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In this study, a piece of filter paper with good flexibility and hygroscopicity was used to support catalysts after a pencil drawing process. A layer of thin Ni film was deposited on the surface of the conductive graphite layer using an electrochemical method at a negative potential. Pd nanoparticles with high electrocatalytic activity for NaBH4 oxidation were introduced by immersing the Ni film-graphite-filter paper (NGF) in PdCl2 solution to obtain a Pd-NGF (PNGF) electrode. The morphology and phase structure of PNGF were characterized using scanning electron microscopy (SEM) equipped with an energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and an X-ray diffractometer (XRD). The PNGF electrode was used as the anode in direct borohydride fuel cells (DBFCs), and the electrochemical properties for NaBH4 oxidation were determined by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS). The oxidation current density reaches 550 mA cm−2 at −0.4 V when the electrolyte contains 2 mol dm−3 NaOH and 0.10 mol dm−3 NaBH4. [ABSTRACT FROM AUTHOR]

CuO/CeO2 catalysts were widely studied as an alternative to precious metal catalysts, and the Cu–Ce synergy was essential to improve the catalytic performance. In this paper, the effects of CuO loading on Cu–Ce synergy in CuO/CeO2 nanorod catalysts and their performance in toluene combustion were systematically investigated. It was found that non-equilibrium plasma facilitated the dispersion of CuO active species on the CeO2 surface. With the increase of the CuO loading from 1 wt% to 4 wt%, the Cu–Ce synergistic effect was gradually improved, which generated Cu+/Cu2+ and Ce3+/Ce4+ redox electron pairs. The highest oxygen vacancy concentration and Cu+ content of CuCe-4 (4 wt%) resulting from strong Cu–Ce synergy accelerated the activation of chemisorbed oxygen and consequently improved the efficiency of toluene catalytic combustion. [ABSTRACT FROM AUTHOR]

Chiral Ph-dbfox (Ph-dbfox = (R,R)-4,6-dibenzofurandiyl-2,2′-bis(4-phenyloxazoline))/Zn(NTf2)2catalyzed enantioselective Friedel–Crafts reactions of β-CF3acrylates with pyrroles and indoles have been investigated, which afforded the corresponding chiral trifluoromethyl pyrrole and indole derivatives in high yields (90–99%) with a range of 66–99% ee values. With the aid of the chiral adduct of the asymmetric Friedel–Crafts reaction, the chiral trifluoromethylated heliotridane has been successfully constructed in good total yield. [ABSTRACT FROM AUTHOR]

Selective oxidation of tetralin by molecular oxygen over mesoporous CrMCM-41 molecular sieve catalyst using supercritical carbon dioxide (scCO2) solvent has been investigated. CrMCM-41 catalyst gave high selectivity (96.2%) and good yield (63.4%) of 1-tetralone. The presence of scCO2medium improves 1-tetralone selectivity and suppresses leaching of chromium from the CrMCM-41. The activity over recycled CrMCM-41 remains nearly the same under the present experimental conditions. The effect of the reaction parameters on CrMCM-41 was also studied in detail along with comparison of its catalytic activities with other mesoporous catalysts, viz.MnMCM-41, CoMCM-41, microporous CrAPO-5, CoMFI, and macroporous Cr/SiO2catalyst, respectively. In addition this catalytic system was also applied for the oxidation of other benzylic compounds such as indane, fluorene, acenaphthene and diphenylmethane. [ABSTRACT FROM AUTHOR]

Developing high-efficiency electrocatalysts for the hydrogen evolution reaction (HER) is of great importance. In this paper, dendrite-free Ni–Cu catalysts were synthesised via one-step pulse electrodeposition under a weak magnetic field (0.5 T). Regardless of the direction of the magnetic field, the ions were affected by the magnetohydrodynamic (MHD) effect, which greatly promoted the mass transfer and dispersion uniformity, and suppressed the uncontrollable agglomeration by electrodeposition. It was found that the nucleation mechanism changed from progressive nucleation under a 0 T magnetic field to instantaneous nucleation under a 0.5 T magnetic field. Large-scale (325 nm, 0 T) dendrite growth on the single-sided plane was successfully suppressed, and replaced by smaller (90 nm, 0.5 T) and uniformly distributed cluster growth around the carbon paper. In addition, the (111) plane was strengthened by the magnetic field. Electrochemical analysis showed that the Ni–Cu catalysts exposed more surface area and exhibited greatly enhanced catalytic activity, which only needed −57.3 mV to deliver the current density of 10 mA cm−2 with a small Tafel slope of 99.4 mV dec−1 in 1 M KOH. Overall, magneto-electrodeposition, especially under weak magnetic field conditions, provides great promise for the preparation of HER catalysts. [ABSTRACT FROM AUTHOR]

Fe, N co-doped carbon electrocatalyst is one of the most attractive alternatives to Pt/C catalysts due to its high catalytic activity, excellent stability and low cost. However, obtaining stable and efficient Fe, N co-doped carbon oxygen reduction reaction (ORR) catalysts based on simple processes is still a challenge. Herein, Fe, N co-doped porous carbon (Fe–N–C) with an open macroporous frame structure is prepared by using inorganic molten salts (FeCl3·6H2O and ZnCl2) and ethylenediaminetetraacetic acid as the template and nitrogen-containing carbon precursor, respectively. The open pore structure of the Fe–N–C material precisely tailored with the inorganic molten salt template exhibits high specific surface area (676.5 m2 g−1) and appropriate pore size, which can promote oxygen adsorption and expand the oxygen reduction interface, resulting in the acceleration of the electron/charge transfer processes and an improved electrocatalytic performance. The optimized Fe3–N–C-800 electrocatalyst exhibits good catalytic activity for ORR, such as high onset potential of 0.998 V and half wave potential of 0.84 V in alkaline media, as well as high stability and methanol tolerance. Furthermore, a novel Zn–air battery assembled with carbon paper containing Fe3–N–C-800 electrocatalyst as air cathode shows high open-circuit voltage (1.485 V), high specific capacity (870 mA h g−1 at 10 mA cm−2), excellent reversibility and stability. The proposed synthetic strategy provides new opportunities to design and construct carbon frame materials with the desired open macroporous structure to improve their electrocatalytic performance. [ABSTRACT FROM AUTHOR]

It is of great significance for chemical energy storage devices, especially for the practical application of rechargeable zinc–air batteries (ZABs), to find efficient and economical bifunctional catalysts. Metal–organic frameworks (MOFs) have recently become hot research materials, and are often used as precursors of catalysts. This paper reports a carbon skeleton-coated bimetallic sulfide derived from MOF nanostructures that were used as cathode catalysts for ZABs. The N,S co-doped carbon-loaded FeS2,CoS2 ((Co,Fe)S2/CNS) catalysts exhibit excellent electrochemical properties in alkaline solutions due to the protection of metal sulfides by the carbon structure, the synergy of bimetallic Fe and Co, and the high surface area of the carbon skeleton. (Co,Fe)S2/CNS catalysts show a very low potential difference (ΔE = 0.68 V), a high specific capacity (759.1 mA h g−1) and good charge–discharge cycling performance (360 cycles/120 h) when applied to ZABs. This indicates that the prepared (Co,Fe)S2/CNS catalysts have a broad application prospect in the field of ZABs. [ABSTRACT FROM AUTHOR]

Liquid phase oxidation of 2-methylnaphthalene (2-MN) is a common synthetic route for the preparation of 2-methyl-1,4-naphthoquinone (2-MNQ). Metal-free carbon materials doped with heteroatoms have been proven to have excellent catalytic potential in various reaction fields. In this paper, the catalytic performance of N, F co-doped benzoxazine carbon materials for the selective oxidation of 2-MN was studied. The results show that the catalyst obtained at a carbonization temperature of 700 °C has the best catalytic performance. Under optimized conditions, the 2-MN conversion is 97.9%, and the 2-methyl-1,4-naphthoquinone selectivity is 84.3%. In addition, this catalyst still exhibits good catalytic activity after five cycles. Based on the experimental and characterization results, graphitic nitrogen species play a key role in the catalytic reaction and there is an almost linear relationship between the F content and the selectivity of 2-MNQ. This work provides a greener and more efficient method for the preparation of 2-MNQ with N/F co-doped mesoporous carbon. [ABSTRACT FROM AUTHOR]

In this paper, the effects of Zr, Al or Sr doped Mn/MCM-41 on NH3-SCR activity, SO2/H2O resistance and mechanism were studied. The results showed that Mn/Zr-MCM-41 has 100% NOx conversion at 175–300 °C while Mn/Al-MCM-41 achieves about 94% N2 selectivity at 120–400 °C. Zr doping significantly enhances the resistance to SO2 at 200 °C while Sr plays a negative role. Doped metal does not change the ordered hexagonal arrangement of MCM-41, but can cause the specific surface area enrichment of Mn while Al doping leads to the entry of Mn into the channel of MCM-41. Mn/MCM-41 has only Lewis acid sites, but Zr, Al or Sr doped catalysts have Lewis and Brønsted acid sites. Moreover, the reaction path on Mn/MCM-41 and Mn/Zr-MCM-41 mainly conforms to the L–H mechanism while Mn–Al or Mn–Sr doped catalysts follow L–H and E–R mechanisms. However, the deposited sulfates change the progress of the NH3-SCR process and cause a decline of SCR activity. [ABSTRACT FROM AUTHOR]

In this paper, the effects of sulfuric acid treatment of a ZrO2 support (ZrO2-S) on the Ca resistance of CeO2 catalysts were investigated. The results showed that the CeO2/ZrO2-S catalyst exhibited much better SCR activity and Ca resistance compared with the CeO2/ZrO2 catalyst. To further reveal the Ca resistance mechanism, BET, XRD, Raman, XPS, H2-TPR, NH3-TPD and in situ DRIFTS were used to characterize the changes in structure and properties of the CeO2/ZrO2 and CeO2/ZrO2-S catalysts before and after the Ca deactivation tests. The Ca poisoning of the CeO2/ZrO2 catalysts was mainly due to the decrease in specific surface area and surface acidity, the loss of reducibility and the enhanced stabilization of adsorbed nitrate/nitrite species. The treatment of ZrO2 with sulfate acid led to an increased specific surface area and highly-dispersed Ce species at the catalyst surface. It was also beneficial to inhibiting the transformation of ZrO2 from the tetragonal to the monoclinic phase. Moreover, it also enhanced the redox properties, Ce3+ species ratio, total surface acidity (especially Brønsted acid sites), and adsorption of NH3 species. The SCR reactions via both Langmuir–Hinshelwood (L–H) and Eley–Rideal (E–R) mechanisms could proceed well even after the CeO2/ZrO2-S catalysts were subjected to Ca poisoning. [ABSTRACT FROM AUTHOR]

In this paper, a Ce-W/TiO2-mSiO2 catalyst was prepared by a co-precipitation method with the addition of silicon acid to enhance and broaden the denitrification (deNOx) efficiency and temperature range of the Ce-W/TiO2 catalyst. The test results of deNOx performance showed that temperature ranges of the 80% and 90% deNOx efficiencies of the Ce-W/TiO2 catalyst with 30% silicic acid were increased by 35 °C and 30 °C, respectively, and the highest deNOx efficiency was increased to 99.53% compared with that without silicic acid. Moreover, the XRD, BET, SEM, XPS, NH3-TPD and H2-TPR analysis revealed that strong water absorption of silicic acid provided more SiO2 for the catalyst to increase its specific surface area. Meanwhile, the volume of a TiO2 cell increased and the crystallinity of CeO2 decreased, which enhanced the number of Lewis and Brønsted acid sites on the catalyst surface and promoted the deNOx reaction. Besides, the ratios of Ce3+ and Oα on the catalyst surface were about doubled with the addition of 30% silicic acid, thus improving the deNOx performance of the catalyst. [ABSTRACT FROM AUTHOR]

Exploring active catalyst components is very important to develop high-performance and highly stable ORR electrocatalysts to replace costly Pt-based catalysts, though it remains an ongoing challenge. In this paper, three ORR catalysts with different active components were obtained by calcination of different proportions of mixed precursors simply and delicately. Among them, precursor 1 (bimetallic polymer Fe/Zn-ZIFs@ZnCO3) played the role of a self-sacrificing template, while precursor 2 (an N, P-co-doped polymer) played the role of a volatile atmosphere. Precursor 2 also embedded N and P heteroatoms into the carbon framework during high-temperature volatilization, which resulted in subtle changes in the active catalyst components. Finally, a hybrid of metal Fe and α-Fe2O3 nanoparticles embedded in N, P-codoped carbon nanotubes with many separated gullies (named α-Fe2O3/Fe@NPC) exhibited excellent ORR catalytic activity in an alkaline solution as compared to commercial Pt/C. This work provides a new strategy for designing controllable active components using volatile precursors. [ABSTRACT FROM AUTHOR]

In this paper, a Co--Fe LDO catalyst was prepared by combining K2Cr2O7 and Cr(NO3)3 to modify the LDH precursor. The catalytic activity of NOx and o-DCB was systematically studied, and the effect of gas composition on the catalytic activity was investigated. The prepared Cr (0.25)/Co--Fe LDO catalyst showed the best catalytic performance, with conversion efficiencies of NOx and o-DCB of 89.0% and 81.6% at 250 °C, respectively. The catalysts were characterized by XRD, BET, SEM, XPS, H2-TPD and NH3-TPD to explore the reaction activity. In addition, the interaction between NH3-SCR and o-DCB oxidation was investigated by changing the gas atmosphere. The results showed that the inhibition at low temperature (< 200 °C) could be attributed to the residues of the by-products of incomplete oxidation. The further oxidation of NO to NO2, and the dissociation of NH3 are the reasons for the mutual promotion of the two reactions in the middle and high temperature sections. Water vapor has little effect on the reaction and the introduction of SO2 will cause irreversible inactivation of the catalyst. [ABSTRACT FROM AUTHOR]

Due to the synergistic effects of different metal sites, the double atom or multiple atomic catalysts are very promising for use in electrocatalysis. This paper focuses on the synthesis of urea [CO(NH2)2] under the synergistic effects of bimetallics. The heteronuclear diatomic molecular catalysts were designed and screened, and the details and energy information of the elementary reactions were provided from the atomic level using theoretical simulation, which provided a new understanding for the study of the reaction mechanism. It was found that the NbVN6C catalyst was the best catalyst for the electrosynthesis of CO(NH2)2 (0.37 eV < 0.44 eV < 0.67 eV < 0.74 eV < 0.84 eV for NbVN6C, TaVN6C, WVN6C, MoVN6C, ReVN6C, respectively), and the optimal path was * → *N2 → *NN → *NNH → *NNH2 → *HNNH2 → *H2NNH2 → *H2NNH2–CO2 → *H2NNH2–COOH → *H2NCONH2. At the same time, compared with the homonuclear diatomic catalyst V2N6C, the heteronuclear diatomic molecular catalyst NbVN6C had a smaller limiting potential (−0.37 V and −0.59 V), which demonstrated the usefulness of this study. [ABSTRACT FROM AUTHOR]

The development of advanced carbon materials as metal-free catalysts holds great importance for mercury catalyst replacement in acetylene hydrochlorination. In this paper, we transform discarded cigarette butts into a porous nitrogen-doped carbon material (N-CB-800), exhibiting characteristics of high specific surface area, large N doping amount, defective structure and strong C2H2 chemical adsorption ability. These unique features endow N-CB-800 with a high catalytic performance with an acetylene conversion of 71.8% at 220 °C and an acetylene space velocity of 100 h−1, making it one of the most active metal-free catalysts. This work will be of great value for the recycling of living waste and provide meaningful guidance for the development of non-mercury catalysts for acetylene hydrochlorination. [ABSTRACT FROM AUTHOR]

The synthesis of propargylamines by traditional methods is limited by several drawbacks such as anhydrous conditions, low temperatures and by-products. A3-coupling reactions (aldehydes, amines, and alkynes), that involve a catalytic amount of metal complexes, have been recently recognized as a powerful alternative for the synthesis of these important scaffolds. In this paper, four new silver and gold complexes (3a, 4a, 3b and 4b), bearing N-heterocyclic carbene (NHC) ligands, were tested in A3-coupling reactions, combining the use of harmless metals as catalysts with sustainable reaction conditions (neat conditions or water as solvent). NHC silver(I) and gold(I) complexes were synthesized and characterized by 1H and 13C NMR spectroscopy, ESI-MS and elemental analysis. The molecular structure of the NHC gold(I) complex 4b was determined by single crystal X-ray diffraction. A comparison of the catalytic behavior in A3-coupling reactions among the synthesized complexes disclosed the higher efficiency of gold catalysts. Computational studies shed light on species possibly involved in the catalytic mechanism. [ABSTRACT FROM AUTHOR]

Precious metal nanoparticles (NPs) are attractive for use in the field of catalysis because of their precisely controlled sizes and shapes. However, NPs exhibit insufficient anti-sintering properties under common operating conditions due to their poor thermal stability at elevated temperatures. In this paper, the preparation of noble metallic NPs (Pd and Au) incorporated inside the pores of an SBA-15 support via a sol-immobilization method, which prevents their aggregation, is reported. The Pd NPs retain their size of ∼5 nm within the channels of SBA-15, even after aging at 800 °C for three days under an air atmosphere. However, Au NPs aggregated at a temperature of calcination above 500 °C. Using a set of characterization methods comprising XRD, STEM, HRTEM, TPR, and DRIFTS analysis, it is revealed that Pd on SBA-15 exhibits better anti-sintering properties than the Au supported system. The catalytic activity and durability of M/SBA-15 (M: Pd or Au) catalysts were studied using CO oxidation with and without steam (10 vol%). Interestingly, a hydrothermally treated (Pd/SBA-15-750-H2O-3d) catalyst leads to the partial re-dispersion of Pd. This helps to attain smaller particles of ∼1.6 nm, which play a prominent role in the catalytic performance. This work provides insight into the design of sintering-resistant metal catalysts, which would be suitable for industrial applications under harsh conditions. [ABSTRACT FROM AUTHOR]

In this paper we introduce the use of molecular metal clusters as precursors for the in situ formation of nanoparticles with a high activity and surprising stability as electrocatalysts in energy conversion. The work is relevant in the present quest for remediation of greenhouse gas production and global warming, where fuel cells and metal and lithium air batteries are intended to play a crucial role. The research for an increased efficiency of these devices needs to solve the problems linked to the Oxygen Reduction Reaction (ORR), which plays a key role in these processes, due to its sluggish electrochemical kinetics that must be increased by a suitable electrocatalyst. Here we describe the facile synthesis of a new cathode material for fuel cells based on CO–Pt molecular clusters that are strongly bound to Vulcan XC72R®. The Pt–CO bond can be removed just after the synthesis, by thermal treatment at 450 K, or once in solution, leaving low-coordinated, highly reactive surface Pt atoms. The materials are investigated thoroughly using identical-location transmission electron microscopy, X-ray diffraction (with pair distribution function) and X-ray absorption measurements, revealing an extremely small, yet controlled, particle size (1–2 nm), with high structural and morphological stability, and lack of any aggregation process after thermal treatment. The surprising stability is related to the quite large number of Pt–C bonds that the nanoparticles form with the support, allowing them to attach stably onto the carbonaceous moiety. At the same time, the nanoparticles are particularly strained, and enclose a high defect density, thus enhancing their catalytic properties. The best performing composite presents a mass activity of 225 mA mgPt−1 @ 0.9 V vs. RHE for the ORR, and a less cathodic onset potential compared with a conventional Pt nanoparticle cathode, used as a benchmark under the same experimental conditions, while in turn having a lower noble metal content. [ABSTRACT FROM AUTHOR]

Dissolved oxygen (DO) is a primary corrosive substance in the transportation process of urban reclaimed water by pipelines. MCM-41 is widely used as a catalyst carrier because of its high specific surface area and low mass transfer resistance. The catalyst, namely Cu/Al-MCM-41 was prepared by doping Cu and Al in MCM-41 using one-step hydrothermal method and was used to catalyze reducing DO in reclaimed water by carbohydrazide. The effects of reaction temperature, the mass concentration of carbohydrazide, the initial pH value of water, and the mass concentration of catalyst on the removal rate of DO from reclaimed water were investigated in this paper. The reusability and catalytic mechanism of Cu/Al-MCM-41, the fresh catalyst, were determined and the used catalyst was characterized by XRD, FTIR, SEM, NH3-TPD, and BET methods. It was concluded that Cu and Al were successfully doped into MCM-41, and the synthesized molecular sieves had a highly ordered hexagonal mesoporous structure. Moreover, the doping of Al metal into MCM-41 improved the acid strength and acid centers significantly. The DO removal rate could reach 98.54% under the temperature of 45 °C, which is 3 times the theoretical feed amount of carbohydrazide, at the initial pH value of 8.5 and the mass concentration of 0.7 g L−1 of the catalyst after 60 min. The Cu/Al-MCM-41 catalyst still showed high catalytic activity after three tests. The active metal Cu could catalyze the decomposition of carbohydrazide into carbon dioxide, nitrogen, and hydrogen atoms The increase of hydrogen atom concentration adsorbed on the catalyst surface led to the rapid reduction of DO. [ABSTRACT FROM AUTHOR]

Carbon materials show great potential in catalytic applications, due to their advantages of wide raw material sources, stable chemical properties, and large specific surface area. In this paper, N-doped biochar was prepared from Pennisetum giganteum for supporting PdLa bimetallic nanoparticles to achieve efficient conversion of acetylene. The results showed that the conversion and ethylene selectivity of the Pd0.25La0.25/N-pgBC bimetallic catalyst could reach 100% and 94.2%, respectively. From the characterization results, it could be inferred that the electron transfer from lanthanum to palladium can weaken the ethylene adsorption onto the negatively charged Pd sites and thus improve the selectivity of Pd0.25La0.25/N-pgBC. It is noted that the bimetallic PdLa/N-pgBC catalyst showed strong component dependence, which may be caused by the difference in electronic or geometric modification caused by different metal ratios. This work has shown that the active site separation effect formed by doping inert metals is of great significance to the whole catalytic field. [ABSTRACT FROM AUTHOR]

Pd/C catalysts are one of the most efficient catalysts for direct synthesis of H2O2 from H2 and O2 (DSH), while pretreating the activated carbon by HNO3 will influence the performance of the Pd/C catalyst. In this paper, a series of HNO3-pretreated and N2-calcinated activated carbon-supported Pd catalysts were prepared and evaluated for the DSH reaction at ambient temperature. The experimental results showed that using HNO3-pretreated activated carbon as the support enhanced H2O2 selectivity greatly, and the highest H2O2 selectivity of 90% was obtained on 20 wt% HNO3-pretreated catalyst. The catalysts were systematically characterized by multiple techniques including transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), N2 adsorption–desorption, Boehm titration and other techniques. It was found that the textural properties of activated carbon did not affect the catalytic performance, while the effects of acid functional groups of activated carbon were supposed to improve the H2O2 selectivity, and lower H2O2 decomposition and hydrogenation capacities of the catalyst. [ABSTRACT FROM AUTHOR]

In this paper, the heterogeneous nature of an amorphous SiO2 support, the exceptional properties of polyamidoamine dendrimers (PAMAM), and the unique properties of pincer ligands (NNN type) were combined for immobilization of a triazine-derived Cu(II)-NNN pincer complex onto the dendritic nanoparticle supports. All of the prepared samples in each step were fully characterized and compared by several techniques, including FTIR, TGA–DTG, elemental analysis (EA), SEM, and TEM. In this regard, two different methods were applied and used for the synthesis and growth of a PAMAM dendrimer onto the SiO2 support via the divergent synthesis method (without and with the catalyst). In the presence of a tetrabutylammonium bromide (TBAB) catalyst, dendritic supports were prepared in a shorter time with better growth. Subsequently, a symmetric and neutral tridentate NNN-pincer ligand derived from trichloro-1,3,5-triazine/2-aminopyridine was immobilized on each of these dendritic nanoparticle supports. The successful immobilization of a pincer ligand on the nanoparticle dendritic support was also supported by the techniques mentioned above. Finally, the reaction of each prepared support with copper(II) chloride at room temperature resulted in the formation of immobilized Cu(II)-NNN pincer complexes as partially supported by EPR and UV-vis spectroscopy. The loading of the copper ions for each sample was measured by ICP/OES analysis. Among the five final immobilized ligands, the NNN pincer-G′1-SiO2 (G′1 = the first generation of PAMAM dendrimers prepared via the second method) showed more suitable ability for copper adsorption. [ABSTRACT FROM AUTHOR]

The catalytic properties of metal–organic frameworks (MOFs) containing triangular Fe(III) clusters in the promotion of organic syntheses and photocatalysis applications have been receiving substantial attention for decades. These clusters are appealing due to the strong Lewis acidity afforded by coordinatively unsaturated sites upon the removal of solvent from the framework. In this paper, triangular Fe(III) cluster-based MOFs were shown to be highly efficient heterogeneous catalysts for the solvent-free one-pot condensation of 2-aminobenzamide and alcohols to form quinazolin-4-ones under microwave irradiation. The Fe-MOF catalysts ranging from microporous to mesoporous structures with a variety of geometrical pore structures were investigated. Because of the open accessible spaces for reactants and high density of active sites, MOF-907, built from trimer Fe clusters and a mixture of two linkers, was more effective than other Fe(III)-MOFs. The catalyst can be used for a broad substrate scope and recycled several times without a significant drop-off in its activity. [ABSTRACT FROM AUTHOR]

In this paper, a new visible-light harvesting photocatalyst denoted as g-C3N4/γ-Fe2O3/TiO2/Pd was successfully fabricated and fully characterized by different techniques including FT-IR, XPS, XRD, TEM, SEM, elemental mapping, VSM, DRS, and ICP analysis. The as-prepared catalyst was utilized as an efficient magnetically separable photocatalyst in the fluoride-free Hiyama and Suzuki–Miyaura cross-coupling reactions at room temperature under visible light irradiation. By using this approach good to excellent yields of biaryls were achieved from the reaction of various aryl iodides/bromides and even chlorides as highly challenging substrates, which are more available and cheaper than aryl iodides and bromides, with triethoxyphenylsilane or phenylboronic acid. The superior photocatalytic activity of g-C3N4/γ-Fe2O3/TiO2/Pd could be attributed to the synergistic catalytic effects of Pd nanoparticles and g-C3N4/γ-Fe2O3/TiO2. Utilizing a sustainable and safe light source, no need to use any additive or heat, using an eco-friendly solvent and long-term stability and magnetic recyclability of the catalyst for at least seven successive runs are the advantages that support the current protocol towards green chemistry. [ABSTRACT FROM AUTHOR]

This paper reports for the first time the preparation of Co3O4 nanorods by simple hydrothermal and annealing methods, which are doped with polyoxometalates that act as an intermediary in electronic transmission to accelerate electron transport. The designed H3PW12O40(PW12)/Co3O4–Cu2S composite film was prepared by the screen printing method to boost its efficiency as the counter electrode for quantum dot-sensitized solar cells, where the preparation process is simple and inexpensive. PW12/Co3O4–Cu2S (Jsc = 16.60 mA cm−2, Voc = 0.636 V, Rct = 0.32 Ω and FF = 0.436) shows better electrocatalytic performance compared to the original Co3O4 and Cu2S. Accordingly, the photoelectric conversion efficiency of PW12/Co3O4–Cu2S is 4.67%, which is 10%, 46%, 55.6%, and 72% higher than those of Co3O4–Cu2S (4.2%), Cu2S (2.54%), PW12/Co3O4 (2.07%), and Co3O4 (1.30%), respectively. Electrochemical impedance spectroscopy and Tafel measurements performed on two CE symmetric virtual cells proved the excellent electrocatalytic activity of PW12/Co3O4–Cu2S. Therefore, this composite film can be used as an alternative option for QDSSC counter electrodes. [ABSTRACT FROM AUTHOR]

In this study, a novel magnetically recoverable Fe3O4@SiO2–BenzIm-Fc[Cl]/BiOCl nano-composite was synthesized using a simple chemical co-precipitation method. This is the first time that a magnetic nano-catalyst bearing ionic liquid, ferrocene and BiOCl is synthesized. The Fe3O4@SiO2–BenzIm-Fc[Cl]/BiOCl nano-composite was characterized by Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX) and field emission scanning electron microscopy (FE-SEM) techniques. The catalytic activities of the novel magnetic nano-composite were evaluated in one-pot three-component synthesis of a wide variety of 2-amino-3-cyano-4H-chromene derivatives under ultrasound irradiation. A simple, facile and highly efficient ultrasound-assisted method was developed to synthesize 4H-chromene derivatives via one-pot, three-component reaction of aldehyde, malononitrile and active phenolic compounds (2-naphthol, 1-naphthol, 3-(dimethylamino)phenol, resorcinol and orcinol) at room temperature. The reaction of aldehyde, malononitrile and orcinol is newly introduced in this paper. The ultrasound-assisted synthesis protocol that was studied in this article exhibits some notable advantages such as short reaction times, operational simplicity, green reaction conditions, high yields and easy work-up and purification steps. In addition, the novel magnetic nano-composite could be easily recovered by an external magnetic field and reused for six-reaction cycles without significant loss of its catalytic activity. [ABSTRACT FROM AUTHOR]

In this paper, the Keplerate nanoball iso-polyoxomolybdate {Mo132} supported on activated carbon (AC) has been synthesized and evaluated as a new, green and cost-effective catalyst for the oxidative desulfurization of a model fuel containing dibenzothiophene (DBT). The {Mo132}/AC catalysts, which were prepared with various {Mo132} contents, were characterized using FT-IR, XRD, SEM, EDX, ICP-OES, H2-TPR and nitrogen adsorption/desorption isotherms. Experimental evaluations showed that the catalyst was highly efficient in the removal of DBT using hydrogen peroxide (H2O2) as the oxidant, which could result in a sulfur removal of up to 99.5% (or even more than that) under optimum reaction conditions. The factors affecting the process including catalyst dosage, temperature, O/S molar ratio, reaction time and initial sulfur content were evaluated, and the optimum operating conditions were determined. In addition, the new catalyst was recoverable and the recovered {Mo132}/AC demonstrated a relatively similar catalytic activity to the fresh one. According to the results of GC-MS analysis, a sulfone species was found to be the only product of DBT oxidation by H2O2 over {Mo132}/AC. Moreover, a mechanism for the oxidative desulfurization of DBT by the new catalyst was proposed. The present study suggested that the {Mo132}/AC composite could be used as an efficient catalyst for the deep oxidative desulfurization and removal of refractory sulfur compounds in fossil fuels. [ABSTRACT FROM AUTHOR]

A new material, MgAl-LDHs/Al2O3 fiber (abbreviated as MAF), was prepared using the classical hydrothermal method with a modification in this paper. The influence of different pH values on the structure and catalytic performance of catalysts for propane dehydrogenation was studied. The as-prepared materials were characterized by XRD, SEM, TEM, SAED, N2-physisorption, NH3-TPD, and TPO. Experimental results show that the pH value of the solution directly controlled the vertical growth of LDH sheets on Al2O3 fibers. After the suitable growth of LDH sheets, the dispersed state of active metal Pt was improved and the sizes were stabilized successfully at high temperature. Due to the effect of these LDH sheets, the BET surface and the regular pore system of the PtSn/15MAF catalysts were enhanced compared with the PtSn/CPMA catalysts. Finally, the propane dehydrogenation performance indicates that, when the pH was equal to 8.5, the catalysts (PtSn/15MAF) showed the highest conversion, selectivity and stability. [ABSTRACT FROM AUTHOR]

In this paper, tris(hydroxymethyl)methylene ammonium acetate supported on GO as a new multifunctional heterogeneous catalyst was synthesized. After its characterization by different techniques such as FT-IR, TEM, FESEM, EDS, XPS, solid-state MAS NMR and elemental analysis, it was used as an efficient catalyst for the synthesis of hexahydroquinolines (HHQs) via a one-pot multi-component reaction. Different HHQs were synthesized in the presence of this heterogeneous metal-free catalyst in good to high yields at room temperature under solvent-free conditions. The catalyst was easily separated and reused at least five times without significant loss of activity. The acidic nature of GO improved the catalytic activity of the supported ILs and also provided heterogeneity to the ILs. This is the first report for the synthesis of HHQs in the presence of a multifunctional heterogeneous catalyst. [ABSTRACT FROM AUTHOR]

In this paper, magnetic Fe3O4@SiO2@mSiO2 microspheres with core–shell structure were chosen as a catalyst support, then hyperbranched polyglycerol (HPG) was successfully grafted onto the exterior surface and mesopore wall of this material under the catalysis of isopropanol aluminum. Subsequently, the terminal hydroxyl groups of HPG were successfully transformed into carboxyl groups after modification with succinic anhydride. Ultimately, palladium nanoparticles (Pd NPs) were successfully anchored onto the surface of the aforementioned magnetic Fe3O4@SiO2@mSiO2 microspheres with high density carboxylic HPG, nanocrystallization by the complexation between Pd2+ ions and carboxyl groups and the subsequent reduction, a novel Fe3O4@SiO2@mSiO2-HPG-COOH-Pd(0) supported catalyst was successfully obtained. This novel supported Pd NP catalyst is very conducive to the transference and exchange of each component in the reaction system for the orderly mesoporous opening structure. Furthermore, the introduction of a magnetism nucleus can provide convenient magnetic separation. More importantly, the numerous terminal carboxyl groups on the surface of the magnetic Fe3O4@SiO2@mSiO2 microspheres can provide plenty of sufficient binding sites for Pd NPs, and the unique hyperbranched structure is very conducive to capture uniformly dispersed nanosized palladium and can effectively enhance the catalytic activity and stability. Research indicates that this novel supported Pd NP catalyst not only possesses extremely high Pd NPs loading capacity but also shows remarkable catalytic activity to the Suzuki cross-coupling reaction between aryl halides and phenylboronic acid. Simultaneously, the catalytic activity of this supported catalyst did not show evident loss after being used at least eight times. [ABSTRACT FROM AUTHOR]

The active species distribution of zeolites significantly influences the catalytic performance. In this paper, titanium silicalite-1 (TS-1) was synthesized from silica sol, TiCl3 and NH3 with tetrapropyl ammonium bromide (TPAB) as the template agent. Modification with ethanolamine altered the distribution of Ti species in TS-1 particles. Some large voids as 50 × 70 nm and 70 × 110 nm existed in the inner part of modified TS-1 crystals and were responsible for improved diffusion properties and accessibility to active sites. The modified TS-1 was examined in continuous cyclohexanone ammoximation. A high conversion of cyclohexanone (98%) and oxime selectivity (100%) was still maintained after the test reaction had been carried out up to 410 h. The modified TS-1 is able to serve as a stable catalyst for continuous cyclohexanone ammoximation. [ABSTRACT FROM AUTHOR]

While the purification of carbon nanotubes may be considered as an already sorted matter, their use in some highly demanding fields such as electrochemistry, biological studies or magnetism may be precluded by the remaining catalyst and carbonaceous impurities. For these purposes, the widely-used purification methods need to be improved. In this paper, a comprehensive study of the well-known gas-phase purification procedure of single wall nanotubes (SWNTs) is performed, which aims at depicting the nature and the amount of the remaining impurities, of both the catalyst and carbon types, and at getting insights into its mechanism. This has been achieved by cross-referencing data emerging from transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), electron diffraction, magnetization measurements, X-ray diffraction (XRD) and Raman spectroscopy. We demonstrate that this method can lead to the elimination of the largest part of the impurities while maintaining fairly good yields. According to the mechanistic picture we have drawn, we suggest some possible improvement to the procedure that should lead to fully purified SWNTs with limited subsequent losses. [ABSTRACT FROM AUTHOR]

As a dual-functional catalyst for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), Ru clusters have great potential, but there are certain difficulties regarding their stability on the substrate and the tunability of their electronic environment. Here, the S doped graphited biochar aerogel electrocatalyst was designed and synthesized using terrestrial lignin and algal polysaccharide as a carbon substrate. The Ru clusters were anchored on the S-doped carbon aerogel (P-Ru/SC) by carefully designing the Ru-S bond via a novel plasma assisted high temperature carbonization treatment. The optimized P-Ru/SC-2 catalyst exhibits excellent electrocatalytic performance for the HER and OER, achieving ultra-small overpotentials of 119.6 mV and 193.4 mV at 10 mA cm-2. The dual-electrode requires only 1.47 V to reach 10 mA cm-2. It is worth noting that a large number of S sites on graphited carbon can strongly interact with the Ru clusters, significantly improving the catalytic activity and stability for the HER and OER. [ABSTRACT FROM AUTHOR]