecture prepared through a facile but effective strategy, which exhibits superior electrocatalytic ORR activity with a half-wave potential of 0.926 V (vs RHE) in alkaline media and 0.8 V (vs RHE) in acidic media while maintaining excellent stability. The superior ORR activity of the as-designed catalyst stems from the unique architecture, where the hierarchically porous architecture contains micropores as Fe SAC anchoring sites, meso-/macro-pores as accessible channels, and concave shell for increasing external surface area. The unique architecture has dramatically enhanced the utilization of previously blocked internal active sites, as confirmed by a high turnover frequency of 3.37 s-1 and operando X-ray absorption spectroscopy analysis with a distinct shift of adsorption edge.

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.

Sawdust-Derived Activated Carbon with Hierarchical Pores for High-Performance Symmetric Supercapacitors.

The recyclable utilization of waste biomass is increasingly important for the development of a sustainable society. Here, the sawdust-derived activated carbon (SD-AC) has been prepared via a convenient H3PO4-based activation method and further trialed as an electrode for use as a high-performance symmetric supercapacitor. The as-prepared SD-AC possesses a hierarchically porous structure with micropores (0.55 nm) and mesopores (2.58 nm), accounting for its high specific surface area of 621 m2 g-1, with a pore volume of 0.35 cm3 g-1. Such a hierarchically porous structure can offer a favorable pathway for fast ion penetration and transportation, enhancing its electrochemical performance. As a result, the SD-AC electrode exhibits a maximum specific capacitance of up to 244.1 F g-1 at 1.0 A g-1, a high rate capability (129.06 F g-1 at 20 A g-1), and an excellent cycling performance, with 87% retention over 10,000 cycles at 10 A g-1. Of particular note is that the SD-AC-based symmetric supercapacitor achieves a maximum energy density of 19.9 Wh kg-1 at the power density of 650 W kg-1, with a long-term cycle lifespan. This work showcases the recyclable utilization of waste biomass for the preparation of high-value activated carbon for efficient energy storage.

Biomass Alginate Derived Oxygen-Enriched Carbonaceous Materials with Partially Graphitic Nanolayers for High Performance Anodes in Lithium-Ion Batteries.

Lithium-ion batteries with high reversible capacity, high-rate capability, and extended cycle life are vital for future consumer electronics and renewable energy storage. There is a great deal of interest in developing novel types of carbonaceous materials to boost lithium storage properties due to the inadequate properties of conventional graphite anodes. In this study, we describe a facile and low-cost approach for the synthesis of oxygen-doped hierarchically porous carbons with partially graphitic nanolayers (Alg-C) from pyrolyzed Na-alginate biopolymers without resorting to any kind of activation step. The obtained Alg-C samples were analyzed using various techniques, such as X-ray diffraction, Raman, X-ray photoelectron spectroscopy, scanning electron microscope, and transmission electron microscope, to determine their structure and morphology. When serving as lithium storage anodes, the as-prepared Alg-C electrodes have outstanding electrochemical features, such as a high-rate capability (120 mAh g-1 at 3000 mA g-1) and extended cycling lifetimes over 5000 cycles. The post-cycle morphologies ultimately provide evidence of the distinct structural characteristics of the Alg-C electrodes. These preliminary findings suggest that alginate-derived carbonaceous materials may have intensive potential for next-generation energy storage and other related applications.

Iron Single Atom Catalyzed Quinoline Synthesis.

The production of high-value chemicals by single-atom catalysis is an attractive proposition for industry owing to its remarkable selectivity. Successful demonstrations to date are mostly based on gas-phase reactions, and reports on liquid-phase catalysis are relatively sparse owing to the insufficient activation of reactants by single-atom catalysts (SACs), as well as, their instability in solution. Here, mechanically strong, hierarchically porous carbon plates are developed for the immobilization of SACs to enhance catalytic activity and stability. The carbon-based SACs exhibit excellent activity and selectivity (≈68%) for the synthesis of substituted quinolines by a three-component oxidative cyclization, affording a wide assortment of quinolines (23 examples) from anilines and acetophenones feedstock in an efficient, atom-economical manner. Particularly, a Cavosonstat derivative can be synthesized through a one-step, Fe1 -catalyzed cyclization instead of traditional Suzuki coupling. The strategy is also applicable to the deuteration of quinolines at the fourth position, which is challenging by conventional methods. The synthetic utility of the carbon-based SAC, together with its reusability and scalability, renders it promising for industrial scale catalysis.

An azine-based polymer derived hierarchically porous N-doped carbon for hydrophilic dyes removal.

In this study, a novel hierarchically porous N-doped carbon (HPNC) material was successfully prepared by soft-templating method. The commercial triblock copolymer of Pluronic F127 and a polyazine derived from hydrazine hydrate & glyoxal were used as soft template and precursor, respectively. The obtained materials were fully characterized and tested as a sorbent for the removal of hydrophilic dyes of Methylene blue (MB), Basic Fuchsin (BF), Eosin Y (EY) and Rhodamine B (RB) from their aqueous effluents. According to the characterization results, the synthesized material of HPNC-1000 presented thick fibrous morphology with micron size in diameter, hierarchically porous structure with surface area of 1853 m2/g, pore volume of 1.59 cm3/g and nitrogen content of 4.5 wt%. Adsorption-desorption investigation reveals that synergistic effect of hydrophobic interaction and hydrogen-bonding formation of the dye molecules with the sorbent was most pronounced in the adsorptions. The maximum adsorption capacities for MB, BF, EY and RB reached 0.83, 0.92, 1.23 and 1.83 mmol g-1, respectively. The adsorption processes well fitted by the pseudo first-order kinetic model and the Liu's isotherm. The sorbent can be regenerated by above 90% of the initial adsorption efficiency after six regeneration cycles.

Embedding Co3O4 nanoparticles in three-dimensionally ordered macro-/mesoporous TiO2 for Li-ion hybrid capacitor.

Lithium-ion hybrid capacitors (LICs) have gained increasing focus owing to their high energy/power densities. The development of anodes with superior rate capability is an effective way to surmount the kinetic mismatch between anodes and cathodes, and thus, enhancing the energy/power densities. Herein, Co3O4 nanoparticles embedded in three-dimensionally (3D) ordered macro-/mesoporous TiO2 (Co3O4@TiO2) are synthesized through an in situ method from dual templates. Differing from the composite prepared by loading active nanoparticles on support, Co3O4 nanoparticles are embedded in TiO2 framework, which can improve the stability of the electrode. Furthermore, the hierarchically porous structure of TiO2 is in favor of the rapid diffusion of ions and electrolyte. As a result, The Co3O4@TiO2-2 composite with an optimized Co3O4 content (~25 wt%) delivers a high capacity of 944.1 mAh g-1 after 100 cycles at 0.1 A g-1 and high-rate capability (405.7 mAh g-1 after 1000 cycles at 5 A g-1). The LIC assembled with Co3O4@TiO2-2 anode and activated carbon (AC) cathode delivers high energy/power densities (maximum, 87.9 Wh kg-1/10208.9 W kg-1) and great cycle stability (88.1%, 6000 cycles, 0.5 A g-1).

Dual-Carbon Electrode-Based High-Energy-Density Potassium-Ion Hybrid Capacitor.

Potassium-ion hybrid capacitors (KIHCs) have attracted growing attention due to the natural abundance and low cost of potassium. However, KIHCs are still limited by sluggish redox reaction kinetics in electrodes during the accommodation of large-sized K+. Herein, a starch-derived hierarchically porous nitrogen-doped carbon (SHPNC) anode and active carbon cathode were rationally designed for dual-carbon electrode-based KIHCs with high energy density. The hierarchical structure and rich doped nitrogen in the SHPNC anode result in a distensible interlayer space to buffer volume expansion during K+ insertion/extraction, offers more electrochemical active sites to achieve high specific capacity, and has highly efficient channels for fast ion/electron transports. The in situ Raman and ex situ TEM demonstrated a reversible electrochemical behavior of the SHPNC anode. Thus, the SHPNC anode delivers superior cycling stability and a high reversible capacity (310 mA h g-1 at 50 mA g-1). In particular, the KIHCs assembled by the SHPNC anode and commercial active carbon cathode can deliver a high energy density of 165 W h kg-1 at a current density of 50 mA g-1 and an ultra-long cycle life of 10,000 cycles at 1 A g-1 (calculated based on the total mass of the anode and cathode).

Coexisting Single-Atomic Fe and Ni Sites on Hierarchically Ordered Porous Carbon as a Highly Efficient ORR Electrocatalyst.

The development of oxygen reduction reaction (ORR) electrocatalysts based on earth-abundant nonprecious materials is critically important for sustainable large-scale applications of fuel cells and metal-air batteries. Herein, a hetero-single-atom (h-SA) ORR electrocatalyst is presented, which has atomically dispersed Fe and Ni coanchored to a microsized nitrogen-doped graphitic carbon support with unique trimodal-porous structure configured by highly ordered macropores interconnected through mesopores. Extended X-ray absorption fine structure spectra confirm that Fe- and Ni-SAs are affixed to the carbon support via FeN4 and NiN4 coordination bonds. The resultant Fe/Ni h-SA electrocatalyst exhibits an outstanding ORR activity, outperforming SA electrocatalysts with only Fe- or Ni-SAs, and the benchmark Pt/C. The obtained experimental results indicate that the achieved outstanding ORR performance results from the synergetic enhancement induced by the coexisting FeN4 and NiN4 sites, and the superior mass-transfer capability promoted by the trimodal-porous-structured carbon support.

Nitrogen, Sulfur Co-Doped Hierarchically Porous Carbon as a Metal-Free Electrocatalyst for Oxygen Reduction and Carbon Dioxide Reduction Reaction.

High-cost and low-efficiency electrocatalysts have hindered oxygen reduction reaction (ORR) in fuel cells and CO2 reduction reaction (CO2RR) for producing fuels and value-added chemicals. Here, a low-cost metal-free electrocatalyst of a N, S co-doped hierarchically porous carbon (NSHPC) for efficient ORR and CO2RR is reported. The NSHPC is prepared by pyrolysis of glucosamine hydrochloride and thiocyanuric acid precursors using SiO2 as hard templates. The N, S co-doping effectively enhances catalytic activity and selectivity, and the hierarchically porous structure largely exposes abundant active sites to reaction species and facilitates electrolyte transport, thereby leading to significantly increased catalytic activities for the NSHPC. The resultant NSHPC exhibits excellent electrocatalytic activities toward ORR in both acidic and alkaline electrolytes and also shows application in proton exchange membrane fuel cells (PEMFCs). More importantly, the NSHPC enables CO2 reduction to CO with 87.8% maximum Faraday efficiency (FE) in aqueous electrolytes. This work offers a novel insight into the development of multifunctional electrocatalysts for producing electricity, fuels, and value-added chemicals.