Theoretical studies on the aqueous phase and graphene heterogeneous degradation of acrylamide and acrylonitrile by HO, ClO, and BrO radicals.

The newly discovered ClO• and BrO• contribute to pollutant degradation in advanced oxidation processes, while acrylamide (AM) and acrylonitrile (ACN) are always the focus of scientists concerned due to their continuous production and highly toxic effects. Moreover, various particles with a graphene-like structure are the companions of AM/ACN in dry/wet sedimentation or aqueous phase existence, which play an important role in heterogeneous oxidation. Thus, this work focuses on the reaction mechanism and environmental effect of AM/ACN with ClO•/BrO•/HO• in the water environment under the influence of graphene (GP). The results show that although the reactivity sequence of AM and ACN takes the order of with HO• > with BrO• > with ClO•, the easiest channel always occurs at the same C-position of the two reactants. The reaction rate constants (k) of AM with three radicals are 2 times larger than that with ACN, and amide groups have a better ability to activate CC bonds than cyanide groups. The existence of GP can accelerate the target reaction, and the k increased by 9-13 orders of magnitude. The toxicity assessment results show that the toxic effect of most products is lower than that of parent compounds, but the environmental risk of products from ClO•/BrO•-adducts is higher than those from HO•-adducts. The oxidative degradation process based on ClO• and BrO• deserves special attention, and the catalytic effect of GP and its derivatives on the oxidation process is non-negligible.

Concentrated solar CO2 reduction in H2O vapour with >1% energy conversion efficiency.

H2O dissociation plays a crucial role in solar-driven catalytic CO2 methanation, demanding high temperature even for solar-to-chemical conversion efficiencies <1% with modest product selectivity. Herein, we report an oxygen-vacancy (Vo) rich CeO2 catalyst with single-atom Ni anchored around its surface Vo sites by replacing Ce atoms to promote H2O dissociation and achieve effective photothermal CO2 reduction under concentrated light irradiation. The high photon flux reduces the apparent activation energy for CH4 production and prevents Vo from depletion. The defects coordinated with single-atom Ni, significantly promote the capture of charges and local phonons at the Ni d-impurity orbitals, thereby inducing more effective H2O activation. The catalyst presents a CH4 yield of 192.75 µmol/cm2/h, with a solar-to-chemical efficiency of 1.14% and a selectivity ~100%. The mechanistic insights uncovered in this study should help further the development of H2O-activating catalysts for CO2 reduction and thereby expedite the practical utilization of solar-to-chemical technologies.

Evaluating combustion kinetics and quantifying fuel-N conversion tendency of shoe manufacturing waste.

Combustion is an effective and cost-efficient thermochemical conversion method for solid waste, showing promise for the resource utilization of shoe manufacturing waste (SMW). However, SMW is generally composed of different components, which can lead to unstable combustion and excessive pollutant emissions, especially NOx. To date, combustion characteristics, reaction mechanism and fuel nitrogen (fuel-N) conversion of different SMW components remain unclear. In this work, the combustion behavior of typical SMW components combustion was investigated using Thermogravimetric coupled with Fourier transform infrared spectrum (TG-FTIR). A simplified single-step reaction mechanism was proposed according to the temperature interval to estimate reaction mechanism of SMW. Additionally, the relationship between fuel-N conversion tendency and fuel properties was established. The results indicate that the values for the comprehensive combustion performance index (S) and flammability index (C) range from 1.65 to 0.44 and 3.98 to 1.37, respectively. This demonstrates the significant variability in combustion behavior among different SMW components. Cardboard, leather and sponge have higher values of S and C, suggesting a better ignition characteristic and a stable combustion process. During the combustion of SMW, nitrogen oxides (NO and N2O) are the main nitrogen-containing compounds in the flue gases, with NO being the major contributor, accounting for over 82.97 % of the nitrogen oxides. NO has a negative correlation with nitrogen content, but it is opposite for N2O, HCN and NH3. Furthermore, the conversion of NO, N2O and NH3 is proportional to logarithmic values of O/N, while its conversion to HCN is proportional to logarithmic values of VM/N. These findings facilitate the prediction of the fuel-N conversion of solid waste combustion. This work might shed light on combustion optimization and in-situ pollutant emission control in solid waste combustion.

Chloramine Disinfection of Levofloxacin and Sulfaphenazole: Unraveling Novel Disinfection Byproducts and Elucidating Formation Mechanisms for an Enhanced Understanding of Water Treatment.

The unrestricted utilization of antibiotics poses a critical challenge to global public health and safety. Levofloxacin (LEV) and sulfaphenazole (SPN), widely employed broad-spectrum antimicrobials, are frequently detected at the terminal stage of water treatment, raising concerns regarding their potential conversion into detrimental disinfection byproducts (DBPs). However, current knowledge is deficient in identifying the potential DBPs and elucidating the precise transformation pathways and influencing factors during the chloramine disinfection process of these two antibiotics. This study conducts a comprehensive analysis of reaction pathways, encompassing piperazine ring opening/oxidation, Cl-substitution, OH-substitution, desulfurization, and S-N bond cleavage, during chloramine disinfection. Twelve new DBPs were identified in this study, exhibiting stability and persistence even after 24 h of disinfection. Additionally, an examination of DBP generation under varying disinfectant concentrations and pH values revealed peak levels at a molar ratio of 25 for LEV and SPN to chloramine, with LEV contributing 11.5% and SPN 23.8% to the relative abundance of DBPs. Remarkably, this research underscores a substantial increase in DBP formation within the molar ratio range of 1:1 to 1:10 compared to 1:10 to 1:25. Furthermore, a pronounced elevation in DBP generation was observed in the pH range of 7 to 8. These findings present critical insights into the impact of the disinfection process on these antibiotics, emphasizing the innovation and significance of this research in assessing associated health risks.

Recyclable N-Heterocyclic Carbene Porous Coordination Polymers with Two Distinct Metal Sites for Transformation of CO2 to Cyclic Carbonates.

Single-component catalysts with integrated multiple reactive centers could work in concert to achieve enhanced activity tailored for specific catalytic reactions, but they remain underdeveloped. Herein, we report the construction of heterogeneous bimetallic porous coordination polymers (PCPs) containing both porphyrin and N-heterocyclic carbene (NHC) metal sites via the coordinative assembly of the NHC functionalities. Three heterobimetallic PCPs (TIPP-Zn-Pd, TIPP-Cu-Pd and TIPP-Ni-Pd) have been prepared to verify this facile synthetic strategy for the first time. In order to establish a cooperative action toward the catalytic CO2 cycloaddition with epoxides, an additional tetraalkylammonium bromide functionality has also been incorporated into these polymeric structures through the N-substituent of the NHC moieties. The resulting heterogeneous bimetallic catalyst TIPP-Zn-Pd exhibits the best catalytic performance in CO2 cycloaddition with styrene oxide (SO) under solvent-free conditions at atmospheric pressure and is applicable to a wide range of epoxides. More importantly, TIPP-Zn-Pd works smoothly and is recyclable in the absence of a cocatalyst under 1.0 MPa of CO2 at 60 °C. This indicates that TIPP-Zn-Pd is quite competitive with the reported heterogeneous catalysts, which typically require a high reaction temperature above 100 °C under cocatalyst-free conditions. Thus, this work provides a new approach to design heterogeneous bimetallic PCP catalysts for high-performance CO2 fixation under mild reaction conditions.

Nondestructive 3D Imaging of Microscale Damage inside Polymers-Based on the Discovery of Self-Excited Fluorescence Effect Induced by Electrical Field.

The development of high-precision, non-destructive, and three-dimensional (3D) in situ imaging of micro-scale damage inside polymers is extremely challenging. Recent reports suggest that 3D imaging technology based on micro-CT technology causes irreversible damage to materials and is ineffective for many elastomeric materials. In this study, it is discovered that electrical trees inside silicone gel induced by an applied electric field can induce a self-excited fluorescence effect. Based on this, high-precision, non-destructive, and 3D in situ fluorescence imaging of polymer damages is successfully achieved. Compared with the current methods, the fluorescence microscopic imaging method enables slicing of the sample in vivo with high-precision operation, realizing the precise positioning of the damaged area. This pioneering discovery paves the way for high-precision, non-destructive, and 3D in situ imaging of polymer internal damage, which can solve the problem of internal damage imaging in insulating materials and precision instruments.

Application of nanomedicine in radiotherapy sensitization.

Radiation therapy is an important component of cancer treatment. As research in radiotherapy techniques advances, new methods to enhance tumor response to radiation need to be on the agenda to enable enhanced radiation therapy at low radiation doses. With the rapid development of nanotechnology and nanomedicine, the use of nanomaterials as radiosensitizers to enhance radiation response and overcome radiation resistance has attracted great interest. The rapid development and application of emerging nanomaterials in the biomedical field offers good opportunities to improve the efficacy of radiotherapy, which helps to promote the development of radiation therapy and will be applied in clinical practice in the near future. In this paper, we discuss the main types of nano-radiosensitizers and explore their sensitization mechanisms at the tissue level, cellular level and even molecular biology and genetic level, and analyze the current status of promising nano-radiosensitizers and provide an outlook on their future development and applications.

Effect of Sulfur on the Reduction of Ilmenite by Syngas in Chemical Looping Combustion.

The reactivity of ilmenite as an oxygen carrier (OC) in the presence of H2S was studied. A simulated syngas (66% CO, 34% H2) was used as the fuel. H2S concentrations were set to 4700 and 6580 ppm. The effect of the presence of CO2 was also investigated. The experiments were carried out using a thermogravimetric analyzer (TGA) at atmospheric pressure, with temperatures varying from 1073 to 1223 K. The results showed that the presence of H2S had no effect on the reduction kinetics of ilmenite. With the presence of only CO2 in the syngas, deposition on ilmenite samples was not observed. In the presence of H2S, deposition was observed regardless of the presence of CO2. Higher H2S concentration led to more pronounced deposition. It was shown that deposition only occurred after the ilmenite sample was sufficiently reduced. For ilmenite oxidation, the mass change curves display a distinct peak followed by a valley when the sample was previously reduced in the presence of H2S, indicating reactions between the sulfur deposit and air. The amount of the sulfur deposit could be calculated using the oxidation curves. Scanning electron microscope-energy dispersive X-ray (SEM-EDX) and X-ray diffraction (XRD) analyses were conducted to examine the surface of the reduced samples and the results from these analyses confirmed the presence of the sulfur deposit on the surface of the samples that were reduced in H2S-containing atmospheres.

New Insight into the Synthesis of Large-Pore Ordered Mesoporous Materials.

Ordered mesoporous materials (OMMs) have received increasing interest due to their uniform pore size, high surface area, various compositions and wide applications in energy conversion and storage, biomedicine and environmental remediation, etc. The soft templating synthesis using surfactants or amphiphilic block copolymers is the most efficient method to produce OMMs with tailorable pore structure and surface property. However, due to the limited choice of commercially available soft templates, the common OMMs usually show small pore size and amorphous (or semicrystalline) frameworks. Tailor-made amphiphilic block copolymers with controllable molecular weights and compositions have recently emerged as alternative soft templates for synthesis of new OMMs with many unique features including adjustable mesostructures and framework compositions, ultralarge pores, thick pore walls, high thermal stability and crystalline frameworks. In this Perspective, recent progresses and some new insights into the coassembly process about the synthesis of OMMs based on these tailor-made copolymers as templates are summarized, and typical newly developed synthesis methods and strategies are discussed in depth, including solvent evaporation induced aggregation, ligand-assisted coassembly, solvent evaporation induced micelle fusion-aggregation assembly, homopolymer assisted pore expanding and carbon-supported crystallization strategy. Then, the applications of the obtained large-pore OMMs in catalysis, sensor, energy conversion and storage, and biomedicine by loading large-size guest molecules (e.g., protein and RNA), precious metal nanoparticles and quantum dots, are discussed. At last, the outlook on the prospects and challenges of future research about the synthesis of large-pore OMMs by using tailor-made amphiphilic block copolymers are included.

Ordered Macro/Mesoporous TiO2 Hollow Microspheres with Highly Crystalline Thin Shells for High-Efficiency Photoconversion.

Well ordered, uniform 3D open macro/mesoporous TiO2 hollow microspheres with highly crystalline anatase thin shells have been successfully synthesized by a simple solvent evaporation-driven confined self-assembly method. The 3D open macro/mesoporous TiO2 hollow microspheres show high energy-conversion efficiency (up to 9.5%) and remarkable photocatalytic activity (with photodegradation of 100% for methylene blue in 12 min under UV light irradiation).

Radially oriented mesoporous TiO2 microspheres with single-crystal-like anatase walls for high-efficiency optoelectronic devices.

Highly crystalline mesoporous materials with oriented configurations are in demand for high-performance energy conversion devices. We report a simple evaporation-driven oriented assembly method to synthesize three-dimensional open mesoporous TiO2 microspheres with a diameter of ~800 nm, well-controlled radially oriented hexagonal mesochannels, and crystalline anatase walls. The mesoporous TiO2 spheres have a large accessible surface area (112 m(2)/g), a large pore volume (0.164 cm(3)/g), and highly single-crystal-like anatase walls with dominant (101) exposed facets, making them ideal for conducting mesoscopic photoanode films. Dye-sensitized solar cells (DSSCs) based on the mesoporous TiO2 microspheres and commercial dye N719 have a photoelectric conversion efficiency of up to 12.1%. This evaporation-driven approach can create opportunities for tailoring the orientation of inorganic building blocks in the assembly of various mesoporous materials.

Ultradispersed Palladium Nanoparticles in Three-Dimensional Dendritic Mesoporous Silica Nanospheres: Toward Active and Stable Heterogeneous Catalysts.

Immobilization of highly monodispersed palladium nanoparticles in colloidal mesoporous silica supports has been successfully achieved. The Pd nanoparticles with a uniform small size of ∼1.2 nm can be homogeneously distributed in individual mesopore channels of amino group-functionalized three-dimensional dendritic mesoporous silica nanospheres (3D-dendritic MSNSs) with a Pd content of ∼2.8%. The 3D-dendritic MSNSs-based nanoreactors show high activity in Suzuki-Miyaura cross-coupling reactions of bromobenzene with phenylboronic acid, obtaining a yield over 99% with 0.075 mol % Pd catalyst at room temperature in the dark within 12 h. More importantly, the excellent catalytic performance can be maintained with a negligible decrease lasting at least six cycles. It further reveals that the mesoporous frameworks of the colloidal silica supports can be well-preserved after four catalytic runs; meanwhile, the Pd nanoparticles in the mesopore channels also can remain the sizes of 1.5±0.3 nm without significant transfer and aggregation. The unique mesostructure of the 3D-dendritic MSNSs with mesopore channels of short length and large diameter is supposed to be the key role in immobilization of active and robust heterogeneous catalysts, and it would have more hopeful prospects in catalytic applications.

Designed fabrication and characterization of three-dimensionally ordered arrays of core-shell magnetic mesoporous carbon microspheres.

A confined interface coassembly coating strategy based on three-dimensional (3-D) ordered macroporous silica as the nanoreactor was demonstrated for the designed fabrication of novel 3-D ordered arrays of core-shell microspheres consisting of Fe3O4 cores and ordered mesoporous carbon shells. The obtained 3-D ordered arrays of Fe3O4@mesoporous carbon materials possess two sets of periodic structures at both mesoscale and submicrometer scale, high surface area of 326 m(2)/g, and large mesopore size of 19 nm. Microwave absorption test reveals that the obtained materials have excellent microwave absorption performances with maximum reflection loss of up to -57 dB at 8 GHz, and large absorption bandwidth (7.3-13.7 GHz, < -10 dB), due to the combination of the large magnetic loss from iron oxides, the strong dielectric loss from carbonaceous shell, and the strong reflection and scattering of electromagnetic waves of the ordered structures of the mesopores and 3-D arrays of core-shell microspheres.

Mesoporous TiO2 Mesocrystals: Remarkable Defects-Induced Crystallite-Interface Reactivity and Their in Situ Conversion to Single Crystals.

Oriented self-assembly between inorganic nanocrystals and surfactants is emerging as a route for obtaining new mesocrystalline semiconductors. However, the actual synthesis of mesoporous semiconductor mesocrystals with abundant surface sites is extremely difficult, and the corresponding new physical and chemical properties arising from such an intrinsic porous mesocrystalline nature, which is of fundamental importance for designing high-efficiency nanostructured devices, have been rarely explored and poorly understood. Herein, we report a simple evaporation-driven oriented assembly method to grow unprecedented olive-shaped mesoporous TiO2 mesocrystals (FDU-19) self-organized by ultrathin flake-like anatase nanocrystals (∼8 nm in thickness). The mesoporous mesocrystals FDU-19 exhibit an ultrahigh surface area (∼189 m(2)/g), large internal pore volume (0.56 cm(3)/g), and abundant defects (oxygen vacancies or unsaturated Ti(3+) sites), inducing remarkable crystallite-interface reactivity. It is found that the mesocrystals FDU-19 can be easily fused in situ into mesoporous anatase single crystals (SC-FDU-19) by annealing in air. More significantly, by annealing in a vacuum (∼4.0 × 10(-5) Pa), the mesocrystals experience an abrupt three-dimensional to two-dimensional structural transformation to form ultrathin anatase single-crystal nanosheets (NS-FDU-19, ∼8 nm in thickness) dominated by nearly 90% exposed reactive (001) facets. The balance between attraction and electrostatic repulsion is proposed to determine the resulting geometry and dimensionality. Dye-sensitized solar cells based on FDU-19 and SC-FDU-19 samples show ultrahigh photoconversion efficiencies of up to 11.6% and 11.3%, respectively, which are largely attributed to their intrinsic single-crystal nature as well as high porosity. This work gives new understanding of physical and chemical properties of mesoporous semiconductor mesocrystals and opens up a new pathway for designing various single-crystal semiconductors with desired mesostructures for applications in catalysis, sensors, drug delivery, optical devices, etc.

An interface-directed coassembly approach to synthesize uniform large-pore mesoporous silica spheres.

A facile and controllable interface-directed coassembly (IDCA) approach is developed for the first time to synthesize uniform discrete mesoporous silica particles with a large pore size (ca. 8 nm) by using 3-dimensional macroporous carbon (3DOMC) as the nanoreactor for the confined coassembly of template molecules and silica source. By controlling the amount of the precursor solution and using Pluronic templates with different compositions, we can synthesize mesoporous silica particles with diverse morphologies (spheres, hollow spheres, and hemispheres) and different mesostructure (e.g., 2-D hexagonal and 3D face centered cubic symmetry), high surface area of about 790 m(2)/g, and large pore volume (0.98 cm(3)/g). The particle size can be tunable from submicrometer to micrometer regimes by changing the macropore diameter of 3DOMC. Importantly, this synthesis concept can be extended to fabricate multifunctional mesoporous composite spheres with a magnetic core and a mesoporous silica shell, large saturated magnetization (23.5 emu/g), and high surface area (280 m(2)/g). With the use of the magnetic mesoporous silica spheres as a magnetically recyclable absorbent, a fast and efficient removal of microcystin from water is achieved, and they can be recycled for 10 times without a significant decrease of removal efficiency for microcystin.

Sol-gel design strategy for ultradispersed TiO2 nanoparticles on graphene for high-performance lithium ion batteries.

The rational design and controllable synthesis of strongly coupled inorganic/graphene hybrids represents a long-standing challenge for developing advanced catalysts and energy-storage materials. Here, we report a simple sol-gel method toward creating ultradispersed TiO2 nanoparticles on graphene with an unprecedented degree of control based on the precise separation and manipulation of nanoparticles nucleated, grown, anchored, and crystallized and the reduction of graphene oxide (GO). The hybrid materials show ultradispersed anatase nanoparticles (~5 nm), ultrathin thickness (≤3 layers), and a high surface area of ~229 m(2)/g and exhibit a high specific capacity of ~94 mA h g(-1) at ~59 C, which is twice as that of mechanically mixed composites (~41 mA h g(-1)), demonstrating the potential of strongly synergistic coupling effects for advanced functional systems.

General synthesis of discrete mesoporous carbon microspheres through a confined self-assembly process in inverse opals.

A general confined coassembly process has been demonstrated to produce discrete uniform mesoporous carbon microspheres with 0.8-1 µm particle size using 3-D-ordered macroporous silica as the template. The obtained mesoporous carbon microspheres (MC-MSs) have uniform and discrete spherical morphology, variable symmetry (hexagonal p6mm or cubic Im3m) of mesostructures, high specific surface areas (500-1100 m(2)/g), large pore volumes (0.6-2.0 cm(3)/g), and highly accessible large mesopores (7-10.3 nm). The particle size of the carbon microspheres can be easily tuned by simply using templates with different macropore sizes. It was found that the smaller MC-MSs (330 nm) with higher surface-to-volume ratio tend to shape into an integral monolithic MC-MS matrix and larger MC-MSs (>800 nm) with lower surface-to-volume ratio to discrete spherical morphology. This feature is attributed to the difference in shrinkage behavior of mesoporous carbon spheres confined in the macropores caused by the interaction between the silica wall and carbon microspheres. Adsorption experiments indicate that the cobalt-based nanoparticle-incorporated mesoporous carbon microspheres exhibit excellent size selectivity for protein adsorption in a complex solution and good magnetic separability for easy recycling.

In-situ crystallization route to nanorod-aggregated functional ZSM-5 microspheres.

Herein, we develop a reproducible in situ crystallization route to synthesize uniform functional ZSM-5 microspheres composed of aggregated ZSM-5 nanorods and well-dispersed uniform Fe(3)O(4) nanoparticles (NPs). The growth of such unique microspheres undergoes a NP-assisted recrystallization process from surface to core. The obtained magnetic ZSM-5 microspheres possess a uniform size (6-9 µm), ultrafine uniform Fe(3)O(4) NPs (~10 nm), good structural stability, high surface area (340 m(2)/g), and large magnetization (~8.6 emu/g) and exhibit a potential application in Fischer-Tropsch synthesis.

Large-pore ordered mesoporous materials templated from non-Pluronic amphiphilic block copolymers.

The self-assembly of small surfactants and Pluronic® amphiphilic copolymers has enabled the synthesis of a range of ordered mesoporous materials with high surface area, diverse compositions, variable pore structures and tunable pore sizes. It has recently been realized that non-Pluronic block copolymers can be used as robust templates for the synthesis of novel and high-performance mesoporous materials with crystalline frameworks, ultra-large pores, and abundant pore symmetries, which are not accessible using the Pluronic counterparts. In this review, we introduce the principle of self-assembly of block copolymers and their phase separations, and summarize recently developed synthetic methods and strategies for ordered mesoporous silicas, metal oxides, carbons and metals which have shown superior performances for applications in various fields, including solar cells, batteries, fuel cells, and sensors.