•MIL-53(Al) acted as a novel green catalyst for hydrothermal conversion of CMC.•A 5-HMF mol yield of 40.3% and a TRS mol yield of 54.2% were obtained.•Water has been used as single green solvent for the catalytic reaction.•It provides new opportunities to convert biomass to value-added chemicals.Catalytic hydrolysis of biomass over solid catalysts can be one of the most efficient pathways for a future sustainable society dependent on cellulose biomass. In this work metal–organic framework MIL-53(Al) without any functionalization was directly employed as an efficient heterogeneous catalyst for the hydrolysis of carboxymethyl cellulose (CMC) to 5-hydroxymethyl-furaldehyde (5-HMF) in aqueous phase. A 5-HMF molar yield of 40.3% and total reducing sugar (TRS) molar yield of 54.2% were obtained with water as single solvent at 473 K for 4 h. The catalyst could be reused three times without losing activity to a greater extent. With the remarkable advantages such as the use of water as single solvent and MIL-53(Al) as a novel heterogeneous green catalyst, the work provides a new platform for the production of value added chemicals and liquid fuels from biomass.

Early diagnosis and the timely treatment of cancer are key to improving patient survival rates at present. Metal–organic frameworks (MOFs) consisting of infinite crystalline lattices with metal clusters and organic linkers may provide opportunities for the detection of cancer cells which have remained undiagnosed. Herein, we report that Fe-MIL-101 possesses an intrinsic enzyme mimicking activity similar to that found in natural horseradish peroxidase and shows highly catalytic activity even at neutral pH. The Michaelis constant (Km) of Fe-MIL-101 with H2O2 as the substrate is about 616-fold (at pH 4.0) and 20-fold (at pH 7.0) smaller than free natural horseradish peroxidase (HRP), indicating a much higher affinity for H2O2 than HRP and most of the peroxidase mimetics. Moreover, Fe-MIL-101 was successfully used to detect cancer cells by conjugating folic acid onto Fe-MIL-101 without any surface modification. The detection limit of the method for HeLa cells was estimated to be 50 cells and the reaction colour produced with 10 cells could also be observed by the naked eye. The proposed method holds considerable potential for simple, sensitive, universal, and specific cancer cell detection.

Although a few systems prepared by using biotemplates have been employed as mesoporous photocatalysts, the natural latex secreted by plants has not been used as a template to synthesize porous materials, let alone for the achievement of high photocatalytic activity under solar light. Herein, one of the most important biosynthesized polymers, natural rubber latex from the rubber tree, Hevea brasiliensis in Xishuangbanna was directly used as a structure-directing agent in synthesis of thermally stable mesostructured TiO2. The as-prepared samples were characterized by XRD, FT-IR, XPS, N2 adsorption/desorption, TEM and UV-vis DRS. The synthesized TiO2 exhibited highly effective photocatalytic activity for the degradation of phenol and rhodamine B under solar light. Furthermore, addition of acetylacetone (ACA) during the synthesis significantly enhanced the photocatalytic activity. The reported strategies provide a new direction of using natural rubber latex as a template to prepare highly effective photocatalysts.

A photoactive compound extracted from a fungus (Hypocrella bambuase), named hypocrellins, was used as template to synthesize thermally stable mesoporous materials. The synthesized mesoporous titania samples were characterized using a combination of various physicochemical techniques, such as N2 adsorption/desorption measurement, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectroscopy (DRS) and Fourier transform infrared spectroscopy (FT-IR). The results of physicochemical characterizations showed that the as-synthesized sample was a composite of highly crystalline mesoporous anatase titania and graphitic carbon (gc–MTiO2), which implies the dual function of hypocrellins as template and “dopant”. The in situ doped graphitic carbon significantly increased the visible-light absorbance of TiO2. The gc–MTiO2 exhibited efficient photocatalytic activity under visible-light for photodegradation of acetaldehyde, a common indoor air pollutant. The photophysics and electron dynamics in this photocatalytic process were studied by time-resolved FT-IR spectra, in particular on the nano- to milli-second time scale. It is observed that electrons were injected into the conduction band of gc–MTiO2 and they were decayed to deep traps caused by graphitic carbon. The reported strategies could open up new uses for mesoporous titania self-doped with carbon in applications such as solar cells, photocatalysts, photoelectrical devices, and photo-induced sensors.

A stable photoactive metal–organic framework UiO-66(Zr) sensitized by adsorbed or directly added rhodamine B dye exhibited photocatalytic activity for hydrogen evolution under visible-light illumination (λ ≥ 420 nm). Using Pt as a co-catalyst, the adsorbed and directly added dye extremely enhanced the photocatalytic activity to 30 and 26 times the value afforded by bare Pt@UiO-66(Zr), respectively.

•Synthesis of mesoporous titania using resin acids and resinates as templates•Cobalt resinate templated mesoporous TiO2 without adding extra cobalt source.•Efficient photocatalysts for degradation of organic dyes under solar lightCobalt doped and undoped mesoporous titania were synthesized using resin acid as template. Moreover, without adding extra cobalt source, cobalt doped mesoporous titania was also synthesized by using cobalt resinate as both template and cobalt source. These mesoporous samples were characterized by a combination of various physicochemical techniques, such as N2 adsorption/adsorption isotherm, UV–vis diffuse reflectance, X-ray diffraction, high resolution transmission electron microscopy, XPS, and FT-IR. They were used for the photodegradation of methyl blue and Rhdamine B under visible light. It was found that P25 and mesoporous TiO2 synthesized using resin acid as template did not exhibit any meaningful activity for the photodegradation of two dyes under visible light. By contrast, cobalt doped mesoporous titania synthesized by using resin acid as template exhibited more significant photocatalytic yield (94%) for Rhdamine B. Moreover, cobalt doped mesoporous titania synthesized by using cobalt resinate as template also exhibited similar high photocatalytic activity for methyl blue to the former.

In this work, mesoporous TiO2 compose of anatase and brookite phases (M-TiO2) has been synthesized using 2,4,5-triphenylimidazole as template. The physical features of the as-prepared catalyst was measured by X-ray diffraction (XRD), low-temperature nitrogen adsorption/desorption, UV–visible diffuse reflectance spectrum, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The photocatalytic performance of the catalyst was evaluated in terms of the degradation of organic dyes. It is found that M-TiO2 exhibits reasonable activity under UV light and can significantly degrade methylthionine chloride, rhodamine B, gentian violet, safranine T, methyl violet and fuchsine basic under visible-light irradiation (λ≥420 nm).

We demonstrated that embedding of CdS on MOFs could significantly increase the photocatalytic efficiency of CdS for visible light-driven hydrogen production.

Adding a small amount of commercial GeO2 into aqueous suspension significantly enhanced the photocatalytic activity of titania-based photocatalysts for the degradation of dyes.

Although photosensitization of titania by organic dyes is one of the conventional ways for visible-light utilization of titania, previous studies have not yet addressed the use of dyes as templates in the synthesis of mesoporous materials, let alone the simultaneous achievement of highly crystalline mesoscopic ordering and visible-light photocatalytic activity. In this work, fourteen commercial synthetic dyes were directly used as structure-directing agents which convert to carbonaceous materials after 400 °C calcination in synthesis of thermally stable mesostructured titania. This in situ carbon enhanced the visible light photocatalytic activities for the degradation of aqueous dyes. The synthesized mesoporous titania samples were characterized by a combination of various physicochemical techniques, such as XRD, SEM, HRTEM, nitrogen adsorption/desorption, TGA–DSC, XPS, diffuse reflectance UV–vis and FT–IR. Most of prepared mesoporous titania photocatalysts exhibited better activity under outside solar light than under artificial UV light, due to the presence of carbonaceous species which were transferred from the dye templates. The reported strategies combine sol-gel chemistry and self-assembly routes directly using dye templates that tune the material's architecture, texture and particularly function, visible-light photocatalysis.

Poly(vinylpyrrolidone) (PVP)-capped copper nanoparticles synthesized by solvent-based polyol reduction were found to be effective catalysts for the polymerization of octadecylsilane and bis-(γ-triethoxysilylpropyl)-tetrasulfide. Comparing with PVP-capped silver nanoparticles, copper nanoparticles exhibited different catalytic activity, and the polymerization products also showed different morphologies. The effects of transition metal ions on the polymerization of octadecylsilane catalyzed by PVP-capped silver nanoparticles were also investigated. It was found that transition of metal ions not only had strong effects on the morphologies of the products of polymerizations, but also resulted in the disappearance of silver oxide. The products were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) and X-ray powder diffraction (XRD).

Allylic oxidation of cychohexene under atmospheric pressure of molecular oxygen was carried out over cobalt resinate in the absence of solvent. It was shown that cobalt resinate exhibited promising catalytic activity for the oxidation of cyclohexene to 2-cyclohexen-1-ol and 2-cychohexen-1-one under mild condition for the first time.

Mesoporous TiO2 with anatase crystalline structure (MTiO2/CAS) has been synthesized by using chrome azurol S (CAS, 2″,6″-dichloro-3,3′-dimethyl-4′-hydroxy-3″-sulfofuchson-5,5′-dicarboxylic acid) as template. It was characterized by X-ray diffraction, nitrogen adsorption/desorption, diffuse reflectance UV–visible and FT-IR spectrometry, and transmission electron microscopy. It was found that MTiO2/CAS had substantial photocatalytic activity in the degradation of methylthionine chloride, rhodamine B, gentian violet, safranin T, methyl violet, and fuchsine basic whereas Degussa P25 (P25) had negligible photodegradation yield (<6%) under visible light irradiation.

Cobalt doped mesoporous silica (Co-SBA-15) was synthesized using templating method and used for the photodegradation of methyl violet and methylthionine chloride under solar light. Co-SBA-15 was characterized by a combination of various physicochemical techniques, such as, N2 physisorption, diffuse reflectance UV–vis, X-ray diffraction and FT-IR. It was found that Co-SBA-15 in the absence of titania exhibited an obviously photocatalytic efficiency of degradation dyes under solar light irradiation, and its photodegradation rate is comparable with that of Degussa P25. By contrast, undoped SBA-15 exhibited high adsorption capacities but photocatalytically inactive under solar light.

Cobalt doped amorphous mesoporous titania–silica with Ti/Si mass ratio of 0.8 (Co–TiO2–SiO2) was synthesized and used for the photodegradation of six cationic dyes (gentian violet, methyl violet, methylene blue, fuchsin basic, safranine T, and Rhdamine B) under UV and visible light illumination. The catalyst was characterized by a combination of various physicochemical techniques, such as N2 physisorption, diffuse reflectance UV–vis, X-ray diffraction, and FT-IR.Co–TiO2–SiO2 exhibited activity under UV light and had better activity under visible light when compared with that of Degussa P25 TiO2. The activity of Co–TiO2–SiO2 was also compared with that of Co-MCM-41, Co doped mesoporous titania with a crystalline framework (Co–MTiO2) and titania-loaded Co doped MCM-41 (TiO2/Co-MCM-41) for the degradation of gentian violet under visible light irradiation. It was also found that the degradation rates of Co–TiO2–SiO2 for gentian violet, methyl violet, methylene blue, fuchsin basic and safranine T were greater in alkaline media than in acid and neutral media, while it did not exhibit any significant activity for the photodegradation of Rhdamine B in alkaline media or in acid media under visible light irradiation.

Transition metal M (M = Mn, Fe, Co, Ni, Cu, and Zn) doped mesoporous titania with a crystalline framework was employed as catalysts for the oxidation of p-bromotoluene (PBT) to p-bromobenzaldehyde (BBD) in acetic acid using aqueous hydrogen peroxide as oxidant. It was found that mesoporous TiO2 doped with those metals (Fe, Co and Ni) whose atomic radii are relatively smaller exhibited higher conversion rate of PBT. Among these catalysts, the Co/meso-TiO2 exhibited high substrate conversion and good product (p-bromobenzaldehyde) selectivity plus it can be reused once with almost the same activity. The effect of different Ti/Co (molar) ratio on the activities of Co/meso-TiO2 was also investigated.

Cobalt doped mesoporous titania–silica with Ti/Si molar ratio of 0.5 (Co–TiO2–SiO2) was synthesized for the oxidation of diphenylmethane in acetic acid using aqueous hydrogen peroxide as oxidant for the first time. Fast hot catalyst filtration experiment proved that the catalyst acted as a heterogeneous one. Recycling of the catalyst indicates that the catalyst can be used a number of times without losing its activity to a greater extent. The effects of reaction time and reaction temperature on the performance of the catalyst were investigated. Moreover, cobalt doped mesoporous titania with a crystalline structure and cobalt doped mesoporous titania–silica with different molar ratio were also studied. It was found that Co–TiO2–SiO2 with Ti/Si molar ratio of 0.5 showed the highest activity.

AgBiS2 microspheres synthesized by using PEG as a template serve as active catalysts for the polymerization of an alkylsilane, C18H37SiH3 with water to form silanols.

In this study, a series of lanthanum doped mesoporous SiO2 (La-meso-SiO2) were synthesized and characterized by X-ray diffraction, N2 adsorption–desorption, and Fourier transform infrared spectroscopy. The effects of different Si/La molar ratio, the amount of La-meso-SiO2 at different contact time, pH and initial concentration of phosphorus solution on phosphate removal have been studied. It was found that La-meso-SiO2 exhibited fast adsorption kinetics as well as high adsorption capacities. The adsorption rate and capacity of La-meso-SiO2 for removal of phosphate increase with the increasing of La/Si molar ratio. The phosphate removal would be near 100% with 0.3 g/L La-meso-SiO2 with Si/La molar ratio ≥10 after 3 h. La-meso-SiO2 with Si/La molar ratio of 10 was found to be recycled once, and 75% of phosphate was removed from this recycled adsorbent without any considerable damage to the solid. The concentrations of residual lanthanum ions in solution at different conditions were also measured. The results show that the Si/La ratio, amount of La-meso-SiO2 and initial concentration of phosphorus had little effect on the concentration of residual lanthanum ions, whereas the concentration of residual lanthanum ions decreased with increase in pH of the solution.

Ce doped FSM-16 (Ce/FSM-16) was synthesized by templating method and its photoactivity for the degradation of methyl violet, safranine T, fuchsin basic and methylthionine chloride under solar light was studied for the first time. Ce/FSM-16 had very high surface area (863 m2 g−1) and pore volume (0.73 cm3 g−1). Doping cerium ions appears important in bringing about sunlight photocatalytic activity. The photoactivity of Ce/FSM-16 is comparable with that of Degussa P25 under solar light. By contrast, undoped FSM-16 exhibited very strong adsorption capacity for these dyes, but did not exhibit significant photoactivity for them. The degradation of dyes catalyzed by Ce/FSM-16 under solar light followed a radical-type mechanism.

Selective oxidation of 4-tert-butyltoluene (TBT) to 4-tert-butylbenzaldehyde (TBBZ) and 4-methylacetophenone (MAP) is reported for the first time using aqueous hydrogen peroxide as oxidant and Co/MCM-41 as the catalyst under mild conditions for the first time. Co/MCM-41 presented reasonable selectivity (82%) of TBBZ with a conversion rate of 15% of TBT without any initiator. Under the suitable reaction conditions, Co/MCM-41 also presented reasonable selectivity (58%) of MAP with a conversion rate of 12% of the substrate. The catalysts can be reused once with almost the same activity.

PVP-capped silver spherical nanoparticles and nanorods serve as active catalysts for the polymerization of alkylsilane C18H37SiH3 with water, to form flower petal-like composite siloxane microspheres.

•Hydrilla templated ZnIn2S4 with hexagonal-cubic phase junctions.•Efficient charge separation of phase junction.•Remarkable light harvesting by hydrilla leaves derived special structures.•Significant enhancement in photocatalytic H2 evolution.The nature provides inspiration for many special structures due to biological diversity. In this report ZnIn2S4 with hexagonal-cubic phase junctions was prepared through a bio-inspired approach using hydrilla as a template and can significantly enhance photocatalytic H2 evolution under visible-light in comparison to those hexagonal or cubic single-phase structures. The enhancement in photocatalytic performance has been shown to be attributed to efficient charge separation and transfer across the hexagonal-cubic phase junction and light harvesting of special hydrilla leaves structure.Download full-size image

Non-surfactant hypocrellins (Hys) is a kind of photosensitizer with strong and broad absorption in visible light region, obtained by isolating from the fungus sacs of hypocrella bambusae. Previous studies have not yet addressed the use of hypocrellins as non-surfactant template in the synthesis of photocatalyst CdS, let alone the achievement of higher efficient photocatalytic activity than Degussa P25. Herein Al doped CdS prepared by using hypocrellins as template (Al-CdS/Hys) can enhance the photocatalytic activity while Al doped CdS without template (Al-CdS) prepared by conventional solvothermal method reduced the photocatalytic activity. Al-CdS/Hys was synthesized and characterized by a combination of various physicochemical techniques, such as XRD, nitrogen adsorption/desorption, diffuse reflectance UV–vis and TEM. Al-CdS/Hys is even more efficient than Degussa P25 for the degradation of organic dye, basic fuchsin under artificial solar irradiation. Moreover, doping Al increased the surface area of CdS to169.1 m2 g–1.

Adding a small amount of commercial GeO2 into aqueous suspension significantly enhanced the photocatalytic activity of titania-based photocatalysts for the degradation of dyes.

AgBiS2 microspheres synthesized by using PEG as a template serve as active catalysts for the polymerization of an alkylsilane, C18H37SiH3 with water to form silanols.

We demonstrated that embedding of CdS on MOFs could significantly increase the photocatalytic efficiency of CdS for visible light-driven hydrogen production.

Although photosensitization of titania by organic dyes is one of the conventional ways for visible-light utilization of titania, previous studies have not yet addressed the use of dyes as templates in the synthesis of mesoporous materials, let alone the simultaneous achievement of highly crystalline mesoscopic ordering and visible-light photocatalytic activity. In this work, fourteen commercial synthetic dyes were directly used as structure-directing agents which convert to carbonaceous materials after 400 °C calcination in synthesis of thermally stable mesostructured titania. This in situ carbon enhanced the visible light photocatalytic activities for the degradation of aqueous dyes. The synthesized mesoporous titania samples were characterized by a combination of various physicochemical techniques, such as XRD, SEM, HRTEM, nitrogen adsorption/desorption, TGA–DSC, XPS, diffuse reflectance UV–vis and FT–IR. Most of prepared mesoporous titania photocatalysts exhibited better activity under outside solar light than under artificial UV light, due to the presence of carbonaceous species which were transferred from the dye templates. The reported strategies combine sol-gel chemistry and self-assembly routes directly using dye templates that tune the material's architecture, texture and particularly function, visible-light photocatalysis.

A stable photoactive metal–organic framework UiO-66(Zr) sensitized by adsorbed or directly added rhodamine B dye exhibited photocatalytic activity for hydrogen evolution under visible-light illumination (λ ≥ 420 nm). Using Pt as a co-catalyst, the adsorbed and directly added dye extremely enhanced the photocatalytic activity to 30 and 26 times the value afforded by bare Pt@UiO-66(Zr), respectively.