Synthesis of APTMS-Functionalized SiO2/TiO2 Transparent Film Using Peroxo Titanic Acid Refluxed Solution for Formaldehyde Removal

Amine-functionalized SiO₂/TiO₂ photocatalytic films have been synthesized using the peroxo titanic acid (PTA) approach coupled with the sol-gel dip-coating method. The 3-aminopropyl-trimethoxysilane (APTMS) and methyltrimethoxysilane (MTMOS) were employed as the amine functional groups and silica precursor. The effects of the ratio of APTMS/MTMOS, PTA refluxed time, and pH of prepared sol on the characteristics and the formaldehyde degradation efficiency were investigated. Physicochemical properties of prepared photocatalysts were characterized with nitrogen adsorption–desorption isotherm measurement, SEM, X-ray diffraction (XRD), UV-vis spectrophotometer, and Fourier transform infrared (FTIR) spectroscopy. The XRD and FTIR results indicated that the obtained photocatalysts consisted of –NH₂ groups, SiO₂, and anatase TiO₂. The photocatalytic films showed high transmittance of 80–90% in the visible light region. The obtained film prepared with the APTMS/MTMOS ratio of 0.03, pH of 1.8, and 10 h of refluxed time possessed high specific surface area (604.0 m² g^?1) and 85% formaldehyde degradation efficiency. The enhancement of formaldehyde degradation efficiency was observed when increasing the PTA refluxed time. The repeatability of photocatalytic film was also tested, and the degradation efficiency was 92.0% of initial efficiency after seven cycles.     

Microstructures and Photocatalytic Properties of Fe3+/Ce3+ Codoped Nanocrystalline TiO2 Films

Fe³⁺ and Ce³⁺ codoped titanium dioxide films with high photocatalytic activity were successfully obtained via the improved sol?Cgel process. The as-prepared specimens were characterized using X-ray diffraction (XRD), high-resolution field emission scanning electron microscopy (FE-SEM), X-ray energy dispersive spectroscopy, Brunauer?CEmmett?CTeller (BET) surface area, X-ray photoelectron spectroscopy, photoluminescence (PL) spectra, and UV?CVis diffuse reflectance spectroscopy. The photocatalytic activities of the films were evaluated by degradation of various organic dyes in aqueous solutions. The results of XRD, FE-SEM, and BET analyses indicated that the TiO₂ film had nanostructure. With the codoping of Fe³⁺ and Ce³⁺, TiO₂ photocatalysts with smaller crystal size, larger surface area, and larger pore volume were obtained. Moreover, codoped ions could obviously not only suppress the formation of brookite phase but also inhibit the transformation of anatase to rutile at high temperature. Compared with pure TiO₂ film, Fe³⁺ doped or Ce³⁺ doped TiO₂ film, the Fe³⁺/Ce³⁺ codoped TiO₂ film exhibited excellent photocatalytic activity. It is believed that the surface microstructure of the films and the doping methods of the ions are responsible for improving the photocatalytic activity.     

Effect of Co-Dopants in TiO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript> Thin films on the Formaldehyde Degradation

Titanium dioxide (TiO₂)–silicon dioxide (SiO₂) thin films were synthesized using the peroxo titanic acid approach (PTA) combined with the sol–gel method at low temperature around 100°C. The effects of type and amount of dopants of ferric (Fe³⁺) or thiourea (N-S) and co-dopants of Fe³⁺ and N-S on the films physicochemical properties and on the photocatalytic degradation of the methylene blue and formaldehyde under UV and visible light irradiation were investigated. Physicochemical properties of photocatalysts were characterized by X-ray diffraction, transmission electron microscopy, wavelength-dispersive X-ray fluorescence spectrometry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and UV–Vis spectroscopy. The results showed that the TiO₂ crystal phases obtained from this method were exclusively anatase and the needle-like crystals have an average diameter of 10–25 nm. Compared with the single dopant of 1.0 wt.% Fe³⁺ or 0.125 wt.% N-S that was the optimal concentration for photocatalytic degradation of methylene blue and formaldehyde, the co-dopants of 0.125 wt.% N-S + 1.0 wt.% Fe³⁺ furthermore increased the degradation efficiency. Co-dopants of 0.125 wt.% N-S + 1.0 wt.% Fe³⁺ in TiO₂–SiO₂ films were considered to play synergistic roles in narrowing TiO₂ band gap resulting in the higher methylene blue and formaldehyde degradation efficiency. Since the crystal grain size of TiO₂–SiO₂ films synthesized by the PTA method is small, in the visible light region, the high transmittance was attainable to 80% with no-doped and dropped to 50–60% with doped thin films.     

Advanced Oxidation Processes in Triton X-100 and Wash-up Liquid Removal from Wastewater Using Modified TiO2/Al2O3 Photocatalysts

Photocatalytic methods were applied to remove the recalcitrant or toxic pollutants from the water. The two models of wastewater containing either non-ionic surfactant Triton X-100 or commercially available wash-up liquid were tested in a self-constructed band reactor during the laboratory studies. The photocatalyst, being typed TiO₂, was supported by porous Al₂O₃ and modified by the addition of Cu, Fe, Zn, Ni, Mo or Co. The photocatalysts were characterised by N₂ adsorption?Cdesorption, XRF, XRD, SEM-EDX, Raman and UV?CVis spectroscopy. All catalysts were efficient in the photocatalytic oxidation of surfactants, and they enabled at least 85?% COD reduction. TiO₂/Al₂O₃ photocatalysts modified by the transition metals were efficient only for more complicated compositions of surfactants. The effect of H₂O₂ (0.01?vol.%) addition was also examined and compared with a type of compound and catalyst used??in this case a positive effect for Triton X-100 was only observed over the photocatalyst modified by Ni. When it comes to the wash-up liquid photoremoval, all studied photocatalysts seem to be slightly influenced by H₂O₂ addition. It was also observed that it is not economically justified to conduct such treatment for more than 2?h.     

Photocatalytic Degradation of Herbicide Quinmerac in Various Types of Natural Water

The efficiency of the photocatalytic degradation of the herbicide quinmerac in aqueous TiO₂ suspensions was examined as a function of the type of light source, TiO₂ loading, pH, temperature, electron acceptors, and hydroxyl radical (^?OH) scavenger. The optimum loading of catalyst was found to be 0.25?mg?mL^?1 under UV light at pH?7.2, with the apparent activation energy of the reaction being 13.7?kJ?mol^?1. In the first stage of the reaction, the photocatalytic degradation of quinmerac (50???M) followed approximately a pseudo-first order kinetics. The most efficient electron acceptor appeared to be H₂O₂ along with molecular oxygen. By studying the effect of ethanol as an ^?OH scavenger, it was shown that the heterogeneous catalysis takes place mainly via ^?OH. The results also showed that the disappearance of quinmerac led to the formation of a number of organic intermediates and ionic byproducts, whereas its complete mineralization occurred in about 120?min. The reaction intermediates (7-chloro-3-methylquinoline-5,8-dione, three isomeric phenols hydroxy-7-chloro-3-methylquinoline-8-carboxylic acids, and 7-chloro-3-(hydroxymethyl)quinoline-8-carboxylic acid) were identified and the kinetics of their appearance/disappearance was followed by LC?CESI?CMS/MS. Tentative photodegradation pathways were proposed and discussed. The study also encompassed the effect of quality of natural water on the rate of removal of quinmerac.     

TiO2 Immobilized Biodegradable Polymer for Photocatalytic Removal of Chlorophenol

This study concentrated on the direct immobilization of anatase nano titanium dioxide particles (TiO₂, 44?nm particle size) into or onto a biodegradable polymer, polycaprolactone, by solvent-cast processes. The photocatalytic properties of the produced materials were tested by photocatalytic removal of organic contaminant 4-chlorophenol. Produced TiO₂ immobilized polymer successfully removed 4-chlorophenol (4-CP, 20?ppm which is equal to 1.56?×?10^?4?M) from aqueous solution without additional pH arrangement employing a UV-A light (365?nm) source. Immobilization of n-TiO₂ onto polycaprolactone (PCL) produced improved 4-CP removal percentages, reaching to nearly 85?%. Increased PCL mass significantly increases the removal percentage of 4-CP. When a UVC lamp emitting 254?nm light is used, the removal percentage reaches to 89?%. UV irradiation did not cause any change in the microstructure of the polymeric material (confirmed with ATR-FTIR analysis). This is an important evidence that the material could be reused for further photocatalytic treatments. Produced material seems to be highly promising for successful removal of organic pollutants beside its biodegradable nature.     

TiO2纳米粒子气固相光催化降解乙烯初探

该文对TiO₂纳米粒子气固光催化降解果蔬贮藏环境乙烯技术进行了初步研究。采用溶胶-凝胶法制备的纳米TiO₂薄膜作光催化剂，利用自行设计的气固光催化实验系统，研究了乙烯浓度、紫外光作用时间对光催化降解反应的影响，探讨了乙烯的光催化降解的动力学。结果显示：该研究所制备的TiO₂锐钛矿型含量为48.766%，比表面积为47.186 m²/g，具有良好的光催化性能；光催化降解乙烯比直接紫外线光降解效果显著，光照10 min时光催化乙烯降解率比直接紫外线光降解提高23.76%；乙烯的降解率随着其浓度的增加而降低；乙烯的光催化降解的动力学可以用Langmuir-Hinshelwood动力学方程加以描述。     

Performance and Bacterial Community Diversity of a Full-Scale Biofilter Treating Leachate Odor in a Sanitary Landfill Site

Odors, such as the malodorous and toxic hydrogen sulfide (H₂S), are released during leachate collection, storage, and treatment. A full-scale biofilter was applied to treat H₂S emitted from a leachate equalization basin in a sanitary landfill site. The inlet concentration of H₂S was 26.3?C213.0?mg?m^?3. In steady state, total removal efficiency was over 90?% in summer and over 80?% in winter. The maximum elimination capacity achieved 9.1?g?m^?3?h^?1 at a loading rate of 10.5?g?m^?3?h^?1. The biofilter was effective at reducing H₂S. Factors on the level of H₂S inlet concentration and performance of the biofilter were investigated. The H₂S inlet load and removal efficiency relied on ambient and biofilter temperature, respectively. The water containing rate and relative humidity presented seasonal variation, according to which the interval period of irrigation could be optimized. The main product of H₂S degradation was sulfate, and sulfur also could be observed from the biofilter. Spatial and temporal shifts in bacterial community composition in the biofilter were determined by polymerase chain reaction-denaturing gradient gel electrophoresis followed by DNA sequence analysis. The present study revealed a correlation between biofilter performance and bacterial community structure, especially in a real application case.     

N,P, K and S uptake response to various levels of CO2 assimilation and growth rate in lettuce

Under conditions of limited nutrient supply, plant nutrient uptake is controlled by the external concentration of the ions. Limited information exists about the whole-plant regulation of nutrient uptake when the supply is adequate. To study the relationship between growth rate and carbon dioxide (CO₂) assimilation with nutrient uptake, growth chamber experiments were conducted with temperatures ranging from 10 to 35°C at medium (600 µmol m^?2 s^?1) and high (1200 µmol m^?2 s^?1) light intensities. Nutrient solution samples were collected every 24 hours and the concentration of ions was analyzed by Inductively coupled plasma -atomic emission spectroscopy (ICP-AES) and nitrate and ammonium (NO₃^?/NH₄⁺) conductivity. Leaf photo-synthesis was measured using a closed gas exchange system and the total amount of CO₂ assimilated was calculated from dry weight increases. The daily absorption of NO₃^?, Total nitrogen (N), dihydrogen phosphate (H₂PO₄^?) and potassium (K⁺) responded linearly to plant growth, while ammonium (NH₄⁺) and sulfate (SO₄^2?) uptake showed a curvilinear response. All the ions studied showed a curvilinear relation with CO₂ assimilation.     

Removal of Phenolic Compounds from Aqueous Solutions Using Sludge-Based Activated Carbons Prepared by Conventional Heating and Microwave-Assisted Pyrolysis

Sludge-derived activated carbons (ACs) were prepared by conventional heating and microwave pyrolysis. The ACs were characterized using several analytical and functional techniques and used for removal of six phenolic compounds from aqueous solutions. The adsorbents exhibited similar features and possessed hydrophobic surfaces. The ACs were assigned mesoporous materials, with specific surface areas of up to 641 and 540 m² g^?1 for CAC-500 and MAC-980, respectively. The preliminary results indicated that phenol removal onto the ACs increased in the order: m-cresol?<?phenol?<?o-cresol?<?2-chrorophenol?<?2-nitrophenol?<?hydroquinone. Hydroquinone exhibited the highest adsorption capacity and was chosen to continue the remaining part of the experimental work—kinetic and isothermal studies. The adsorption kinetic and isotherm data were well described by the Avrami fractionary order and Redlich–Peterson models, respectively. The maximum amounts (Q _max) of hydroquinone adsorbed at 25 °C were too high, reaching 1218.3 and 1202.1 mg g^?1 for CAC-500 and MAC-980, respectively. The mechanism of adsorption was proposed in this work, and it was suggested that donor–acceptor complex and π–π interactions play major roles in the adsorption process. The adsorbents were also tested on simulated effluents. The two ACs displayed good efficiency for the treatment of industrial simulated effluents.     

Trends of Major Inorganic Species at the Small Watershed Ecosystem in Northern Tama Hills, the Western Tokyo Metropolitan Area, Japan

Acid rain impacts on the small forested watershed in northern Tama Hills in the western Tokyo metropolitan area Japan were investigated by surveying the trends of major inorganic species in rain and spring water during the years from 1991 to 1997. The ecosystem had been stressed by the annual H⁺-deposition of around 0.43 kmol/ha. The spring water outflow corresponded to ca. 27% of the precipitation. Budgets for the precipitation input and spring water output gave good balance for Cl^?,?0.01 ±0.09 kmol/ha, net gains for H⁺, NO₃ ^? and SO₄ ^2?, and to the contrary, relatively large net losses for Na⁺, Mg²⁺, Ca²⁺, Si(as H₄SiO₄) and HCO₃ ^?, thus suggesting the dissolution of chemical weathered products of silicate minerals. Further, in spring water, some concentration relationships were found: CNa⁺ = 376.5?2.05CCl^? (R²=0.748), CNa⁺=12.69+0.5556CHCO₃ ^? (R²=0.872) and CH₄SiO₄=130.0 + 1.108CHCO₃ ^? (R²=0.816). Evidently, the spring water chemistry reflected probable geochemical changes in the soil layer of the watershed. Mass balance in the ecosystem and estimation of the spring water output of chemical weathered products were investigated     

Co(II) Adsorption in Aqueous Media by a Synthetic Fe–Mn Binary Oxide Adsorbent

Co(II) adsorption on high-purity amorphous Fe?CMn binary oxide adsorbent was investigated. The Co(II) adsorption behavior of this synthetic material was studied and discussed as a function of contact time, pH and initial concentration. The Langmuir and Freundlich isotherm models were applied to fit the Co(II) adsorption data on Fe?CMn binary oxide with mesoporous particles of irregular surface morphology and a specific surface area of 201.8?m²?g^?1 with a maximum capacity of 32.25?mg?g^?1. Various kinetic models applied to the adsorption rate data of the Co(II) ion were evaluated. The results show that the pseudo-second order and the intra-particle mass transfer diffusion models correlated best with the experimental rate data. The adsorption activation energy was found to be 9.07?kJ?mol^?1 indicating that it corresponds to a physical adsorption. The evaluated thermodynamics parameters of the adsorption values indicated the endothermic and spontaneous nature of the adsorption. The results obtained confirmed that Fe?CMn binary oxide had the potential to be utilized as a low-cost and relatively effective adsorbent for Co(II) removal from wastewater.     

Surface Modification of Sporopollenin with Calixarene Derivative

In this study, p-tert-butylcalix[4]-aza-crown (CAC) immobilized sporopollenin (Sp) was used as a sorbent for the removal of Cu(II), Pb(II) and Zn(II) from aqueous media. Sporopollenin was firstly functionalized with 3-chloropropyltrimethoxysilane (CPTS) in order to obtain chloro-sporopollenin (Sp-Cl). The Sp-Cl was reacted subsequently with CAC yielding CAC-bonded sporopollenin (Sp-Cl-CAC). The new sorbent was characterized by infrared spectroscopy (FTIR), thermal analysis (TG/DTG) and scanning electron microscopy (SEM). The sorption properties of modified sorbent (Sp-Cl-CAC) are also investigated. The optimum pH values for the separation of metal ions from aqueous solution onto Sp-Cl-CAC were 5.0 for Pb(II) and Cu(II) and 5.5 for Zn(II). The maximum sorption capacities for Cu(II), Pb(II) and Zn(II) were 0.07 (4.44?mg?g^?1), 0.07 (4.58?mg?g^?1) and 0.14 (29.00?mg?g^?1) mmol?g^?1, respectively. Sorption thermodynamic parameters of such as free energy (?G ^o), enthalpy (?H ^o), and entropy (?S ^o) were evaluated.     

The association of cobalt with easily reducible manganese in some acidic permanent grassland soils

The association of cobalt with manganese oxides was examined in some surface and sub-soils from areas of permanent grassland in England. Hydroquinone (0.2% in ammonium acetate at pH 7.0) was used to extract easily reducible Mn oxides from the soils. Two sequential extractions with this reagent removed significant proportions of the total Co along with the Mn; no significant amounts of iron were extracted. Mn-rich iron concretions were isolated from two of the soils and these contained from 230 to 880 μg g^?1 Co. Approximately 30% of the Co in the concretions was dissolved by two sequential extractions with hydroquinone with concurrent release of considerable amounts of Mn, but, as with the soils, not of Fe. The concretions contained 20–41 mg g^?1 Mn and 62–171 mg g^?1 Fe that were soluble in acidified H₂O₂. It was concluded that significant proportions of the Co in soils is associated with Mn oxides, and will show the same sensitivity to changes in acidity and redox potential as Mn.     

Effects of grazing on CO2 balance in a semiarid steppe: field observations and modeling

Purpose

Carbon (C) dynamics in grassland ecosystem contributes to regional and global fluxes in carbon dioxide (CO₂) concentrations. Grazing is one of the main structuring factors in grassland, but the impact of grazing on the C budget is still under debate. In this study, in situ net ecosystem CO₂ exchange (NEE) observations by the eddy covariance technique were integrated with a modified process-oriented biogeochemistry model (denitrification–decomposition) to investigate the impacts of grazing on the long-term C budget of semiarid grasslands.

Materials and methods

NEE measurements were conducted in two adjacent grassland sites, non-grazing (NG) and moderate grazing (MG), during 2006–2007. We then used daily weather data for 1978–2007 in conjunction with soil properties and grazing scenarios as model inputs to simulate grassland productivity and C dynamics. The observed and simulated CO₂ fluxes under moderate grazing intensity were compared with those without grazing.

Results and discussion

NEE data from 2-year observations showed that moderate grazing significantly decreased grassland ecosystem CO₂ release and shifted the ecosystem from a negative CO₂ balance (releasing 34.00 g C?m^?2) at the NG site to a positive CO₂ balance (absorbing ?43.02 g C?m^?2) at the MG site. Supporting our experimental findings, the 30-year simulation also showed that moderate grazing significantly enhances the CO₂ uptake potential of the targeted grassland, shifting the ecosystem from a negative CO₂ balance (57.08?±?16.45 g C?m^?2?year^?1) without grazing to a positive CO₂ balance (?28.58?±?14.60 g C?m^?2?year^?1) under moderate grazing. The positive effects of grazing on CO₂ balance could primarily be attributed to an increase in productivity combined with a significant decrease of soil heterotrophic respiration and total ecosystem respiration.

Conclusions

We conclude that moderate grazing prevails over no-management practices in maintaining CO₂ balance in semiarid grasslands, moderating and mitigating the negative effects of global climate change on the CO₂ balance in grassland ecosystems.     

Carbon assimilation and microbial activity in soil

In order to characterise the term microbial ?activity”? three different microbial populations belonging to a luvisol (I), a phaeozem (II) and a rendzina (III) were used for studying kinetic parameters such as substrate affinity, growth rate, yield and turnover time and the metabolic quotient of basal respiration. Glucose was used as a carbon source. Specific growth rate values (μ) varied between 0.0037 and 0.015 h^?1 depending on soil type and glucose concentration and were far below the potential μ_max. The calculated turnover time was 3–11 days, respectively. The yield coefficient was in the range between 0.37 and 0.53. The maximal uptake rate of glucose–C of soil population (II) was 0.041 g C g^?1 biomass-C h^?1. The determined affinity constant (K_m) was 57 μg C g^?1 soil. The affinity to glucose was higher for the glucose-mediated CO₂ evolution with K_m values of 15.2 and 17.5 than for the glucose uptake system itself. The observed qCO₂ values of the basal respiration at temperature increments from 0 to 45° C were almost identical for the soils (I) and (II). The calulated Q₁₀ lay in the range between 1.4 and 2.0.     

Simultaneous Removal of H2S, NH3, and Ethyl Mercaptan in Biotrickling Filters Packed with Poplar Wood and Polyurethane Foam: Impact of pH During Startup and Crossed Effects Evaluation

The present work discusses the startup and operation of different biotrickling filters during the simultaneous removal of NH₃, H₂S, and ethyl mercaptan (EM) for odor control, focusing on (a) the impact of pH control in the stability of the nitrification processes during reactor startup and (b) the crossed effects among selected pollutants and their by-products. Two biotrickling filters were packed with poplar wood chips (R1 and R2A), while a third reactor was packed with polyurethane foam (R2B). R2A and R2B presented a pH control system, whereas R1 did not. Loads of 2?C10?g N?CNH₃ m^?3?h^?1, 5?C16?g S?CH₂S m^?3?h^?1, and 1?C6?g EM m^?3?h^?1 were supplied to the bioreactors. The presence of a pH control loop in R2A and R2B proved to be crucial to avoid long startup periods and bioreactors malfunctioning due to biological activity inhibition. In addition, the impact of the presence of different concentrations of a series of N species (NH ₄ ⁺ , NO ₂ ^? , and NO ₃ ^? ) and S species (SO ₄ ^2? and S^2?) on the performance of the two biotrickling filters was studied by increasing their load to the reactors. Sulfide oxidation proved to be the most resilient process, since it was not affected in any of the experiments, while nitrification and EM removal were severely affected. In particular, the latter was affected by SO ₄ ^2? and NO ₂ ^? , while nitrification was significantly affected by NH ₄ ⁺ . The biotrickling filter packed with polyurethane foam was more sensitive to crossed effects than the biotrickling filter packed with poplar wood chips.     

Acetylene reduction in soil and litter from pine and eucalypt forests in south-eastern Australia

Rates of C₂H₂-reduction in surface soil and litter from pine and eucalypt forests were measured for 1 yr. Rates of reduction increased significantly with moisture content, and mean rates (nmol kg^?1 h^?1) decreased in the order pine litter (339), eucalypt litter (220), eucalypt soil (54), pine soil (7). Asymbiotic N₂-fixation in litter and surface soil was estimated to be 108 mg m^?2 yr^?1 in eucalypt forest and 64 mg m^?2 yr^?1 in pine forest. About 80% of total fixation in eucalypt was in the soil, while 80% of the total in pine was in the litter. N₂ase was active in rotting wood but not in fresh foliage.     

The cation denudation rate as a quantitative index of sensitivity of eastern Canadian rivers to acidic atmospheric precipitation

A model has been developed that relates the cation denudation rate (CDR) of a watershed (the rate that cations derived from chemical weathering are carried off by runoff), the atmospheric load of excess SO₄, and the pH of the river. Chemical and discharge data for rivers in Nova Scotia and Newfoundland were used to develop and test the model, which is based upon the common major ion chemistry of soft surface waters, and may be expressed by three statements: (1) CDR (meq m^?2 yr^?1) ? Excess SO₄ ^?? load (meq m^?2 yr^?1) = HCO₃ ^? (meq m^?2 yr^?1), (2) HCO₃ ^? (meq m^?2 yr^?1)/Runoff (m³ m^?2 yr^?1) = HCO₃ ^? (meq m^?3), (3) pH = pK + \(pP_{CO_2 } \) ? pHCO₃ ^?. The model in concentration form applies well to lakes. A detailed analysis of the data for the Isle aux Morts River, Newfoundland, is presented, showing that the CDR varies throughout the year, affected by both discharge and seasonal pattern.     

Efficient Photocatalytic Reduction of CO<Subscript>2</Subscript> Present in Seawater into Methanol over Cu/C-Co-Doped TiO<Subscript>2</Subscript> Nanocatalyst Under UV and Natural Sunlight

Photocatalytic reduction of CO₂ in seawater into chemical fuel, methanol (CH₃OH), was achieved over Cu/C-co-doped TiO₂ nanoparticles under UV and natural sunlight. Photocatalysts with different Cu loadings (0, 0.5, 1, 3, 5, and 7 wt%) were synthesized by the sol–gel method and were characterized by XRD, SEM, UV–Vis, FTIR, and XPS. Co-doping with C and Cu into TiO₂ remarkably promoted the photocatalytic production of CH₃OH. This improvement was attributed to lowering of bandgap energy, specific catalytic effect of Cu for CH₃OH formation, and the minimization of photo-generated carrier recombination. Co-doped TiO₂ with 3.0 wt% Cu was found to be the most active catalyst, giving a maximum methanol yield rate of 577 μmol g-cat^?1 h^?1 under illumination of UV light, which is 5.3-fold higher than the production rate over C-TiO₂ and 7.4 times the amount produced using Degussa P25 TiO₂. Under natural sunlight, the maximum rate of the photocatalytic production of CH₃OH using 3.0 wt% Cu/C-TiO₂ was found to be 188 μmol g-cat^?1 h^?1, which is 2.24 times higher than that of C-TiO₂, whereas, no CH₃OH was observed for P25.