Selective Adsorption of Hazardous Substances from Wastewater by Hierarchical Oxide Composites: A Review.

Large volumes of wastewater containing toxic contaminants (e.g., heavy metal ions, organic dyes, etc.) are produced from industrial processes including electroplating, mining, petroleum exploitation, metal smelting, etc., and proper treatment prior to their discharge is mandatory in order to alleviate the impacts on aquatic ecosystems. Adsorption is one of the most effective and practical methods for removing toxic substances from wastewater due to its simplicity, flexibility, and economics. Recently, hierarchical oxide composites with diverse morphologies at the micro/nanometer scale, and the combination advantages of oxides and composite components have been received wide concern in the field of adsorption due to their multi-level structures, easy functionalization characteristic resulting in their large transport passages, high surface areas, full exposure of active sites, and good stability. This review summarizes the recent progress on their typical preparation methods, mainly including the hydrothermal/solvothermal method, coprecipitation method, template method, polymerization method, etc., in the field of selective adsorption and competitive adsorption of hazardous substances from wastewater. Their formation processes and different selective adsorption mechanisms, mainly including molecular/ion imprinting technology, surface charge effect, hard-soft acid-base theory, synergistic effect, and special functionalization, were critically reviewed. The key to hierarchical oxide composites research in the future is the development of facile, repeatable, efficient, and scale preparation methods and their dynamic adsorption with excellent cyclic regeneration adsorption performance instead of static adsorption for actual wastewater. This review is beneficial to broaden a new horizon for rational design and preparation of hierarchical oxide materials with selective adsorption of hazardous substances for wastewater treatment.

A dew-responsive pectin-based herbicide for enhanced photodynamic inactivation.

5-aminolevulinic acid (5-ALA) has been fully demonstrated as a biodegradable, without resistance, and pollution-free pesticide. However, the lack of targeting and the poor adhesion result in a low utilization rate, limiting its practical application. Herein, a dew-responsive polymer pro-pesticide Pec-hyd-ALA was successfully synthesized by grafting 5-ALA onto the pectin (PEC) backbone via acid-sensitive acylhydrazone bonds. When the pro-pesticide is exposed to acid dew on plant surfaces at night, 5-ALA is released and subsequently converted to photosensitize (Protoporphyrin IX, PpIX)in plant cells, leading to its accumulation and promoting photodynamic inactivation (PDI). An inverted fluorescence microscope has verified the accumulation of tetrapyrrole in plant cells. In addition, the highly bio-adhesive PEC backbone effectively improved the wetting and retention of 5-ALA on leaves. The pot experiment also demonstrated the system's control effect on barnyard grass. This work provides a promising approach to improving the herbicidal efficacy of 5-ALA.

Enhanced adsorption of roxarsone on iron-nitrogen co-doped biochar from peanut shell: Synthesis, performance and mechanism.

Efficient removal of organic arsenic (roxarsone, ROX) from wastewater is highly demanded on the purpose of human health and environmental protection. This work aims to prepare Fe-N co-doped biochar (Fe-N-BC) via one-pot hydrothermal method using waste peanut shell, FeCl3·6H2O and urea, followed by pyrolysis. The effect of Fe-N co-doping on biochar's physicochemical properties, and adsorption performance for ROX were systematically investigated. At the pyrolysis temperature of 650 °C, Fe-N-BC-650 shows a significantly increased specific surface area of 358.53 m2/g with well-developed micro-mesoporous structure. Its adsorption capacity for ROX reaches as high as 197.32 mg/g at 25 °C, with > 90 % regeneration efficiency after multiple adsorption-desorption cycles. Correlation and spectral analysis revealed that the pore filling, π-π interactions, as well as hydrogen bonding play the dominant role in ROX adsorption. These results suggest that the Fe-N co-doped biochar shows great potential in the ROX removal from wastewater with high efficiency.

A pectin-based photoactivated bactericide nanosystem for achieving an improved utilization rate, photostability and targeted delivery of hematoporphyrin.

Photoactivated pesticides have many advantages, such as high activity, low toxicity, and no drug resistance. However, poor photostability and a low utilization rate limit their practical application. Herein, the photosensitizer hematoporphyrin (HP) was used as a photoactivated pesticide, covalently linked with pectin (PEC) via ester bonds, to prepare an amphiphilic polymer pro-bactericide, and subsequently self-assembled in aqueous solutions to obtain an esterase-triggered nanobactericide delivery system. The fluorescence quenching effect due to the aggregation of HP in nanoparticles (NPs) enabled the inhibition of photodegradation of HP in this system. Esterase stimulation could trigger HP release and increase its photodynamic activity. Antibacterial assays have shown that the NPs had potent antibacterial capacity, almost completely inactivating bacteria after 60 min of exposure to light. The NPs had good adherence to the leaves. Safety assessment indicated that the NPs have no obvious toxic effects on plants. Antibacterial studies on plants have shown that the NPs have excellent antibacterial effects on infected plants. These results provide a new strategy for obtaining a photoactivated bactericide nanosystem with a high utilization rate and good photostability and targeting ability.

What governs the electrocatalytic N2 reduction activity of sp-hybridized boron?

Electrocatalytic nitrogen reduction reactions (NRRs) have attracted intensive scientific attention, and boron in various forms has been shown promising for the activation of N2. In this work, we assessed the NRR activities of sp-hybridized-B (sp-B) doped into graphynes (GYs) using first-principles calculations. Eight inequivalent sp-B sites on five graphynes were considered. We found that boron doping greatly modifies the electronic structures at the active sites. Both the geometric effects and electronic effects play vital roles in the adsorption of the intermediates. Some intermediates prefer the sp-B site while others are bonded to both the sp-B and sp-C sites, which leads to two descriptors: the adsorption energy of the end-on N2 and the side-on N2. The former correlates well with the p-band center of sp-B while the latter correlates well with both the p-band center of sp-C and the formation energy of sp-B-doped GYs. The activity map demonstrates that the limiting potentials of the reactions are very small (-0.57 V to -0.05 V for the eight GYs). The free energy diagrams reveal that the distal path is normally the most favorable pathway, and the reaction may be limited by the adsorption of N2 when its binding free energy is higher than 0.26 eV. All eight B-doped GYs locate near the top of the activity volcano, suggesting that there are very promising candidates for the efficient NRR. This work provides a comprehensive understanding of the NRR activity of sp-B-doped GYs, and it should help guide the design of sp-B-doped catalysts.

Correction: High-throughput computational screening of hypothetical metal-organic frameworks with open copper sites for CO2/H2 separation.

Correction for 'High-throughput computational screening of hypothetical metal-organic frameworks with open copper sites for CO2/H2 separation' by Mengmeng Li et al., Phys. Chem. Chem. Phys., 2022, 24, 18764-18776, https://doi.org/10.1039/D2CP01139E.

High-throughput computational screening of hypothetical metal-organic frameworks with open copper sites for CO2/H2 separation.

It is challenging to identify the optimal metal-organic framework (MOF) adsorbents for gas adsorption and membrane-based separation from the large-scale material databases. The high-throughput computational screening (HTCS) method was adopted to discover the optimal materials for CO2/H2 separation from thousands of MOFs. First, a hierarchical strategy was used to select 1092 MOFs from 13 512 MOFs, and their adsorption capacity towards the equimolar CO2/H2 mixture at 298 K and 10 bar was further calculated using the grand canonical Monte Carlo (GCMC) simulations. The results show that those MOFs with lvtb topology and organic linker 1,2,4,5-tetrazine are conducive to exhibiting high performance CO2/H2 adsorption separation among top-100 MOFs with high performance. The MOFs with pore limited diameter (PLD), largest cavity diameter (LCD), gravimetrical surface area (GSA), and void fraction in the range of 4-12 Å, 5-12 Å, 5500-6500 m2 g-1 and 0.80-0.85, respectively, have high adsorption capacity towards CO2. Second, the dynamic adsorption properties of the top-4 MOFs were simulated by the breakthrough curves of the binary (CO2/H2) and quinary (CO2/H2/CH4/CO/N2) mixtures in the fixed adsorption bed. MOF-4641 exhibits a high breakthrough time of 130 for the quinary mixture. Finally, the adsorption mechanism of CO2 in the top-4 MOFs was investigated by the radial distribution function (RDF), the mass center probability density distribution, etc. The atomic insights from HTCS and breakthrough curve predictions in this work will be helpful in developing novel porous materials and obtaining superior CO2 separation performance.

Preparation and properties of O-chitosan quaternary ammonium salt/polyvinyl alcohol/graphene oxide dual self-healing hydrogel.

A simple method had been developed through O-chitosan quaternary ammonium salt (O-HACC), polyvinyl alcohol (PVA) and graphene oxide (GO) to prepare O-HACC/PVA/GO dual self-healing bacteriostatic hydrogels. Then the hydrogels and materials were characterized by FT-IR, X-RD, 1H NMR, SEM and TG. The hydrogel's compressive strength, equilibrium swelling and bacteriostatic efficiency were systematically studied. The research results showed that the maximum equilibrium swelling rate of hydrogel was 720%, the maximum compressive strength was 1500 Pa, and could self-heal within 12 h. In addition, the hydrogel could effectively inhibit E. coli and S. aureus, and also showed a good release behavior for bovine serum albumin (BSA). The CCK-8 method proved that the hydrogel was non-toxic to murine fibroblasts and could promote cell proliferation and growth to a certain extent. This research has potential significance for the application of self-healing hydrogel materials in the field of biomedicine.

A new antibacterial nano-system based on hematoporphyrin-carboxymethyl chitosan conjugate for enhanced photostability and photodynamic activity.

To promote bactericidal activity, improve photostability and safety, novel antibacterial nanoparticle system based on photodynamic action (PDA) was prepared here through conjugation of photosensitizer hematoporphyrin (HP) onto carboxymethyl chitosan (CMCS) via amide linkage and followed by ultrasonic treatment. The system was stable in PBS (pH 7.4) and could effectively inhibit the photodegradation of conjugated HP because of aggregation-caused quenching effect. ROS produced by the conjugated HP under light exposure could change the structure of nanoparticles by oxidizing the CMCS skeleton and thereby significantly promote the photodynamic activity of HP and its photodynamic activity after 6 h was higher than that of HP·2HCl under the same conditions. Antibacterial experiments showed that CMCS-HP nanoparticles had excellent photodynamic antibacterial activity, and the bacterial inhibition rates after 60 min of light exposure were greater than 97%. Safety evaluation exhibited that the nanoparticles were safe to mammalian cells, showing great potential for antibacterial therapy.

One-pot hydrothermal preparation of manganese-doped carbon microspheres for effective deep removal of hexavalent chromium from wastewater.

Mn-doped activated carbon microspheres (MnOx/ACS) with super-high adsorption capacities and deep removal capability for hexavalent chromium (Cr(VI)) were successfully prepared via an ammonium persulfate-assisted hydrothermal method followed by potassium oxalate activation using KMnO4 and sucrose as raw materials. Their -physical and chemical properties, as well as those of Mn-doped non-activated carbon spheres (MnOx/CS), were characterized by XRD, SEM, TEM, EDS-mapping, XPS, N2 adsorption-desorption, ICP-AES, and elemental analysis. It was found that the manganese oxide (MnOx) particles were uniformly embedded within the carbon spheres via layer-by-layer capture, and the MnOx/ACS exhibited strong redox activity because of the multivalent nature of MnOx, resulting in excellent adsorption performance via reduction. In particular, MnOx/ACS-4 with a Mn content of 1.06 wt% and a specific surface area of 1405.7 m2 g-1 achieved a maximum adsorption capacity of 660.7 mg g-1; this can reduce Cr(VI) content to less than 0.05 mg L-1, which meets the corresponding Chinese drinking water quality standard when the initial concentration of Cr(VI) is less than 400 mg L-1. Furthermore, this highly efficient method can be extended to prepare V-, Mo-, or W-doped carbon microspheres with significantly enhanced adsorption performance for Cr(VI) compared to bare activated carbon sphere, indicating their good application prospect for the deep removal for heavy metal ions from wastewater.

Preparation and properties of polyvinyl alcohol/N-succinyl chitosan/lincomycin composite antibacterial hydrogels for wound dressing.

Hydrogels are three-dimensional polymeric networks capable of absorbing large amounts of water or biological fluids with the properties resembling natural living tissues. Herein, polyvinyl alcohol (PVA)/N-succinyl chitosan (NSCS)/lincomycin hydrogels for wound dressing were prepared by the freezing/thawing method, then characterized by FTIR, SEM, and TGA. The compression strength, swelling behavior, water retention capacity, antibacterial activity, drug release and cytotoxicity were systematically investigated. The results showed that the introduction of NSCS remarkably enhanced the swelling capacity, leading to the maximum swelling ratio of 19.68 g/g in deionized water. The optimal compression strength of 0.75 MPa was achieved with 30 % NSCS content.Additionally, the incorporation of lincomycin brought a remarkable antibacterial activity against both Escherichia coli and Staphylococcus aureus. Specifically, 77.71 % of Staphylococcus aureus was inhibited with 75 µg/mL lincomycin, while the MTT assay demonstrated the nontoxic nature of the composite hydrogels. In summary, this PVA/NSCS/lincomycin hydrogel showed promising potential for wound dressing.

Engineering Bismuth-Tin Interface in Bimetallic Aerogel with a 3D Porous Structure for Highly Selective Electrocatalytic CO2 Reduction to HCOOH.

Electrochemical reduction of CO2 (CO2 RR) into valuable hydrocarbons is appealing in alleviating the excessive CO2 level. We present the very first utilization of metallic bismuth-tin (Bi-Sn) aerogel for CO2 RR with selective HCOOH production. A non-precious bimetallic aerogel of Bi-Sn is readily prepared at ambient temperature, which exhibits 3D morphology with interconnected channels, abundant interfaces and a hydrophilic surface. Superior to Bi and Sn, the Bi-Sn aerogel exposes more active sites and it has favorable mass transfer properties, which endow it with a high FEHCOOH of 93.9 %. Moreover, the Bi-Sn aerogel achieves a FEHCOOH of ca. 90 % that was maintained for 10 h in a flow battery. In situ ATR-FTIR measurements confirmed that the formation of *HCOO is the rate-determining step toward formic acid generation. DFT demonstrated the coexistence of Bi and Sn optimized the energy barrier for the production of HCOOH, thereby improving the catalytic activity.

Controlled synthesis of Cu-based SAPO-18/34 intergrowth zeolites for selective catalytic reduction of NOx by ammonia.

Cu-based SAPO-18, SAPO-18/34 intergrowth and SAPO-34 zeolites were applied for the selective catalytic reduction of NOx by ammonia (NH3-SCR) catalysts. Comprehensive characterization results revealed that the SAPO-18/34 with higher amount and strength of acid sites could facilitate the generation of more isolated copper ions (Cu2+ and Cu+) and suppress the formation of CuOx, which might account for the fact that intergrowth crystal structure of Cu-SAPO-18/34 exhibited higher fresh NH3-SCR activity, more robust hydrothermal durability and better SO2-resistance ability than that Cu-SAPO-18 and Cu-SAPO-34. In situ DRIFTS results provided the formation of reaction intermediates, such as -NH2, NH4+, NO3-, NO2-, etc. Eley-Rideal (E-R) and Langmuir-Hinshelwood (L-H) reaction mechanisms were both involved in Cu-based SAPO-18 and SAPO-18/34 intergrowth zeolites, but the L-H mechanism dominated the NH3-SCR reaction, in addition, Cu-SAPO-34 only followed "L-H" mechanism.

Hydroxypropyl chitosan-based dual self-healing hydrogel for adsorption of chromium ions.

A facile, environmentally benign approach had been developed for the preparation of dual self-healing and adsorption hydrogel through hydroxypropyl chitosan (HPCS), polyacrylamide (PAM) and polyvinyl alcohol (PVA). The self-healing capability of the hydrogels without any external stimulus was ascribed to dynamic Schiff-base bonds, borate bonds and hydrogen bonds, while the adsorption capacity of hydrogels came from the protonated amino group effect at a specific pH. It was demonstrated that the HPP DN hydrogel had a maximum equilibrium swelling ratio of 643% and a maximum compressive strength of 267 kPa. The weight loss of HPP DN hydrogel was 14.26% lower than that of HPCS/PAM single network hydrogel, furthermore, HPP DN hydrogel could achieve self-healing within 10 h. Due to the large number of active groups, the adsorption capacity of Cr6+ reached 95.31 mg/g. It could adsorb in a wide pH range of 1 to 6, and could describe by pseudo-first-order kinetic model and Langmuir adsorption isotherm model, which would provide a new idea for the adsorption and removal of heavy metal ions. In short, the prepared HPP hydrogel had dual self-healing ability, adsorption capacity and mechanical strength, which would make it a promising candidate for long-life adsorbent.

N,N-dimethylformamide assisted facile hydrothermal synthesis of boehmite microspheres for highly effective removal of Congo red from water.

A series of boehmite microspheres with highly effective adsorption performance for Congo red (CR) were successfully prepared via amides assisted hydrothermal method at 180 °C. Effects of dosages and hydrolysates of N,N-dimethylformamide (DMF), amides species including DMF, N-methylformamide (MF) and formamide (FA), and reaction times on their physicochemical properties were studied in detail. It was found that increase on their crystallinity and shell thickness results from the different hydrolysis rates of the amides; amorphous alumina hydrate, boehmite core-shell structure and hollow microspheres were obtained at hydrothermal times of 60, 140 and 360 min, respectively due to the Ostwald ripening. Especially, dimethylamine (DMA) as a hydrolysate of DMF, can effectively regulate the morphologies of the boehmites together with the sulfate ions, and make their pore sizes distribution (PSD) centering at 3-4 nm. Importantly, the boehmite microspheres with specific surface area of 221.3 m2/g shows the maximum adsorption capacity of 847.5 mg/g for CR calculated from Langmuir isotherm model, and its adsorption amount reached a high value of 484.1 mg/g at 60 min due to the mentioned PSD. This template-free hydrothermal method using DMF as precipitant provides an alternative approach for preparing high-performance hydrated alumina for environmental applications.

A sodium alginate-based nano-pesticide delivery system for enhanced in vitro photostability and insecticidal efficacy of phloxine B.

To improve in vitro photostability and enhance insecticidal activity, a novel esterase/glutathione (GSH) responsive photoactivated nano-pesticide delivery system was synthesized by conjugation of photoactivated pesticide phloxine B(PB) to sodium alginate (SA) via esterase/GSH sensitive phenolic ester bond followed by ultrasonic dispersion. The system was stable in PBS (pH 7.4) and could protect effectively the conjugated PB from in vitro photodegradation because of aggregation-caused quenching effect, whose maximum photodegradation rate did not exceed 10 % after 270 min illumination. However, upon exposure to esterase-6 or GSH stimulus, high photoactivity was observed due to the destruction of the system and accompanied by PB release. The combined stimulation could trigger more PB release than any single stimulus and thus resulting in a higher photoactivity. Compared with free PB, The system showed a higher phototoxicity on Sf9 insect cells and the in vitro light exposure had little influence on the phototoxicity.

Photo-Fenton removal of tetracycline hydrochloride using LaFeO3 as a persulfate activator under visible light.

In this work, LaFeO3 nanoparticles were fabricated by a facile sol-gel method and applied to degrade tetracycline hydrochloride (TC-HCl) through heterogeneous activation of persulfate under visible-light illumination. The structure, compositions, photocatalytic properties, and morphological features of the as-obtained sample were investigated by XRD, XPS, DRS, and FESEM techniques. Optimizations of dosage of LaFeO3 (0-0.4 g/L), dosage of PS (0-4 g/L), concentration of TC-HCl (10 ppm-80 ppm), and pH of initial solution (2.09-9.59) were conducted. Radical trapping experiments indicated that SO4- was the dominant radical for TC-HCl removal while OH was also involved. In addition, LaFeO3 was proved with excellent stability and reusability in degrading TC-HCl molecules in the Vis/LaFeO3/PS system. The findings of this work revealed the potential application of the Vis/LaFeO3/PS system toward degrading organic pollutants in wastewater.

Rapid degradation of tetracycline hydrochloride by heterogeneous photocatalysis coupling persulfate oxidation with MIL-53(Fe) under visible light irradiation.

This work demonstrates a facile route to assemble MIL-53(Fe) by solvothermal method. Sulfate radical-based advanced oxidation processes (SR-AOPs) coupling with photocatalysis based on MIL-53(Fe) were investigated under visible light. The catalytic effect of MIL-53(Fe) for the degradation of tetracycline hydrochloride (TC-HCl) was systematically studied, as well as the reusability of the catalyst and the effect of operating parameters. The results indicated that 99.7 % of TC (300 mg/L) could be degraded within 80 min in the SR-AOPs coupling with photocatalysis processes, as compared to 71.4 % for the SR-AOPs and only 17.1 % for the photocatalysis. The trapping experiments and electron spin-resonance spectroscopy (ESR) showed the photogenerated electrons of MIL-53(Fe) under visible light irritation were trapped by persulfate to generated sulfate radicals which effectively suppressed the recombination of photogenerated carriers. And also, the SO4- could be formed by the conversion between Fe (Ⅲ) and Fe (Ⅱ) in MIL-53(Fe). Moreover, OH and O2- generated by the reaction increased significantly due to the increase of SO4- which generated more OH and reduced photogenerated carrier recombination respectively. Thus, the degradation efficiency of TC-HCl was improved. Furthermore, the degradation pathway for TC-HCl was proposed using the theoretical calculations and liquid chromatography coupled with mass spectrometry.

Surfactant-free preparation of mesoporous solid/hollow boehmite and bayerite microspheres via double hydrolysis of NaAlO2 and formamide from room temperature to 180 °C.

The transformation from solid boehmite microspheres to hollow bayerite microspheres at room temperature (25 °C) was successfully realized via the double hydrolysis of NaAlO2 and formamide (FA) solution. Effects of reaction time, temperature and FA dos on the transformation process were studied in detail. The results show that hollow boehmite microspheres were obtained via increasing the temperature above 120 °C and the FA dos above 12 mL; amorphous alumina hydrate, solid boehmite and hollow bayerite microspheres were also obtained at 25 °C for 1 h, 2 h and 24 h reactions, respectively; solid bayerite microspheres were obtained by decreasing the FA dos below 4 mL at 25 °C. Because of the slow change of pH from 12.9 to 8.7, simultaneous dissolution and regeneration for different aluminum hydroxide were the key factors for forming hollow boehmite/bayerite microspheres. The Al yield for boehmite microspheres reached 41.4% at 25 °C for a 2 h reaction; when increasing the temperature to 180 °C, the Al yield for hollow boehmite microspheres with higher crystallinity increased to 82.7%. Moreover, the solid/hollow boehmite microspheres with high surface areas showed outstanding adsorption capacities of 751.9 mg/g and 694.4 mg/g, respectively, for Congo red. This significant transformation of structure and morphology provides an effective strategy for preparing mono-phase hydrated alumina with excellent adsorption performance.

Oxygen Vacancy-Rich In-Doped CoO/CoP Heterostructure as an Effective Air Cathode for Rechargeable Zn-Air Batteries.

An efficient and low-cost electrocatalyst for reversible oxygen electrocatalysis is crucial for improving the performance of rechargeable metal-air batteries. Herein, a novel oxygen vacancy-rich 2D porous In-doped CoO/CoP heterostructure (In-CoO/CoP FNS) is designed and developed by a facile free radicals-induced strategy as an effective bifunctional electrocatalyst for rechargeable Zn-air batteries. The electron spin resonance and X-ray absorption near edge spectroscopy provide clear evidence that abundant oxygen vacancies are formed in the interface of In-CoO/CoP FNS. Owing to abundant oxygen vacancies, porous heterostructure, and multiple components, In-CoO/CoP FNS exhibits excellent oxygen reduction reaction activity with a positive half-wave potential of 0.81 V and superior oxygen evolution reaction activity with a low overpotential of 365 mV at 10 mA cm-2 . Moreover, a home-made Zn-air battery with In-CoO/CoP FNS as an air cathode delivers a large power density of 139.4 mW cm-2 , a high energy density of 938 Wh kgZn -1 , and can be steadily cycled over 130 h at 10 mA cm-2 , demonstrating great application potential in rechargeable metal-air batteries.