Journal of Physical Chemistry C
·
2025
·
IF 3.2
Yanan Qiao,Ziqian Gao,Rui Hua,Houde She,Helin Ye,Lei Wang,Jingwei Huang,Qizhao Wang
In this study, hollow CuPc nanotubes were synthesized using a one-step solvothermal technique and loaded with TiO2 nanoparticles based on electrostatic interactions thereby overcome the inherent limitations of TiO2. The interfacial electric field formed by electrostatic coupling between CuPc and TiO2 effectively promoted spatial charge separation, as evidenced by a 12-fold enhancement in CO yield compared to pure TiO2 under visible light irradiation. Through energy band analysis and DFT calculations, the Z-type heterojunction mechanism between CuPc and TiO2 has been revealed. This mechanism facilitates the migration of photogenerated electrons from the conduction band of TiO2 to the lowest unoccupied molecular orbital of CuPc, while directing holes to migrate in the opposite direction. This spatial charge separation preserves the electrons’ high reduction capability, allowing them to participate effectively in the CO2 reduction reaction. This work highlights the potential of Z-scheme heterojunctions in designing efficient photocatalysts for CO2 reduction, offering a foundation for future research in advanced photocatalytic materials.
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RSC Advances
·
2025
·Vol. 15
·期 35
·28659-28665
·
IF 4.6
Chenyang Li,Zhihan Liu,Huimin Li,Yunsen Xiao,Ying Huang,Yuting Lin,Jie Liu,Bin Wu,Fuweng Zhang,Huidong Zheng,Longfei Yan
Borneol, a pharmaceutically important monoterpenoid, has emerged as a key ingredient in modern medicinal formulations. Here, we report a highly efficient heterogeneous catalytic system using transition metal-doped Co/TiO2 catalysts for the continuous-flow isomerization of isoborneol to borneol. Through systematic screening of bimetallic combinations, we demonstrate that Cu and Ni dopants synergistically enhance the redox properties of Co species, particularly improving hydrogenation–dehydrogenation efficiency in the isomerization of isoborneol. The optimized 1Cu–3Co/TiO2 catalyst (Cu : Co = 1 : 3 mass ratio) enabled a two-stage continuous-flow system, achieving 58% molar yield of borneol with <0.4% camphor byproduct formation after solvent removal. Remarkably, the catalyst maintained >99% metal retention during a total of 200 h of continuous reaction. This work not only provides fundamental insights into promoter effects in bimetallic catalysis but also establishes a commercially viable platform for continuous production of high-purity botanical therapeutics.
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AICHE JOURNAL
·
2024
·
IF 3.5
Jinyan Zhang,Yan Shao,Feng Zeng,Huanhao Chen
Secondary-metals promotion is key to tune the CO 2 hydrogenation performance of Rh-based catalyst. We describe the addition of Cu or Co in TiO 2 nanorods supported Rh catalyst (viz., RhM x /TiO 2 ), showing significant impact on the CO 2 hydrogenation activity and productivity. Cu addition can promote the partial hydrogenation to alcohols (methanol and ethanol), whereas Co led to the deep hydrogenation to alkanes (CH 4 , C 2 H 6 ). Comparative time-resolved in situ DRIFTS studies with H 2 /D 2 isotopic exchange further reveal that both surface adsorbed CO* and formates could be the key reaction intermediates during the CO 2 hydrogenation over RhM x /TiO 2 (especially the RhCu 2.5 /TiO 2 ), in which the interaction strength of CO* regulated by secondary-metals addition was key to tune the reaction pathways and productivity. The findings suggested that rational design of active metal sites, for example the synergy between Rh and secondary-metals, is highly needed to promote the CO insertion and C C coupling to produce ethanol.
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2025
·
IF 8.3
Qiuyu Wang,Xingyu Huo,Jun Wang,Huanyu Chen,Ziwen Wang,Zhe Yin,Binglin Tang,Guoping Yu,Bo Lv
With the escalating energy crisis, clean and renewable hydrogen energy has emerged as a focal point of research. This study utilizes titanium concentrate as the primary raw material and employed a more convenient and efficient mechanical activation-oxidation-reduction-acid leaching process to effectively enrich TiO 2 , thereby producing a highly active and stable TiO 2 photocatalyst substrate. To further enhanced its photocatalytic performance, this research developed a heterostructured mineral-derived material g-C 3 N 4 /TiO 2 -6/Pt. Experimental results indicated that the hydrogen evolution rate of the g-C 3 N 4 /TiO 2 -6/Pt composite material reached 6.42 mmol/g/h within 5 h, whereas that of g-C 3 N 4 /P25/Pt was only 5.92 mmol/g/h. This study underscores the significance of extracting TiO 2 from titanium concentrate and its subsequent applications. By effectively utilizing titanium resources, it aims to address the increasing industrial demand for TiO 2 while providing innovative solutions to combat environmental pollution and mitigate the energy crisis. These findings hold substantial theoretical and practical implications for advancing related fields.
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ENVIRONMENTAL RESEARCH
·
2025
·
IF 7.7
Jinqiang Fu,Fenglan Liang,Wenjing Zhong,Tao Kuang,Ziyuan Yin,Yongshi Li,Zhenggui Huang,Hongli Liu,Deyun Ma
Establishing a simple and consistent strategy to adjust the photocatalyst surface to improve the photocatalytic performance is crucial but remains challenging. Herein, a photocatalyst of TiO 2 -Q-Pd is obtained through one-step quenching of TiO 2 (derived from NH 2 -MIL-125(Ti)) into an aqueous solution of sodium tetrachloropalladium, which displayed a significant improvement in photocatalytic activity, achieving 97 % tetracycline degradation within 60 min and 95 % mineralization at 5 h. The mineralization reaction rate (0.6321 h −1 ) was 2.75 times that of the commercial TiO 2 . Our findings show that quenching leads to the creation of numerous zigzag surfaces and the near-surface palladium atom doping, therefore adjusting the chemical environment of Ti, which accelerates electron-hole pair separation and transfer, and thereby improves the photocatalytic performance. This finding introduces a novel approach to activating metal oxide catalysts derived from MOFs and expands the role of quenching chemistry in catalytic processes.
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CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Yanxu Wang,Lijia Huang,Tian C. Zhang,Yan Wang,Shaojun Yuan
Ammonia gas (NH 3 ) is a notorious malodorous pollutant with detrimental effects on environment and human health. Removing NH 3 through photocatalytic oxidation remains a challenging task due to unclear reaction mechanisms. In this study, DFT simulation results revealed that C doped TiO 2 could extend the photo-response range to the visible region, but the introduction of deep impurity levels was found to accelerate photogenerated carrier recombination. Fortunately, the rational doping of Mo was found to mitigate this negative effect. Accordingly, Mo, C co-doped TiO 2 was synthesized via a facile low-temperature calcination process, resulting in unique band structure that enhanced the photocatalytic oxidation of NH 3 . Notably, in-situ DRIFTS and DFT results demonstrated that the gradual reaction of NH 3 adsorbed on Mo atoms with oxygen species through the N 2 H 4 mechanism, promoting the formation of N 2 . These findings offer insights into the design of efficient photocatalysts for NH 3 removal under visible light, and present a promising technology for indoor air pollution control.
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NANOTECHNOLOGY
·
2024
·Vol. 35
·期 49
·495704
·
IF 2.9
Gang Xiao,Zishuai Wang,Yu Jin,Fengping Wang
The selective cleavage of lignin C–C bonds is a highly sought-after process with the goal of obtaining low-molecular-weight aromatic chemicals from renewable resources. However, it remains a challenging task to achieve under mild conditions. Photocatalysis is a potentially promising approach to address this issue, but the development of efficient photocatalysts is still in progress. In this study, we introduce the heterostructured TiO2@g-C3N4 photocatalyst for the development of a visible light photocatalytic procedure for the selective cleavage of lignin C–C bonds under mild conditions. The photocatalyst displays favourable visible light absorption, efficient charge separation efficiency, and promising reusability. A typical β–O–4 dimer model, 2-phenoxy-1-phenylethanol, was effectively (96.0% conversion) and selectively (95.0 selectivity) cleaved under visible light at ambient conditions. This photocatalytic procedure was also effective when subjected to solar irradiation or other lignin dimer models with β–O–4 or β-1 linkages. This reaction occurred through a Cβ-centred radical intermediate and a six-membered transition state with photogenerated holes as the primary active species. The Cα–OH oxidative dehydrogenation of the substrate could also take place but was a relatively minor route. This study provides a new photocatalytic procedure for visible-light-driven lignin valorisation and sheds light on the design of high-performance nanocomposite photocatalysts for C–C bond cleavage.
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Journal of Materials Chemistry A
·
2025
·
IF 9.5
Can Liu,Danyang Li,Shu Zhao,Hao Li,Fujie Li,Guangrong Zeng,Hai-Chao Chen,Chao Wang,Xiu Song Zhao
Nickle-rich layered oxides (NCMs) are promising cathode materials for high energy-density lithium-ion batteries (LIBs). However, NCMs suffer from poor cycling stability because of severe interfacial side reactions and phase transitions during cycling. Here, we show that by coating a thin and uniform layer of titanium dioxide (TiO2) on the surface of NCM83 (LiNi0.83Co0.11Mn0.06O2) using the atomic layer deposition (ALD) method, its cycling stability is significantly improved with 87.3% capacity retention after 100 cycles at 1C, in sharp contrast to NCM83 without TiO2 coating with only 44.3% capacity retention under the same electrochemical measurement conditions. XPS and ToF-SIMS characterization results reveal that the coated TiO2 layer promotes the formation of a LiF-rich stable cathode/electrolyte interphase (CEI), which effectively suppresses interfacial side reactions and mitigates phase transitions. In-situ XRD characterization results show that the TiO2 coating layer regulates the phase transition process due to mechanical confinement effects, which alleviates crystal distortion and stress accumulation. This work offers an effective approach to modifying nickel-rich cathode materials for high energy-density LIBs.
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ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Hao Liu,Xiao Zhang,Qiang Xu,Yanmei Jin,Shuliang Lv,Haihui Liu
Silicon-based anodes, with a theoretical capacity of ∼4200 mAh/g, are promising candidates for lithium-ion batteries. However, significant volume expansion during cycling leads to electrode fragmentation and poor cycling stability. This study presents a novel approach leveraging metal oxide coatings to simultaneously enhance the mechanical stability and the electronic and ionic diffusion capabilities of silicon-based anodes. TiO2–x/SiOx nanocomposites with a Maudan-like structure were synthesized via hydrolysis and subjected to high-temperature reduction in a H2/Ar atmosphere. The unique heterogeneous structure of these composites features oxygen vacancies in TiO2–x, which induce localized electronic states and generate embedded electric fields at the interface with TiOx. The oxygen vacancies provide additional pathways for electron transport and ion storage, while the embedded electric fields further optimize the electronic and ionic transport properties of the material. This synergistic effect significantly enhances the diffusion of electrons and lithium ions at the interface, effectively mitigating volumetric strain during electrochemical cycling. At a current density of 1 C, the TiO2–x/SiOx composite electrode maintains a capacity of 608.4 mAh/g after 1000 cycles. The synergistic effects of oxygen vacancies and embedded electric fields in TiO2–x/SiOx provide new avenues for silicon-based anode materials, particularly in electric vehicles and energy storage systems.
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MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING
·
2025
·
IF 4.6
Xiaoting Mo,Yue Tian,Heming Wang,Jiahao Dai,Fuzhen Cao,Rongyi Huang,Lizhen Long,Jun Liu
The controllable synthesis TiO 2 with desired morphology and phase composition is essential for achieving the properties required in various applications. Herein, TiO 2 nanotube arrays were synthesized through anodic oxidation followed by calcination in an argon atmosphere. The effects of fluoride ion (F - ) concentration in the electrolyte, oxidation time, and calcination temperature on morphology and phase composition were systematically investigated. The optimal conditions for producing well-defined mixed-phase TiO 2 nanotubes were determined to be anodizing at 60 V for 2 h in an electrolyte consisting 0.4 wt% F - . The mixed-phase TiO 2 obtained at 600 °C exhibited the highest photocurrent, which is 2.7 and 3.4 times that of single anatase phase and rutile phase, respectively. The total amount of hydrogen evolution over the optimized mixed-phase TiO 2 photoelectrode reached 387.1 μmol/cm 2 within 160 min under UV–vis illumination at an applied bias of −1.5 V. The corresponding degradation efficiency for RhB (Rhodamine B) at the platinum electrode was approximately 13 %. The enhanced PEC (photoelectrocatalytic) performance of mixed-phase TiO 2 can be attributed to the synergistic effects arising from extended visible-light absorption, a well-defined one-dimensional nanotube structure, and efficient separation of photogenerated carriers at hetero-phase junction. This work provides valuable guidance for synthesizing mixed-phase TiO 2 electrode using controllable methods.
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JOURNAL OF ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Zhen-Kun He,Yun Mei,Di Xie,Hongkun Niu,Aimin Liu,Xianwei Hu,Zhongning Shi
Copper contamination in industrial wastewater poses serious environmental and health risks, while the depletion of copper ores necessitates efficient recovery strategies. Photocatalytic reduction has emerged as a sustainable approach for both heavy-metal remediation and resource recycling, where the structure-dependent charge separation behavior of photocatalysts is the core determinant of their photocatalytic reactivity. In this work, TiO 2 nanomaterials with distinct morphologies were systematically studied to clarify the structure-carrier separation-photocatalytic performance relationship in metal ion reduction processes. Among the tested samples, thin-walled TiO 2 nanotubes stood out for their optimized structural features: transient photocurrent and open-circuit voltage decay analyses confirmed that the nanotubular architecture significantly enhances charge separation efficiency, accelerates electron transport dynamics, and extends photogenerated carrier lifetime. Specifically, the nanotubes achieved a Cu 2 + reduction rate of 0.3722 mmol/L·min (over three times higher than commercial P25 nanoparticles, 0.1149 mmol/L·min). Furthermore, the introduction of methanol as a hole scavenger further promotes charge utilization efficiency, ultimately enabling 66.7 % recovery of metallic copper. This work emphasizes that the rational design of TiO 2 nanostructures to enhance charge separation is critical for improving photocatalytic metal ion reduction performance. It not only establishes a clear structure-carrier separation-photoreactivity correlation for TiO 2 -based photocatalysts but also provides mechanistic insights and a sustainable strategy for advancing wastewater remediation and circular economy practices.
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Foods
·
2025
·Vol. 14
·期 12
·2062
·
IF 5.1
Lina Zhao,Zhengdong Sun,Ye Shen,Zhiyang Chen,Yang Zhang,Jiyong Shi,Haroon Elrasheid Tahir,Xuechao Xu,Meng Zhang,Xiaobo Zou,Kaiyi Zheng
(1) Background: Asomate, as a dithiocarbamate compound, is moderately toxic to the human body; thus, it is necessary to develop a rapid and efficient method for detection. To meet this need, this study introduced a rapid, non-destructive, and efficient method for detecting asomate residues on the surface of apples based on surface-enhanced Raman spectroscopy (SERS) combined with flexible substrates. (2) Methods: Concave Au nanorods (AuCNAs) were synthesized in advance. Then, the AuCNAs were loaded on an electrostatically spun film to generate a flexible TiO2/ZrO2/AuCNAs substrate for detection. (3) Results: The flexible substrate exhibited strong SERS activity, with an enhancement factor (EF) up to 9.40 × 107for 4-MBA. Meanwhile, the finite-difference time-domain (FDTD) simulation showed that the localized surface plasmon resonance (LSPR) effects related to the enhancement of the SERS signal are mainly generated from the ‘hot spots’ in AuCNAs. The density functional theory (DFT) simulation detailedly revealed that the SERS peaks could be generated by the interaction among asomate molecules, disassociated Au atoms, and Au facets. Moreover, the asomate in apple peel was analyzed with the limit of detection (LOD) as low as below 10 nM, allowing for the rapid detection of asomate directly on apple peels. (4) Conclusions: The flexible TiO2/ZrO2/AuCNAs film can be used for the in situ detection of asomate in apple peel at low concentrations. Moreover, the simulation methods, including FDTD and DFT, explained the mechanism of SERS from the flexible substrates.
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