Monolithic Catalysts Supported by Emulsion-Templated Porous Polydivinylbenzene for Continuous Reduction of 4-Nitrophenol.

A monolithic catalyst was fabricated through an emulsion-templating method, postpolymerization modification, and in situ loading of active constituents. To achieve a high specific surface area, divinylbenzene (DVB) was solely employed as the monomer, while the porous structure was adjusted with the porogen content and the types of initiators. Then, anchor points were introduced on the pore wall through nitration and amination of the polymeric scaffold. Using a controlled "silver mirror reaction", monolithic catalysts were obtained after loading of silver nanoparticles (Ag NPs), which was verified from morphological and crystallinity characteristics. The catalytic performance of the resultant monolithic catalyst was determined with the model reduction of 4-nitrophenol (4-NP). In static catalysis, the monolithic catalyst was proved to have a reactively high apparent rate constant and a good reusability. Furthermore, a flow reactor was fabricated with the monolithic catalyst, showing a high efficiency and long-term durability for the continuous reduction of 4-NP. This work broadened the adjustment of porous structures and the subsequent application for emulsion-templated monoliths.

Development of Plasmonic Attapulgite/Co(Ti)Ox Nanocomposite Using Spent Batteries toward Photothermal Reduction of CO2.

The rapid development of the battery industry has brought about a large amount of waste battery pollution. How to realize the high-value utilization of waste batteries is an urgent problem to be solved. Herein, cobalt and titanium compounds (LTCO) were firstly recovered from spent lithium-ion batteries (LIBs) using the carbon thermal reduction approach, and plasmonic attapulgite/Co(Ti)Ox (H-ATP/Co(Ti)Ox) nanocomposites were prepared by the microwave hydrothermal technique. H-ATP had a large specific surface area and enough active sites to capture CO2 molecules. The biochar not only reduced the spinel phase of waste LIBs into metal oxides including Co3O4 and TiO2 but also increased the separation and transmission of the carriers, thereby accelerating the adsorption and reduction of CO2. In addition, H-ATP/Co(Ti)Ox exhibited a localized surface plasmon resonance effect (LSPR) in the visible to near-infrared region and released high-energy hot electrons, enhancing the surface temperature of the catalyst and further improving the catalytic reduction of CO2 with a high CO yield of 14.7 µmol·g-1·h-1. The current work demonstrates the potential for CO2 reduction by taking advantage of natural mineral and spent batteries.

Janus Hemispheres through Controlled Polymerization-Induced Phase Separations within Wax Droplets.

A series of Janus hemispheres with a patchy hemispherical surface and a flat undersurface were synthesized through controlled polymerization-induced phase separation within emulsified wax droplets. The hemispherical shape was generated through the polymerization of styrene within wax droplets, followed by the grafting of hydrophilic polymers on the exposed surface. Then, the patchy hemispherical surface was achieved after introducing the hydrophobic acrylate monomers within wax droplets and controlling the polymerization-induced phase separation. The morphological evolution of patches was recorded via the reaction time, followed by their morphological regulation through the type, feeding amount, and cross-linking degree of acrylate monomers. A functional monomer, vinyl benzyl chloride (VBC), was also used to copolymerize the patches for grafting a zwitterionic polymer via surface-initiated atom transfer radical polymerization (SI-ATRP). The as-obtained Janus hemispheres were employed to fabricate robust coatings with wettability tuned from superhydrophobicity to underwater superoleophobicity by the grafted zwitterionic polymers.

Self-Assembled Zeolitic Imidazolate Framework/CdS Hollow Microspheres with Efficient Charge Separation for Enhanced Photocatalytic Hydrogen Evolution.

Enhanced interfacial charge separation is of great importance to high-efficiency photocatalytic hydrogen production. Herein, we successfully fabricated novel ZIF-67/CdS hollow sphere (HS) and ZIF-8/CdS HS heterostructures through an in situ self-assembly process, in which ZIF-67 and ZIF-8 are closely coated on CdS HSs to form "double-shell"-like structures. This hierarchical heterostructure with porous outer layers on the surface of CdS HSs can expose accessible active sites and possess close contact. Upon visible-light illumination, the optimal proportion of ZIF-67/CdS HS displays a hydrogen generation rate of 1721 µmol g-1 h-1, which is 11.9 and 3.1 times higher than that of a pure CdS HS (145 µmol g-1 h-1) and ZIF-8/CdS HS (555 µmol g-1 h-1), respectively. The proposed photocatalytic mechanism is explored: ZIF-8/CdS HS follows the type-II mechanism, and ZIF-67/CdS HS follows the Z-scheme mechanism. The reason for the higher photocatalytic activity of ZIF-67/CdS HS is that ZIF-67 not merely with a porous structure facilitates the diffusion of H2 gas, but with a well-matched band structure promotes charge transfer and separation.

In Situ Self-Assembled ZIF-67/MIL-125-Derived Co3O4/TiO2 p-n Heterojunctions for Enhanced Photocatalytic CO2 Reduction.

Photocatalytic CO2 reduction to carbon fuels is regarded as an ideal and sustainable way to provide clean energy and solve environmental crisis. Herein, a p-n Co3O4/TiO2 heterojunction photocatalyst was synthesized by one-step pyrolysis of self-assembly ZIF-67/MIL-125, which was used in photocatalytic CO2 reduction for the first time. Co3O4 nanocages were highly dispersed on the surface of TiO2 nanoplates with an intimate contact. The optimal Co3O4/TiO2 exhibited a significantly enhanced CO evolution rate of 1256 µmol g-1 h-1 under simulated solar light, which was 2.4 times higher than that of pure Co3O4. The high photocatalytic performance of Co3O4/TiO2 was attributed to its enriched active sites and formed p-n heterojunctions. According to the electrocatalytic measurements, the possible mechanism and photoinduced charge transfer process were discussed in detail. We believe that this research provides a facile and efficient approach to fabricate MOF-derived heterojunction photocatalysts for CO2 reduction.

Si-thiol supported atomic-scale palladium as efficient and recyclable catalyst for Suzuki coupling reaction.

Atomic-scale catalysts leverage the advantages of both heterogeneous catalysts for their stability and reusability and homogeneous catalysts for their isolated active sites. Here, a palladium catalyst supported by Si-thiol, a commercially available mercaptopropyl-modified and TMS-passivated amorphous silica, was synthesized and characterized by SEM,TEM, aberration-corrected STEM-HAADF, XRD, FT-IR and XPS. Statistical analysis revealed that the catalytic Pd species predominantly consisted of intermediate sized nanoparticles (<2 nm), small amounts of essentially isolated atoms (ca. 0.1 nm), and limited amounts of somewhat larger nanoparticles (<5 nm). The nanoscale atomic clusters dominated the reactivity and served as the key active sites for Suzuki coupling. The outcomes of the reaction were greatly affected by the choice of solvents, and Pd/Si-thiol was demonstrated to be reusable for more than three times without a noticeable loss of catalytic activity. [Formula: see text].

Synthesis, Characterization and Catalytic Properties of Attapulgite/CeO2 Nanocomposite Films for Decomposition of Rhodamine B.

ATP(attapulgite)/CeO2 nanocomposite films were prepared on the glass substrates via a sol-gel and dip-coating route. The ATP/CeO2 nanocomposite films were characterized by Powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), transmission electron microscopy (TEM), atomic force microscopy (AFM) and fourier transform infrared spectroscopy (FT-IR). The results showed that the ATP/CeO2 nanocomposite films were free from cracks and the nanoparticles were attached onto the surface of attapulgite. The ATP/CeO2 nanocomposite films displayed excellent catalytic activity for decomposition of Rhodamine B. The COD (chemical oxygen demand) removal rate of rhodamine B using ATP/CeO2 nanocomposite films as catalyst reached as high as 94% when the weight ratio of ATP to CeO2 was 2:1.

Effective adsorption of zeolite/carbon composite molecular sieve synthesized from spent bleaching earth.

Spent bleaching earth (SBE) as an industrious solid rubbish seriously causes the environmental pollution problem. The resourceful utilization of SBE has become increasingly important. In this work, silicon and carbon ingredients derived from SBE were coincidently employed to synthesize a 4A zeolite/carbon composite molecular sieve (4A/CMS). Therein, the graphite carbon components in the form of porous lamellar scattering among the interlayer, surface, and periphery of 4A zeolite promote the rate of mass transfer for the lipophilic gas, which can effectively improve the adsorption property for the volatile organic compounds. The obtained 4A/CMS has large specific surface area, hierarchical pore structure, satisfactory adsorption capacity, and regeneration performance, and its equilibrium adsorption capacity of p-xylene can achieve 209.57 mg·g-1. The pseudo-first-order rate equation is appropriate for the adsorption kinetics. In the end, the formation mechanism of 4A/CMS was illuminated in detail. □ Spent bleaching earth (SBE) as an industrious solid rubbish were utilized resourcefully. Silicon and carbon ingredients from SBE were coincidently employed to synthesize 4A/CMS. Graphitic carbon with hierarchical pore promoted the rate of mass transfer of organic gas. 4A/CMS exhibited excellent adsorption capacity and regeneration performance of p-xylene.

Boosting photocatalytic reduction of nitrate to ammonia enabled by perovskite/biochar nanocomposites with oxygen defects and O-containing functional groups.

Photocatalytic ammonia synthesis from waste nitrate has emerged as a promising strategy in water treatment; however, the conversion and selectivity still remain a great challenge. Herein, recyclable magnetic perovskite (LaFeO3)/biochar nanocomposites were successfully synthesized by the co-pyrolysis of the lotus biomass and Fe/La salts without extra organic complexants. Results showed that the lotus interacted with the iron ions (Fe3+) and the lanthanum ions (La3+) changing the surface and structural characteristics of catalysts. Oxygen defects of LaFeO3 were enhanced due to biomass introduction, which accelerated the separation of electron-hole pairs. On the other hand, Fe/La salts participated in the modification process of the biochar surface during the carbonization, which promoted the exposure of oxygen-containing functional groups and aromatic structures facilitating the nitrate adsorption. Notably, the redox-active quinone/phenol groups on the biochar surface contributed to the photogenerated electrons exchange favoring the ammonium ion (NH4+) selectivity as direct electron donor. Nitrate conversion reached 98% and ammonia selectivity reached 97% over the LaFeO3/biochar photocatalyst under visible light irradiation, when the mass ratio of lotus and Fe/La salts was optimized. Our findings may potentially provide a green and cost-effective way for ammonia recovery from nitrate contaminants.

Full spectrum driven SCR removal of NO over hierarchical CeVO4/attapulgite nanocomposite with high resistance to SO2 and H2O.

Removal of hazardous NO at low temperature via photo-assisted selective catalytic reduction (photo-SCR) strategy is promising, however fully harvesting of solar energy and achieving high SO2/H2O tolerance still remain a challenge. Herein, the phosphoric acid modified natural attapulgite(P-ATP) was employed as a matrix to immobilize CeVO4 by microwave hydrothermal method. Results show that P-ATP provides abundant active sites facilitating the in situ grow of CeVO4 nanorods on its surface which hierarchically construct a dendritic-like photocatalyst. The near-infrared (NIR) light is upconverted to visible and UV light through CeVO4 which not only broaden the absorption range of solar light, but also build Z-scheme heterostructure with P-ATP enhancing the redox potential of charge carriers. The CeVO4/P-ATP nanocomposite can reach as high as 92 % for NO conversion under full-spectrum solar irradiation, while retaining nearly 60 % conversion under NIR light. Moreover, the catalyst exhibits outstanding tolerance with SO2 and H2O due to the presence of Ce species which can prevent NH3 from being sulfated, while ATP prevent catalyst from being corroded by H2O. This work may open up a new window for full-spectrum driven SCR of NO based on cost-effective mineral catalyst.

Photo-assisted SCR removal of NO by upconversion CeO2/Pr3+/attapulgite nanocatalyst.

The emission of nitrogen oxides has caused severe harm to the ecosystem; thus, the development of low-cost and high-efficiency denitrification catalysts and new methods are of great significance. In this work, a co-precipitation method was employed to prepare Pr-doped CeO2/attapulgite (CeO2/Pr3+/ATP) nanocomposites. X-ray diffraction (XRD), photoluminance spectroscopy (PL), ultraviolet-visible diffuse reflectance (UV-Vis), Fourier transform infrared (FT-IR), and high-resolution transmission electron microscopy (HRTEM) were utilized to characterize the products. Results showed that the CeO2/Pr3+ nanoparticles were uniformly coated on the surface of ATP and demonstrated outstanding upconversion effect which converted the visible light to ultraviolet light. The upconversion luminescence of CeO2/Pr3+/ATP was strongest when the molar doping amount of Pr was 1 mol%, and the photo-SCR denitrification achieved the highest of 90% conversion and 95% selectivity when the loading amount of CeO2/Pr3+ was 40 wt%. The ATP and CeO2/Pr3+ constructed an indirect Z-type heterojunction structure mediated by oxygen vacancy which benefited the separation of charge carriers and enhanced the reduction-oxidation potentials, both are responsible for the remarkable denitrification performance.

Direct Z-scheme La1-xCexMnO3 catalyst for photothermal degradation of toluene.

A series of Ce-doped LaMnO3 (La1-xCexMnO3) were prepared and were tested for gaseous toluene oxidation in order to investigate the effect of cerium doping in LaMnO3 on activity under photothermal conditions. It was found that the activity and CO2 yield of the catalyst can be effectively increased when x = 0.25. A group of characterization is used to characterize the morphology, composition, and physical properties of the as-prepared catalysts. Results show that the Ce-doped LaMnO3 can form coexistence of La1-xCexMnO3 and CeO2, the reaction of CeO2/La1-xCexMnO3 under photothermal conditions follows the Mars-van Krevelen redox cycle mechanism, and the prepared CeO2/La1-xCexMnO3 can form a highly efficient Z-scheme heterojunction, which can enhance the electrons transfer speed of the catalyst. Moreover, in the photothermal catalytic degradation, lattice oxygen is the most important active substance, a small amount of cerium doping can increase the lattice oxygen content of perovskite and increase the activity of the reaction.

Z-Scheme Photocatalyst Constructed by Natural Attapulgite and Upconversion Rare Earth Materials for Desulfurization.

The Er3+:CeO2/ATP (attapulgite) nanocomposites were prepared by a facile precipitation method. The samples were characterized by various measurements. XRD and TEM showed that Er3+:CeO2 nanoparticles were well-crystallized and loaded on the surface of ATP. The visible light was converted into ultraviolet light by Er3+:CeO2 as evidenced by upconversion photoluminance (PL) analysis. The mass ratio of Er3+:CeO2 to ATP on the desulfurization efficiency was investigated. Results showed that the desulfurization rate reached 87% under 4 h visible light irradiation when the mass ratio was 4:10. The mechanism was put forward as follows. Er3+:CeO2 and ATP formed Z-scheme heterostructure intermediated by oxygen vacancy, leading to the enhanced separation of photogenerated charges and preservation of high oxidation-reduction potential, both of which favored for the generation of radicals to oxidize sulfur species.

In situ growth of Au nanocrystals on graphene oxide sheets.

Au nanocrystals (AuNCs) with a size of 10-20 nm decorated on graphene oxide (GO) were fabricated successfully through a hydrothermal reduction and crystallization route without any extra reductants and capping agents. The hydrophobic areas of GO benefit the formation of nanocrystals (NCs) with {111} facets totally exposed; however, the hydrophilic areas are detrimental to the crystallization. The morphology of AuNCs could be tailored by the degree of oxidation on the GO surface. The shape-controllable and reducing properties of GO are in favor of "clean" synthesis of noble metal NCs decorated on graphene.

Transformation of ZnO polycrystalline sheets into hexagon-like mesocrystalline ZnO rods (tubes) under ultrasonic vibration.

The mesoscale assembly process is sensitive to additives that can modify the interactions of the crystal nucleus and the developing crystals with solid surfaces and soluble molecules. However, the presence of additives is not a prerequisite for the mesoscale transformation process. In this study, ZnO sheet networks were synthesized on Al foils by a hydrothermal process. Scanning electron microscopy and transmission electron microscopy images confirmed that under ultrasonic vibration, monolithic polycrystalline ZnO sheets transformed into hexagon-like mesocrystalline tubes or rods. The formation mechanism was discussed.