CHEMICAL ENGINEERING JOURNAL
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2024
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IF 13.3
Nana Wang,Bing Wang,Xueyang Zhang
The combined contamination of antibiotics and heavy metals usually occurs in aquaculture wastewater and has high ecological toxicity. Currently, most research only focuses on the removal of a single heavy metal or antibiotics, and there is little research on the simultaneous removal of both. Therefore, to effectively treat them, this study prepared TiO 2 -loaded phosphogypsum-modified biochar (TYBC450) for adsorption and photocatalytic removal of ofloxacin (OFL) and copper (Cu 2+ ). The removal performance and mechanisms of OFL and Cu 2+ were explored, and their ecological toxicity was assessed through zebrafish acute toxicity experiments. The results suggested a synergistic effect between OFL and Cu 2+ . The adsorption efficiencies of TYBC450 for OFL and Cu 2+ were 88.16% and 90.87% (the adsorption capacities were 1.75 and 3.65 mg/g, respectively). Bridging, precipitation, and complexation effects were the main co-adsorption mechanisms. The photocatalytic efficiencies of OFL and Cu 2+ were 91.23% and 72.09% (the rate constants were 0.0101 and 0.0045 min - 1 , respectively). OFL acted as a hole-trapping agent, while Cu 2+ acted as an electron acceptor, hindering the combination of e - and h + . There were 12 intermediates in the OFL degradation process, which had lower toxicity than the mother organism. Both the cyclic regeneration and actual aquaculture wastewater application tests indicated that TYBC450 had potential application prospects.
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Environmental Technology & Innovation
·
2024
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IF 6.7
Renhua Zheng,Diwen Jia,Haiqin Yang,ZhiYuan Chen,Jiayi Chen,Jingle Chen,Haichang Guo,Cheng Hu,Huali Chen,Ting Wang
To achieve the effective removal of low-concentration antibiotic pollutants present in seawater, floating photocatalytic spheres loaded with ytterbium-doped titania-loaded reduced graphene oxide (Yb-doped TiO 2 /RGO) as active catalytic components were prepared and tested for the degradation of tetracycline (TC) in simulated seawater. Three solvothermal reduction processes were employed to promote TiO 2 crystallization in the Yb-doped TiO 2 /RGO powder catalyst prepared via adsorption-layer nanoreactor synthesis, while simultaneously achieving the surface modification of the GO carrier in the active component. Doping with Yb and reduction reaction during solvothermal treatment converted a small amount of Ti 4+ ions in TiO 2 into Ti 3+ and introduced a low content of lattice oxygen vacancies, which extended the visible light response region of Yb-doped TiO 2 /RGO. Under weak visible light excitation, the three Yb-doped TiO 2 /RGO samples and their corresponding polyurethane (PU) sponge-filled photocatalytic spheres could effectively degrade TC in simulated seawater, with the highest degradation rates of 92 % (within 5 h) for the powder active component and 81 % (within 15 h) for the photocatalytic floating spheres. Use of ethanol and ethylene glycol as solvents led to the significant reduction in the hydrophilic groups of the Yb-doped TiO 2 /RGO powder active component after heat treatment, effectively enhancing their TC adsorption performance in seawater. The eco-friendly PU sponge-filled photocatalytic spheres presented in this study exhibit a promising potential for effective removal of organic pollutants from seawater.
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Journal of Cleaner Production
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2024
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IF 9.7
Taotao Cai,Ying Zhang,Shili Zheng,Peiyi Yan,Yi Zhang
Titanium is a highly valued material. Developing a lower-cost titanium (Ti) metal powder production process, potentially substituting the conventional Kroll-HDH method, has challenged the titanium community for decades. The ease of aluminum forming alloys with titanium and the strong chemical affinity of titanium to oxygen rule out the possibility of fabricating pure Ti metal directly by aluminum reduction of TiO 2 . Based on the demonstrated enhanced deoxidation of Ti using Mg metal, this paper proposes an Al–Mg combined stepwise reduction of TiO 2 to fabricate Ti metal powder. Critical challenges overcome in this research include predicting reaction thermodynamics and preparing Ti 2 O intermediate by Al reduction of TiO 2 without significant Al alloying, which is made possible by forming mild-acid soluble Ca 12 Al 14 O 32 Cl 2 byproduct. Various Al reduction conditions were investigated and optimized. To the best of our knowledge, it is the first report to fabricate Ti 2 O powder by Al reduction of TiO 2 with a highly stable chemical composition. The difficulty of sintering the Ti 2 O intermediate before Mg deoxidation to reduce the surface oxygen contribution is mitigated by mixing a certain amount of low-oxygen titanium powder with the Ti 2 O powder. This allows the densification temperature to be lowered from 1400 °C for sintering pure Ti 2 O powder to 1100 °C. Even with as much as around 15 wt% oxygen, the sintered powder can be effectively deoxidized by Mg with the help of hydrogen. A titanium metal powder with an oxygen content of 0.134 wt%, an Al content of 0.123 wt%, and other impurities meeting the standard of pure titanium metal powder (GB/T 34486-2017 FTA1) is successfully prepared by the Al reduction-Mg deoxidation combined process. It is a promising alternative for producing titanium metal powder and its derivatives.
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2024
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IF 9.4
Feng Yue,Mengke Shi,Cong Li,Yang Meng,Shuo Zhang,Lan Wang,Yali Song,Jun Li,Hongzhong Zhang
Directly capturing CO 2 in ambient air and converting it into value-added fuels using photocatalysis is a potentially valuable technology. In this study, Cu-porphyrin (tetrakis-carboxyphenyl porphyrin copper, CuTCPP) was innovatively anchored on the surface of TiO 2 (titanium dioxide) nanosheets to form an S-scheme heterojunction. Based on this, a photocatalytic reaction system for stably converting CO 2 in ambient air into value-added fuels at the gas–solid interface was constructed without addition of sacrificial agents and alkaline liquids. Under the illumination of visible light and sunlight, the evolution rate of CO is 56 μmol·g −1 ·h −1 and 73 μmol·g −1 ·h −1 , respectively, with a potential CO 2 conversion rate of 35.8 % and 50.4 %. The enhanced of photocatalytic performance is attributed to the introduction of CuTCPP, which provides additional active sites, significantly improves capture capacity of CO 2 and the utilization of electrons. Additionally, the formation of S-scheme heterojunction expands the redox range and improves the separation efficiency of photo-generated charges.
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Inorganic Chemistry Frontiers
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2025
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IF 6.4
Guangxia Wang,Wenhui Wang,Yaozhong Yu,Tao Hu,Juan Ding,Yongming Sui
Active and durable catalysts are crucial for the hydrogen evolution reaction (HER). In the volcano plot, rhodium (Rh) and platinum (Pt) are positioned closely, while the activity and stability of Rh are much inferior to those of Pt. Here, we developed a Rh/TiO2/Ti electrocatalyst to mitigate Pt dependency. The in situ formed TiO2 with oxygen vacancies was prepared utilizing Ti foam as the Ti source. The TiO2 support can confine Rh nanoparticles and ensure charge accumulation at the Rh site, while Rh can enhance the conductivity of TiO2. DFT calculations demonstrate that the strong interaction between Rh and TiO2 could regulate the electronic structure of Rh, thereby accelerating water dissociation and optimizing the adsorption strength of *H. Consequently, compared to Rh/Ti, Rh/TiO2/Ti exhibits significantly enhanced HER activity, requiring overpotentials of only 37.3 and 34.3 mV to reach 10 mA cm−2 in the alkaline and acidic HER, respectively. Furthermore, the vertical nanoarray structure, surface roughness, and metal–support interaction endow Rh/TiO2/Ti with remarkable durability. It works in both alkaline and acidic media for 120 hours at 10 mA cm−2 with unnoticeable activity decline, outperforming commercial Pt/C. This work provides a strategy to overcome the activity and stability limitations of Rh-based catalysts, providing references for promising catalysts for water electrolysis.
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METALLURGICAL AND MATERIALS TRANSACTIONS B-PROCESS METALLURGY AND MATERIALS PROCESSING SCIENCE
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2024
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IF 2.4
Zhu Liguo,Zhang Zuqing,Kong Lingxin,Wang Chengyuan,Yang Bin,Xu Baoqiang
Ti is produced by the Kroll method, mainly by carbothermic chlorination, magnesiothermic reduction, and vacuum distillation, which result in complex processes, low efficiency, and high cost. Although Ti has many excellent properties, its high production costs limit its widespread applications. There is an urgent need to develop new Ti extraction processes to reduce the cost of Ti production. In this study, we propose a new method for the direct preparation of low-oxygen Ti powder from TiO 2 using Mg as a reducing agent and the formation of CeOCl (2Mg ( l ) + TiO 2 ( s ) + 2CeCl 3 ( l ) = Ti ( s ) + 2CeOCl ( s ) + 2MgCl 2 ( l )). First, a deoxidization experiment of Ti with Mg as a deoxidizer was conducted, and the ability of Mg to deoxidize Ti was demonstrated. At 1273 K, when the activity of CeCl 3 was 1, the oxygen concentrations of Ti-A and Ti-B were 380 and 270 ppm, respectively. Subsequently, the TiO 2 reduction experiment was conducted using Mg as the reducing agent. The results showed that MgO activity was effectively reduced by the formation of CeOCl (MgO( s ) + CeCl 3 ( l ) = MgCl 2 ( l ) + CeOCl( s )). When the system reached the Mg/MgCl 2 /CeOCl/CeCl 3 equilibrium, low-oxygen Ti powder below 1000 ppm was directly produced from TiO 2 .
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ENERGY & FUELS
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2024
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IF 5.2
Dechao Wang,Lin Chen,Xun Zhu,Dingding Ye,Yang Yang,Hong Wang,Rong Chen,Qiang Liao
Development of a highly performing heterojunction photoanode is significantly important for photoelectrochemical cells. Herein, a novel strategy is proposed to construct a protonated g-C3N4 nanosheets/nitrogen-doped TiO2 photoanode inspired by polydopamine microspheres. The polydopamine microspheres can enhance the adsorption of protonated g-C3N4 nanosheets via electrostatic interaction, facilitating heterojunction formation. Moreover, the addition of the polydopamine microspheres into the preparation process can not only dope a nitrogen element into TiO2, improving solar energy utilization, but also create a vigorous pore structure in the photoanode, promoting mass transport and light scattering. Besides, the specific surface area can also be increased. Owing to these merits, the photoelectrochemical activity of this newly developed photoanode is greatly improved. Furthermore, the superiority of this photoanode is evaluated by integrating it into a photoelectrochemical cell for simultaneous wastewater treatment and power generation. The maximum power density generated by the newly developed protonated g-C3N4 nanosheets/nitrogen-doped TiO2 photoanode is about 138.5% and 40.9% higher than the TiO2 photoanode and the protonated g-C3N4 nanosheets/TiO2 photoanode prepared without using the polydopamine microspheres, respectively. The present study provides a novel strategy for developing a highly performing heterojunction photoanode.
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FUEL
·
2025
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IF 7.5
Zhangkai Qian,Jia-qi Bai,Mei Ma,Huangfei Liu,Mengdie Cai,Jingshuai Chen,Song Sun
N -methylation of amines, nitro compounds and nitriles with CO 2 and H 2 offers a promising strategy for CO 2 utilization. However, developing highly efficient and stable Cu-based catalysts for selective mono- N -methylation of aniline remains challenging. Herein, we report the successful synthesis of a Cu-ZnO/TiO 2 catalyst, with the optimized 5 %Cu-7.5 %ZnO/TiO 2 catalyst achieving a 96.7 % yield of N -methylaniline (MA) and an initial turnover frequency (TOF) of 7.4 h −1 after 6 h under 453 K, 2 MPa CO 2 and 4 MPa H 2 . This performance surpasses all reported Cu-based catalysts and rivals noble metal-based systems. The catalyst demonstrated reusability at least four cycles and versatility in the N -methylation of various amines, nitro compounds, and nitriles. Kinetic studies revealed reaction orders of 0 with respect to aniline concentration and CO 2 pressure, and 1 with respect to H 2 pressure. Based on kinetics and extensive characterization, we propose a reaction mechanism over 5 %Cu-7.5 %ZnO/TiO 2 , identifying Cu nanoparticles as the active sites. The process proceeds via N -phenylcarbamic acid and N -phenylformamide intermediates, with the hydrogenation of N -phenylcarbamic acid as the rate-determining step.
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CHEMICAL ENGINEERING JOURNAL
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2024
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IF 13.3
Yacong Yang,Zhihao Cao,Tianhan Shen,Junyang Zhang,Zuofei Gu,Mingwan Zhao,Zongli Xie,Yingchun Miao,Yuning Huo,Hexing Li
The photocatalytic membrane systems show great potential for water purification and wastewater treatment with efficient energy utilization. Herein, we develop a synergistic photocatalytic-photothermal route, based on Pd-TiO 2 /PEDOT composite immobilized in PVDF membrane, for effective water permeability and reutilization property. Novel Pd-TiO 2 /PEDOT/PVDF ultrafiltration membrane is prepared by the phase inversion method with immobilizing Pd-TiO 2 /PEDOT obtained by ultrasonic irradiation. During the removal of HA under light irradiation, Pd-TiO 2 /PEDOT/PVDF membrane presents an unexpected increasing in water flux, when compared to pristine PVDF, Pd-TiO 2 /PVDF and PEDOT/PVDF membranes, with the highest normalized flux reaches up to 2.1 and remains as 1.3 even after 300 min of irradiation. This significantly enhances the water transport, along with the achieved high rejection and anti-fouling performance. It can be attributed to synergistic photocatalytic-photothermal effect of Pd-TiO 2 /PEDOT, which is realized by their strong interaction and uniform distribution. The addition of PEDOT promotes photocatalytic effect of Pd-TiO 2 by enhancing separation of photo-induced charges. High photothermal conversion efficiency of Pd-TiO 2 /PEDOT and low temperature difference in Pd-TiO 2 /PEDOT/PVDF membrane facilitate effective thermal storage, beneficial for water transport. Meanwhile, thermal energy promotes generation of more ∙OH and ∙O 2 – radicals to remove pollutants. Synergistic photocatalytic-photothermal contribution in Pd-TiO 2 /PEDOT/PVDF membrane shows significant potential for practical application.
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MICROCHEMICAL JOURNAL
·
2025
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IF 5.1
Zhiyue Wang,Yaru Wang,Shihong Xin,Xueqing Yong,Qixin Wang,Yunlin Chen
Hydrogen (H 2 ) leakage poses critical safety hazards and environmental risks in clean energy systems, driving urgent demands for cost-effective hydrogen sensors with high sensitivity, high selectivity, and rapid response time. Herein, high-performance hydrogen sensor based on photonic crystals (PCs) assembled by CAU-1, nickel (Ni) -doped CAU-1, and TiO 2 are prepared. Comparing with the CAU-1/TiO 2 and CAU-1Ni 15% /TiO 2 PC sensors, CAU-1Ni 25% /TiO 2 PC sensor shows a high sensitivity of hydrogen response to be 0.083 nm/ppm with a good linear relationship in the concentration range of 9–90 ppm hydrogen. Density-functional theory (DFT) adsorption energy calculations quantitatively validate the enhanced hydrogen adsorption capacity through Ni-induced electronic structure modulation. The CAU-1Ni 25% /TiO 2 PC sensor exhibits an ultrafast optical response time of 3 s and a recovery time of 12 s with exceptional repeatability and reliability. Moreover, the CAU-1Ni 25% /TiO 2 PC sensor displays exceptional selectivity toward H 2 by comparing with CO 2 , NH 3 , and O 2 , which is important for practical hydrogen detection applications. This work presents incorporating Ni into CAU-1 enhances hydrogen adsorption energy through electronic structure modulation, enabling the CAU-1Ni 25% /TiO 2 PC to achieve rapid optical sensing response to hydrogen, which establish a new pathway for developing high-efficiency photonic crystal-based optical hydrogen sensors.
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ACS Nano
·
2025
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IF 16
Bei Li,Wen Xie,Jiari He,Xiangxiang Zhang,Zeyan Wang,Yuanyuan Liu,Peng Wang,Hefeng Cheng,Ying Dai,Baibiao Huang,Zhaoke Zheng
The manipulation of exposed anisotropic facets and surface microstructures facilitates the directional migration of photoinduced charge carriers, offering a promising strategy for enhancing the photocatalytic activity. However, the charge dynamics behavior associated with facet engineering remains unclear and elusive. Herein, the critical role of the {001}/{101} facet ratio on carrier lifetime was determined by precisely monitoring the charge redistribution in the micronano regions of individual TiO2 microcrystals via single-particle fluorescence spectroscopy in situ. The results demonstrate that TiO2 with a medium ratio of oxidative and reductive sites exhibits the longest PL lifetimes on both {001} and {101} facets due to the synergistic effect of the facets promoting efficient charge carrier migration. Correspondingly, the optimal utilization of electron–hole pairs was also demonstrated in the further toluene oxidation process. Furthermore, in situ monitoring of the fluorine (F) removal process via annealing of a single TiO2 particle confirms that the formation of oxygen vacancy (OV) after Ti–F bond breakage, rather than the removal of F, is the key factor in further promoting charge separation. In addition, real-time observation of toluene oxidation on a single TiO2 microcrystal was conducted at the single-particle level, indicating that the effective charge transfer between TiO2 and toluene is beneficial for the preferential formation of benzaldehyde on the TiO2-{101} facet. This work provides feasible monitoring methods and strong evidence for facet engineering to promote charge separation, which is beneficial for guiding the rational design of photocatalysts.
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LANGMUIR
·
2025
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IF 3.9
Hanli Wang,Bianli Quan,Jun Xu,Dongyu Li
In this study, the corrosion environment in the evaporation stage of alumina production by the Bayer process was simulated, and TiO2-MMT/EP composite coating was prepared on the surface of Q235 steel. Montmorillonite (MMT) was functionalized via cation exchange and surface grafting using 3-aminopropyl triethoxysilane (KH550), enabling the introduction of organic groups onto the MMT surface and intercalation into its interlayer spacing. After compounding with titanium dioxide, the interlayer spacing of MMT was enlarged (from 1.27 to 2.13 nm) and its hydrophobicity was enhanced (contact angle from 48.14° to 105.6°). TiO2-MMT was added to epoxy resin (EP) to prepare a composite coating with multidimensional synergistic effect. The results show that the composite material can effectively fill the EP microhole defects, and the surface roughness of the coating is only 1.7 nm (pure EP is 65.5 nm). Electrochemical tests reveal that the corrosion current density (Icorr) was 1.126 × 10–5 A·cm–2, the protection efficiency was 98.40%, and the charge transfer resistance (Rct) reached 696.1 Ω·cm2, indicating that the coating effectively prolonged the diffusion pathways of corrosive ions through.
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