Corrigendum: Improving yields by switching central metal ions in porphyrazine-catalyzed oxidation of glucose into value-added organic acids with SnO2 in aqueous solution.

[This corrects the article DOI: 10.3389/fchem.2023.1114454.].

Improving yields by switching central metal ions in porphyrazine-catalyzed oxidation of glucose into value-added organic acids with SnO2 in aqueous solution.

Photocatalysis has exhibited huge potential in selective conversion of glucose into value-added chemicals. Therefore, modulation of photocatalytic material for selective upgrading of glucose is significant. Here, we have investigated the insertion of different central metal ions, Fe, Co, Mn, and Zn, into porphyrazine loading with SnO2 for access to more efficient transformation of glucose into value-added organic acids in aqueous solution at mild reaction conditions. The best selectivity for organic acids containing glucaric acid, gluconic acid, and formic acid of 85.9% at 41.2% glucose conversion was attained by using the SnO2/CoPz composite after reacting for 3 h. The effects of central metal ions on surficial potential and related possible factors have been studied. Experimental results showed that the introduction of metalloporphyrazine with different central metal ions on the surface of SnO2 has a significant effect on the separation of photogenerated charges, changing the adsorption and desorption of glucose and products on the catalyst surface. The central metal ions of cobalt and iron contributed more to the positive effects toward enhancing conversion of glucose and yields of products, and manganese and zinc contributed more to the negative effects, resulting in the poor yield of products. The differences from the central metals may attribute to the surficial potential change of the composite and the coordination effects between the metal and oxygen atom. An appropriate surficial potential environment of the photocatalyst may achieve a better interactive relationship between the catalyst and reactant, while appropriate ability of producing active species matched with adsorption and desorption abilities would gain a better yield of products. These results have provided valued ideas for designing more efficient photocatalysts in selective oxidation of glucose utilizing clean solar energy in the future.

A Facile One-Pot Synthesis of Biomimetic Photocatalyst Zn(II)-Porphyrin-Sensitized 3D TiO2 Hollow Nanoboxes and Synergistically Enhanced Visible-Light Degradation.

A serials of biomimetic photocatalyst zinc(II) meso-tetra(4-carboxyphenyl)porphyrinato (ZnTCP)-sensitized 3D hierarchical TiO2 hollow nanoboxes (TiO2-HNBs) assembled by six ordered nanosheets with dominant {001} facets exposure (ZnTCP@TiO2-HNBs) have been successfully synthesized by a facile one-pot solvothermal method via a topological transformation process with TiOF2 as template. Infrared spectra (IR), UV-vis spectroscopy, and X-ray photoelectron spectroscopy (XPS) confirmed that ZnTCP played a decisive role in constructing 3D hollow nanoboxes through the formation of ester bond combined to TiO2-HNBs, which also provided a transferring photo excited electrons bridge to sensitize TiO2-HNBs for enhancing visible-light response. Due to the superior sensitization and biomimetic activity of ZnTCP, the photodegradation rate of rhodamine B (RhB) of as-prepared ZnTCP@TiO2-HNBs with ZnTCP/TiOF2 mass ratio of 2% (T-2p) improves 3.6 times compared to that of TiO2-HNBs with a degradation yield of 99% for 2 h under simulated sunlight irradiation (> 420 nm). The enhanced photodegradation ability was attributed to synergistic visible photocatalytic mechanism of biomimetic catalyst, which can not only produce hydroxyl radical (•OH) and superoxide radical (•O2-) coming from the excitation process of ZnTCP sensitized TiO2-HNBs, but also generate singlet oxygen (1O2) that was only provided by biomimetic enzyme porphyrins. Furthermore, the photocatalyst showed good recycling stability and dispersibility after five rounds, ascribed to ZnTCP strong chemical bonding to the support TiO2-HNBs. By means of electrochemical cyclic voltammetry analysis, the effect of central zinc ions and parent porphyrin rings on the redox property of biomimetic catalyst was studied.

Synergistic photocatalytic performance of cobalt tetra(2-hydroxymethyl-1,4-dithiin)porphyrazine loaded on zinc oxide nanoparticles.

A new ZnO/CoPz(hmdtn)4 composite as a highly efficient photocatalyst was successfully prepared by cobalt tetra(2-hydroxymethyl-1,4-dithiin)porphyrazine (CoPz(hmdtn)4) impregnated onto the surface of ZnO nanoparticles, the photocatalytic performance of ZnO/CoPz(hmdtn)4 under both simulated sunlight and visible light (λ ≥ 400 nm) irradiation was assessed by degradation of Rhodamine B (RhB) and phenol in aerated conditions. The ZnO/CoPz(hmdtn)4 manifested much higher photocatalytic activity than pure ZnO and pure CoPz(hmdtn)4, originating from the synergistic effect between CoPz(hmdtn)4 and ZnO. Furthermore, the XPS analysis revealed that there may be strong interaction between CoPz(hmdtn)4 and ZnO. Thereby ZnO/CoPz(hmdtn)4 with excellent stability can maintain high photocatalytic activity over five runs on the basis of the reusability test. The active species generated in the photocatalytic system were verified by electron spin resonance (ESR) technology. A possible mechanism of the synergistic effect between CoPz(hmdtn)4 and ZnO was also proposed.

Metal- and Additive-Free Oxidation of Sulfides into Sulfoxides by Fullerene-Modified Carbon Nitride with Visible-Light Illumination.

Photocatalytic selective oxidation has attracted considerable attention as an environmentally friendly strategy for organic transformations. Some methods have been reported for the photocatalytic oxidation of sulfides into sulfoxides in recent years. However, the practical application of these processes is undermined by several challenges, such as low selectivity, sluggish reaction rates, the requirement of UV-light irradiation, the use of additives, and the instability of the photocatalyst. Herein, a metal-free C60 /graphitic carbon nitride (g-C3 N4 ) composite photocatalyst was fabricated by a facile method, and well characterized by TEM, SEM, FTIR spectroscopy, XRD, X-ray photoelectron spectroscopy, diffuse reflectance spectroscopy, and photoluminescence spectroscopy. The C60 /g-C3 N4 catalyst exhibited a high photocatalytic activity at room temperature for the selective oxidation of sulfides into the corresponding sulfoxides in the presence of other functional groups, due to the synergetic roles of C60 and g-C3 N4 . Several important parameters have been screened, and this method afforded good to excellent yields of sulfoxides under optimal conditions. The superoxide radical (. O2- ) and singlet oxygen (1 O2 ) were identified as the oxidative species for the oxidation of sulfides into sulfoxides by exploring EPR experiments, and hence, a plausible mechanism for this oxidation was proposed. Moreover, the C60 /g-C3 N4 catalyst can be easily recovered by filtration and then reused at least four times without loss in activity.

One-step topological preparation of carbon doped and coated TiO2 hollow nanocubes for synergistically enhanced visible photodegradation activity.

Various three-dimensional TiO2 hollow structures have attracted strong scientific and technological attention due to their excellent properties. 3D hierarchical TiO2 hollow nanocubes (TiO2-HNBs) are not good candidates for industrial photocatalytic applications due to their large energy gap which is only activated by UV light. Herein, visible-light-responsive carbon doped and coated TiO2-HNBs (C@TiO2-HNBs) with a dominant exposure of {001} facets have been prepared via a template-engaged topotactic transformation process using facile one-step solvothermal treatment and a solution containing ethanol, glucose and TiOF2. The effects of reaction time and glucose/TiOF2 mass ratio on the structure and performance of C@TiO2-HNBs were systematically studied. We found that glucose played an important role in providing H2O during the topological transformation from self-templated TiOF2 cubes into 3D hierarchical TiO2 hollow nanocubes versus dehydration reactions, where its main function was as a carbon source. Coated carbon was deposited predominantly on the surface as sp2 graphitic carbon in extended p conjugated graphite-like environments, and doped carbon mainly replaced Ti atoms in the surface lattice to form a carbonate structure. The results were confirmed using TEM SEM, EDS, XRD, FT-IR, XPS and Raman spectroscopic studies. The C@TiO2-HNBs achieved greatly improved RhB photodegradation activity under visible light irradiation. The catalyst prepared with glucose/TiOF2 at a mass ratio of 0.15 (T24-0.15) showed the highest photodegradation rate of 96% in 40 min, which is 7.0 times higher than those of the TiO2-HNBs and P25. This new synthetic approach proposes a novel way to construct carbon hybridized 3D hierarchical TiO2 hollow nanocubes by combining two modification methods, "element doped" and "surface sensitized", at the same time.

Selective oxidation of benzyl alcohols to benzoic acid catalyzed by eco-friendly cobalt thioporphyrazine catalyst supported on silica-coated magnetic nanospheres.

A novel magnetically recoverable thioporphyrazine catalyst (CoPz(S-Bu)8/SiO2@Fe3O4) was prepared by immobilization of the cobalt octkis(butylthio) porphyrazine complex (CoPz(S-Bu)8) on silica-coated magnetic nanospheres (SiO2@Fe3O4). The composite CoPz(S-Bu)8/SiO2@Fe3O4 appeared to be an active catalyst in the oxidation of benzyl alcohol in aqueous solution using hydrogen peroxide (H2O2) as oxidant under Xe-lamp irradiation, with 36.4% conversion of benzyl alcohol, about 99% selectivity for benzoic acid and turnover number (TON) of 61.7 at ambient temperature. The biomimetic catalyst CoPz(S-Bu)8 was supported on the magnetic carrier SiO2@Fe3O4 so as to suspend it in aqueous solution to react with substrates, utilizing its lipophilicity. Meanwhile the CoPz(S-Bu)8 can use its unique advantages to control the selectivity of photocatalytic oxidation without the substrate being subjected to deep oxidation. The influence of various reaction parameters on the conversion rate of benzyl alcohol and selectivity of benzoic acid was investigated in detail. Moreover, photocatalytic oxidation of substituted benzyl alcohols was obtained with high conversion and excellent selectivity, specifically conversion close to 70%, selectivity close to 100% and TON of 113.6 for para-position electron-donating groups. The selectivity and eco-friendliness of the biomimetic photocatalyst give it great potential for practical applications.

Selective Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid Using O2 and a Photocatalyst of Co-thioporphyrazine Bonded to g-C3N4.

Selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is one of the key reactions for producing chemical commodities from biomass and their derivatives. The challenge for this reaction is to develop an efficient catalytic process that can be conducted under mild conditions (room temperature and atmospheric pressure, using oxygen molecules in air as the oxidant) and a recyclable catalyst. Herein we report a photocatalyst of cobalt thioporphyrazine (CoPz) dispersed on g-C3N4 (abbreviated as CoPz/g-C3N4), which exhibits excellent catalytic activity toward the selective oxidation of HMF into FDCA under simulated sunlight using oxygen molecules in air as a benign oxidant. For example, an FDCA yield of 96.1% in an aqueous solution at pH = 9.18 is achieved at ambient temperature and air pressure. At lower pH (4.01), the product generated is 2,5-diformylfuran. Hence, it is possible to control the reaction outcome by control of the pH of the reaction system. g-C3N4 itself is not a suitable catalyst for the selective oxidation because under the experimental conditions g-C3N4 generates hydroxyl radicals that initiate processes that oxidize HMF directly to CO2 and H2O. CoPz on the other hand activates O2 to give singlet oxygen (1O2), which more controllably oxidizes HMF to FDCA albeit at a more moderate yield (36.2%). The strong interaction between the CoPz and g-C3N4 in the CoPz/g-C3N4 catalyst is experimentally evidenced, which not only improves accessibility of the CoPz sites and makes the catalyst recyclable but also disables the hydroxyl radical generation by g-C3N4 and promotes 1O2 generation on the CoPz sites, significantly enhancing the catalytic performance. This study demonstrates the potential for efficient non-noble metal photocatalysts for organic transformations driven by sunlight.

High performance of a cobalt-nitrogen complex for the reduction and reductive coupling of nitro compounds into amines and their derivatives.

Replacement of precious noble metal catalysts with low-cost, non-noble heterogeneous catalysts for chemoselective reduction and reductive coupling of nitro compounds holds tremendous promise for the clean synthesis of nitrogen-containing chemicals. We report a robust cobalt-nitrogen/carbon (Co-N x /C-800-AT) catalyst for the reduction and reductive coupling of nitro compounds into amines and their derivates. The Co-N x /C-800-AT catalyst was prepared by the pyrolysis of cobalt phthalocyanine-silica colloid composites and the subsequent removal of silica template and cobalt nanoparticles. The Co-N x /C-800-AT catalyst showed extremely high activity, chemoselectivity, and stability toward the reduction of nitro compounds with H2, affording full conversion and >97% selectivity in water after 1.5 hours at 110°C and under a H2 pressure of 3.5 bar for all cases. The hydrogenation of nitrobenzene over the Co-N x /C-800-AT catalyst can even be smoothly performed under very mild conditions (40°C and a H2 pressure of 1 bar) with an aniline yield of 98.7%. Moreover, the Co-N x /C-800-AT catalyst has high activity toward the transfer hydrogenation of nitrobenzene into aniline and the reductive coupling of nitrobenzene into other derivates with high yields. These processes were carried out in an environmentally friendly manner without base and ligands.

Transformation of TiOF2 cube to a hollow nanobox assembly from anatase TiO2 nanosheets with exposed {001} facets via solvothermal strategy.

Hierarchical nanostructures have attracted increasing interest due to their exceptional properties and widespread potential applications. In this paper, anatase TiO2 hollow nanoboxes (TiO2-HNBs) are formed by assembly of nanosheets with exposed {001} facets by solvothermal treatment of TiOF2 cubes in alcohols (tert-butanol and ethanol) at 180 °C. It was found that phase transformation of TiOF2 to anatase TiO2 begins at corners and edges of TiOF2 cubes due to in situ hydrolysis of TiOF2, where water was produced by dehydration of alcohol molecules. With extension the reaction time, TiO2-HNB assemblies from nanosheets with exposed high-energy {001} facets were formed due to the steady inside-outside dissolution-recrystallization process. However, the resulting hierarchical TiO2-HNBs are unstable, which can decompose to discrete high-energy TiO2 nanosheets if the reaction time is further extended. The hierarchical TiO2-HNBs show higher photocatalytic activity than discrete high-energy TiO2 nanosheets and P25 TiO2 due to the unique structures of TiO2-HNBs.

Microwave-assisted rapid conversion of carbohydrates into 5-hydroxymethylfurfural by ScCl3 in ionic liquids.

In this study, synthesis of HMF from carbohydrates was carried out in ionic liquids 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) catalyzed by ScCl3 under microwave irradiation. Under the optimal reaction conditions, HMF was obtained in a high yield of 73.4% in 2 mins with the microwave power at 400 W. Compared with the conventional oil-bath heating manner, the use of microwave irradiation not only reduced reaction times from hours to minutes, but also improved HMF yield. This catalytic system could be reused several times without losing its catalytic activity. This efficient catalytic system will generate a promising application strategy for biomass transformation.

Effect of structure-directing agents on facile hydrothermal preparation of hierarchical γ-Al2O3 and their adsorption performance toward Cr(VI) and CO2.

Hierarchical flower-like and sphere-like mesoporous γ-Al2O3 microparticles were successfully prepared by a facile hydrothermal method followed by a calcination process using sodium aluminate as aluminum source, urea as precipitating agent, and Pluronic F127 (EO106PO70EO106), polyacrylic acid sodium (PAAS), and mixed F127-PAAS as structure-directing agents (SDAs), respectively. Effects of the SDAs on the phase structure, morphology, textural properties, surface alkaline, and the adsorption performance toward Cr(VI) and CO2 of the as-prepared samples were comparatively studied by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), N2 adsorption-desorption, CO2 temperature programmed desorption (CO2-TPD), and UV-Vis spectrophotometric method. The results indicate that the sphere-like γ-Al2O3 obtained by using F127 as the SDA shows the best adsorption performance toward Cr(VI) with a high adsorption rate of 95% and adsorption capacity of 5.7 mg/g when the adsorption reaches equilibrium for 4h at room temperature. However, the flower-like γ-Al2O3 obtained by using PAAS as the SDA has the biggest CO2 adsorption capacity of 1.04 mmol/g at room temperature. This work provides a simple and practical way to prepare potentially bifunctional γ-Al2O3 adsorbent for the removal of pollutants in water and air treatment from cheap sodium aluminate by using different SDAs.

[µ-N (1),N (2)-Bis(pyridin-2-yl)hydrazine-1,2-dicarbothio-amidato]bis-[chlorido-copper(II)].

The binuclear title compound, [Cu2(C12H10N6S2)Cl2], possesses twofold rotational symmetry. The Cu(II) atom occupies a four-coordinate pseudo-tetra-hedral environment bound to one S atom, one imine N atom and one pyridine N atom from the N(1),N(2)-bis-(pyridin-2-yl)hydrazine-1,2-dicarbo-thio-amidate ligand, and one Cl(-) anion. The metal atoms are connected via the bis-tridentate ligand into a binuclear structure. The mol-ecule is bow-shaped with the pyridine rings inclined to one another by 51.56 (14)°. In the crystal, N-H⋯Cl hydrogen bonds lead to the formation of ribbons propagating along [001]. These ribbons are connected via C-H⋯Cl, C-H⋯S and π-π inter-actions [centroid-centroid distance = 3.6146 (19) Å], leading to the formation of a three-dimensional structure.

Increasing visible-light absorption for photocatalysis with black BiOCl.

Black BiOCl with oxygen vacancies was prepared by UV light irradiation with Ar blowing. The as-prepared black BiOCl sample showed 20 times higher visible light photocatalytic activity than white BiOCl for RhB degradation. The trapping experiment showed that the superoxide radical (O(2)(•-)) and holes (h(+)) were the main active species in aqueous solution under visible light irradiation.

Six new metal-organic frameworks with multi-carboxylic acids and imidazole-based spacers: syntheses, structures and properties.

Six new metal-organic frameworks [Cu(obba)(bimb)·(obbaH(2))](n) (1), [Cu(obba)(bimb)](n) (2), [Zn(2)(obba)(2)(bimb)(2)(DMF)(2)(H(2)O)(3.5)](n) (3), [Ni(3)(2,2',4,4'-bptcH)(2)(bimb)(2)(H(2)O)(2)·(H(2)O)(2)](n) (4), [Ni(2)(bimb)(3)(H(2)O)(6)·(aobtc)·(DMF)(2)·(H(2)O)(2)](n) (5) and [Cd(3,3',4,4'-bptcH(2))(H(2)O)·(bimb)](n) (6), were obtained by reactions of 4,4'-bis(1-imidazolyl)biphenyl (bimb) and multi-carboxylic acids of 4,4'-oxybis(benzoic acid) (obbaH(2)), 2,2',4,4'-biphenyltetracarboxylate acid (2,2',4,4'-bptcH(4)), azoxybenzene-3,3',5,5'-tetracarboxylic acid (aobtcH(4)), and 3,3',4,4'-biphenyltetracarboxylate acid (3,3',4,4'-bptcH(4)) with corresponding metal salts under hydro/solvothermal conditions, respectively. Complexes 1-3 have entangled structures with different topologies: 1 is a 3-fold interpenetrating NbO three-dimensional (3D) network; 2 is a 3-fold interpenetrating dmp 3D net; 3 is a 6-fold interpenetrating dia 3D chiral net containing rare 1D helical chains with the same handedness. Complex 4 is an uninodal 6-connected network with a Schäfli symbol of (4(8)6(4)8(3)) based on the trinuclear Ni(II) subunits, while complexes 5 and 6 are 1D chains. Interestingly, compound 6 represents the rare example of MOFs that exhibit high photocatalytic activity for dye degradation under visible light and shows good stability towards photocatalysis. Complexes 3 and 6 exhibit intense blue emissions in the solid state at room temperature whereas 3 appears to be a good candidate of novel hybrid inorganic-organic NLO material.

Photodegradation activity of polyvinyl chloride (PVC)-perchlorinated iron (II) phthalocyanine (FePcCl16) composite film.

In this paper, a novel kind of photodegradable PVC-FePcCl(16) composite film was prepared by homogeneous embedding FePcCl(16) into the commercial PVC plastic. The photodegradation performance of as-prepared film has been investigated in the ambient air under UV light irradiation by means of weight loss monitoring, FT-IR spectroscopy, UV-Vis spectroscopy. In comparison with the pure PVC film, higher weight loss rate, increasing carbonyl peak intensity and accelerating dehydrochlorination were observed. These results indicate that the PVC-FePcCl(16) composite film has a higher photodegradation activity owing to the FePcCl(16). Moreover, FePcCl(16) has good photostability in the photoreaction. The possible photodegradation mechanism of PVC-FePcCl(16) composite film was also discussed.

High photocatalytic degradation activity of the polyvinyl chloride (PVC)-vitamin C (VC)-TiO2 nano-composite film.

A novel photodegradable polyvinyl chloride (PVC)-vitamin C (VC)-TiO(2) nano-composite film was prepared by embedding VC modified nano-TiO(2) photocatalyst into the commercial PVC plastic. The solid-phase photocatalytic degradation behavior of PVC-VC-TiO(2) nano-composite film under UV light irradiation was investigated and compared with those of the PVC-TiO(2) film and the pure PVC film, with the aid of UV-Vis spectroscopy, scanning electron microscopy (SEM), weight loss monitoring, and X-ray diffraction spectra (XRD). The results show that PVC-VC-TiO(2) nano-composite film has a high photocatalytic activity; the photocatalytic degradation rate of it is two times higher than that of PVC-TiO(2) film and fifteen times higher than that of pure PVC film. The optimal mass ratio of VC to TiO(2) is found to be 0.5. The mechanism of enhancing photocatalytic activity is attributed to the formation of a Ti(IV)-VC charge-transfer complex with five-member chelate ring structure and a rapid photogenerated charge separation is thus achieved.

Synergistic effects of hollow structure and surface fluorination on the photocatalytic activity of titania.

To study the synergistic effects of hollow structure and surface fluorination on the photoactivity of TiO(2), TiO(2) hollow microspheres were synthesized by a hydrolysis-precipitate method using sulfonated polystyrene (PS) as templates and tetrabutylorthotitanate (TBOT) as precursor, and then calcined at 500 degrees C for 2h. The calcined samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and N(2) sorption. Photocatalytic activity was evaluated using reactive brilliant red X3B, an anionic organic dye, as a model pollutant in water. The results show that the photocatalytic activity of TiO(2) hollow microspheres is significantly higher than that of TiO(2) nanoparticles prepared in the same experimental conditions. At pH 7 and 3, the apparent rate constants of the former exceed that of the latter by a factor of 3.38 and 3.15, respectively. After surface fluorination at pH 3, the photoactivity of hollow microspheres and nanoparticles further increases for another 1.61 and 2.19 times, respectively. The synergistic effect of surface fluorination and hollow structure can also be used to prepare other highly efficient photocatalyst.

Oxidative degradation of dye pollutants over a broad pH range using hydrogen peroxide catalyzed by FePz(dtnCl2)4.

The oxidative degradation of rhodamine B (RhB) with hydrogen peroxide activated by iron(II) tetra-(5,6-dichloro-1,4-dithiin)-porphyrazine (abbreviated as FePz(dtnCl(2))(4)) was studied by means of UV-Vis spectra, GC-MS and TOC analysis, in which the effects of pH, light, concentration of hydrogen peroxide and the degraded products of the RhB were investigated. The results indicate that FePz(dtnCl(2))(4) was found to exhibit high catalytic activity to activate hydrogen peroxide for the oxidative degradation of RhB and good stability over a broad pH range under visible light irradiation (lambda>420 nm). The conversions of RhB in 80 min were 99%, 85%, 52% and the TOC removals in 240 min were 91%, 64%, 18% when the initial solutions pHs were 2, 7, 11, respectively. HO(.) radicals were testified to generate in the biomimetic catalytic system both at pH 2 and 7 by means of spin-trapping electron spin resonance. However, control experiment with scavenging of HO() radicals displayed the quite different results at pH 2 and 7. Based on experiment results together with theoretic deduction, a mechanism for RhB oxidation involving two kinds of reactive oxidizing species was proposed, the homolytic cleavage generating the HO(.) radicals and the heterolytic cleavage generating the Pz(.)(+)Fe(IV)=O radicals.

(Bi, C and N) codoped TiO2 nanoparticles.

Bi, C and N codoped TiO2 photocatalysts were prepared by doping TiO2 with BiCl3 and KSCN in a sol-gel process (denoted as (Bi,SCN)-TiO2). The catalyst samples were then characterized by XRD, TEM, diffuse reflectance spectra (DRS), XPS, FT-IR and N2 sorption. Bi, C and N elements were detected both by XPS and elemental analysis, while S element was not found, suggesting that SCN- group may have decomposed during the sol-gel process. The effects of the doping on the properties and photocatalytic activity of the TiO2 were investigated. It was found that the cation and the anion affected the properties of TiO2 differently. The optical absorption onset of TiO2 red shifted in the presence of Bi3+, while long tail occurred in the presence of SCN-. The order of photoreactivity for TiO2 samples was as follow: (Bi,SCN)-TiO2>Bi-TiO2>undoped TiO2>p25 TiO2, whatever under UV or visible light illumination. The high photoreactivity of the doped TiO2 was also discussed.