CHEMICAL ENGINEERING JOURNAL
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2022
·
IF 16.744
Chuanjian Su,Chaolin Li,Ruhong Li,Wenhui Wang
Piezocatalytic molecular oxygen activation has been regarded as a promising and low energy-cost strategy for environment remediation, yet the piezocatalytic activity is still far from satisfactory and little is known on its activation mechanism, which greatly hinders its further development. Herein, the piezocatalyst Bi 2 Fe 4 O 9 nanosheets (BFO NSs) are synthesized via a facile hydrothermal method, which exhibit excellent piezocatalytic performance for sulfamethoxazole degradation. O 2 ∙ - generated via the molecular oxygen reduction reaction by piezo-electrons and the piezo-holes were confirmed as major active species for organic pollutants degradation. Further theoretical calculations and XPS analyses confirm the Fe 2+ sites as active centers activate molecular oxygen into O 2 ∙ - via donating the electrons to molecular oxygen and the piezo-electrons reduce Fe 3+ to Fe 2+ . This work provides atomic-scale insights into the active sites of piezocatalytic molecular oxygen activation, which can inspire the development of more efficient piezocatalysts for environment application.
研究领域:
环境科学
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材料科学
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产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2025
·
IF 9.5
Chang'an Wang,Zuoshuai Xi,Tao Ban,Zhiyuan Liu,Yibin Luo,Hongyi Gao,Ge Wang,Xingtian Shu
The fine design and regulation of the microenvironment surrounding active sites in metal–organic frameworks (MOFs) are crucial for optimizing electron distribution and enhancing oxygen activation, thereby achieving superior catalytic performance in epoxidation reactions. In this study, we focus on the synergistic modulation of the cobalt (Co) microenvironment in MOF-74 through the introduction of lanthanum (La) sites and defect engineering. The incorporation of rare-earth La species effectively redirects the electron density of Co sites, enhancing their oxygen activation capabilities. Additionally, the presence of coordination-unsaturated Co sites facilitates rapid electron transfer from active sites to substrates, promoting the generation of superoxide radicals. Notably, the Co0.50La0.50-MOF-74-4eq sample demonstrates exceptional molecular oxygen utilization and epoxidation performance, achieving a cyclohexene conversion of 92.2% with a selectivity of 93.9% for 1,2-epoxycyclohexane at 40 °C within 1 hour. Furthermore, this catalyst exhibits broad applicability across different substrates. Density functional theory calculations, complemented by in situ analysis, confirm that molecular oxygen activation occurs at Co sites while suppressing the allylic oxidation pathway, thus favoring the conversion of cyclohexene to epoxides. This work elucidates how strategically tailoring the electronic properties around catalytic sites can dramatically influence catalytic behavior in heterogeneous catalysis, providing new insights for the rational design of advanced catalysts.
研究领域:
催化化学
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材料科学
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2017
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IF 9.446
Shao-jia Liu,Fa-tang Li,Yi-lei Li,Ying-juan Hao,Xiao-jing Wang,Bo Li,Rui-hong Liu
The mismatches of lattices and energy bands in heterojunction are the dominant factors restricting the generation efficiency of reactive oxygen species (ROS) that are powerful tools for water purification and anti-bacteria. In this paper, the mediated lattice matching role of amorphous Al 2 O 3 is presented for constructing the ternary g-C 3 N 4 /Al 2 O 3 /ZnO heterojunctions, which exhibit higher molecular oxygen activation performance than binary g-C 3 N 4 /ZnO and g-C 3 N 4 /Al 2 O 3 heterojunctions. The oxygen activation ability and the ROS generation were testified by the electron paramagnetic resonance (EPR) measurement, transformation of nitroblue tetrazolium (NBT) and degradation of methylene blue (MB). The ROS include superoxide anion radical ( O 2 − ) and consequent product of hydroxyl radical ( OH). The superior oxygen activation performance of the ternary heterojunctions can be attributed to the lattices matching of the mediated amorphous Al 2 O 3 and the resultant efficient cascade electron transfer.
研究领域:
材料科学
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环境科学
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化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2019
·
IF 14.229
Xin Hu,Huiping Zhao,Ying Liang,Rong Chen
Solar-driven molecular oxygen activation is of great importance for reactive oxygen species (ROS) production in environmental remediation. In this work, a convenient bromine doping strategy was developed to mediate the energy level of Bi 2 O 2 CO 3 for molecular oxygen activation. The band structure and DFT calculation demonstrate that the Fermi level of Bi 2 O 2 CO 3 elevates after bromine doping, which promotes the molecular oxygen activation and ROS production. The Br-doped Bi 2 O 2 CO 3 exhibits remarkably enhanced photocatalytic ability and could degrade 95% of the ciprofloxacin within 30 min. Moreover, HPLC-MS analysis elucidates that the pyrrolidone ring degradation process is the dominate pathway in ciprofloxacin degradation over Br-doped Bi 2 O 2 CO 3 , resulting in the decrease of antimicrobial activity of the degradation products and the risk of drug-resistance. This work not only provides a molecular oxygen activation strategy via energy level mediation, but also helps us to further understand the relationship between the elemental doping and molecular oxygen activation.
研究领域:
环境科学
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材料科学
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化学
✓ 已验证
DOI
高影响因子
Inorganic Chemistry Frontiers
·
2022
·Vol. 9
·期 6
·1300-1312
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IF 7.779
Nangui Lv,Chenhu Sun,Xueqin Wang,Chan Wang,Yuanyuan Yue,Xiaojun Bao
Synthesizing CHA-type zeolite via template-free interzeolite transformation has been considered as a green method, but the resultant zeolite exhibits low activity in the selective catalytic reduction of NOx by ammonia (NH3-SCR). Herein we report a highly active NH3-SCR catalyst (Cu-CHAUSY) derived from CHA-type zeolite (CHAUSY) that is synthesized via template-free interzeolite transformation from ultra-stable Y (USY). The ultra-high activity is attributed to the specific silicon and aluminum configurations in USY which are distinctly different from those in the conventionally used parent NaY, although they have similar SiO2/Al2O3 ratios. This characteristic endows CHAUSY with more single Al atoms in a six-membered ring, benefiting the self-reduction of [Cu(OH)]+ and the activation of O2 during the NH3-SCR reaction. Moreover, Cu-CHAUSY is demonstrated to outperform the two reference catalysts prepared from the aluminosilicate gel by conventional hydrothermal crystallization with the assistance of organic templates. Our work provides a new strategy for preparing highly active NH3-SCR catalysts.
研究领域:
化学工程
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催化科学
✓ 已验证
DOI
高影响因子
ENVIRONMENTAL POLLUTION
·
2024
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IF 7.6
Xiaoman Yu,Menglin Liu,Haiming Xu,Jian Xu,Jiarui Yi
Enhancing adsorption ability of photocatalyst by vacancy is a fascinating strategy. Thus, Bi 2 WO 6 /BiOCl with millefeuille-like was successfully prepared via multi-pots method. Experimental results discern that BOW-10 can degraded 75.19% doxycycline hydrochloride (DOC, 20 mg/L) in 1 h, which is 1.3 and 3.5-fold larger than Bi 2 WO 6 and BiOCl, respectively. The mechanism revealed that OVs (oxygen vacancies) not only promote the adsorption of DOC and O 2 but also augment the activation ability of molecular oxygen. Therefore, photo-induced electrons can rapidly transfer from BiOCl to Bi 2 WO 6 via carrier transport channels formed by interface oxygen vacancies (IOVs) under interfacial electric field (IEF) to reduce the adsorbed O 2 . Finally, DOC was eliminated by O 2 ˙ - and h + . Moreover, the relationship of surface areas, OVs concentration and the separation efficiency of photo-generated carriers was constructed. Meanwhile, the degradation paths of DOC and the toxicity of the intermediates were comprehensively investigated through DFT theoretical calculation. This research provides an innovation approach to regulate the capability of pollution adsorption and molecular oxygen activation by vacancy engineering and heterostructure engineering.
研究领域:
环境科学
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材料科学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Xi Chen,Xiaoyan Wang,Ziliang Jia,Chao Yang,Zhihong Liu,Yuexing Wei,Mengxue Wang,Meisheng Liang
K-doped Mn–Ce solid solution catalysts were synthesized using a combination of coprecipitation and hydrothermal methods, demonstrating excellent performance in benzene oxidation. The catalyst K 1 Ce 5 Mn 5 exhibited comparable activity to noble metal catalysts, achieving a 90 % benzene conversion at approximately 194 ℃. Durable tests under dry and moist conditions revealed that the catalyst could maintain its activity for 50 h at 218 ℃ and 236 ℃, respectively. Characterization results indicated that the catalyst’s enhanced activity resulted from the weakened Mn–O bonding caused by the introduction of K + , facilitating the activation of oxygen and its involvement in the reaction. CeO x , the main crystalline phase of Mn–Ce solid solutions, provided abundant oxygen vacancies for capturing and activating oxygen molecules for the weakened Mn–O structures. This conclusion was further supported by partial density of state analysis from density functional theory computations, revealing that the introduction of K + weakened the orbital hybridization of Mn3d and O2p. Finally, in situ diffuse reflectance infrared Fourier-transform spectroscopy ( in situ DRIFTS) studies on Ce 5 Mn 5 and K 1 Ce 5 Mn 5 catalysts suggested that the introduction of K + promoted the conversion of adsorbed benzene. Furthermore, intermediate products were transformed more rapidly for K 1 Ce 5 Mn 5 compared to Ce 5 Mn 5 .
研究领域:
催化化学
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环境科学
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED SURFACE SCIENCE
·
2024
·
IF 6.3
Siwen Gong,Gangqiang Zhu,Xiaoqian Xie,Fei Rao,Lujun Zhu,Yurong An,Xianjin Shi,Yu Huang,Peng Liu,Mirabbos Hojamberdiev
A novel interface of MnO 2 with CuO with multivalent conversion is fabricated by the deposition-precipitation method for low-temperature and efficient CO oxidation. It is found that the temperature for CO thermal-catalytic oxidation to reach a complete conversion significantly decreases to 105 °C for the CuO/MnO 2 . A combination of experimental and theoretical studies demonstrates the successful formation of the CuO/MnO 2 interface, inducing a pronounced effect that promotes CO oxidation. The CuO/MnO 2 interface leads to the formation of Cu-O-Mn, a superior redox system with multivalent conversion (Cu + + Mn 4+ ↔ Cu 2+ + Mn 3+ , Cu + + Mn 3+ ↔ Cu 2+ + Mn 2+ ), abundant active sites, excellent ability to activate O 2 , the rapid oxygen transfer, and more suitable adsorption energy for O 2 , CO, and CO 2 . These characteristics are advantageous to Cu x O-Mn x O y for achieving a 100 % removal of CO at a lower temperature. Furthermore, the computational study reveals that the CO oxidation process follows two mechanistic pathways (Eley-Rideal (E-R) and Mars-van Krevelen (M-K)), indicating that there is no competitive adsorption of CO and O 2 on the CuO/MnO 2 . This study shows that the interface created between suitable metal oxides can improve the catalytic performance and provides new perspective for catalyst design and performance enhancement mechanisms.
研究领域:
材料科学
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催化化学
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DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2022
·Vol. 32
·期 45
·2205121
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IF 19.924
Lixuan Zhang,Kai Wang,Yanqi Jia,Liping Fang,Chen Han,Jiaquan Li,Zongping Shao,Xinyong Li,Jieshan Qiu,Shaomin Liu
Piezoelectric polarization portrays a promising technology to regulate the photogenerated charge carrier separation and transfer behaviors, and the design of multifunctional catalysts with piezo-phototronic effect is a key step. One strategy is to prepare a composite catalyst combining the ideal properties from each individual component. Herein, a facial dopant-induced self-assembling strategy is reported to fabricate an ultracompact nanocomposite (LaFeO 3 /ZnFe 2 O 4 /La 2 O 3 ) with enhanced efficiency for piezo-photocatalysis. The composite is synthesized at 800 °C from the one-pot method, thus the self-constructed interface is created during multi-phase formation, providing the intimate grain-to-grain contact between the semiconductive LaFeO 3 and piezoelectric ZnFe 2 O 4 /La 2 O 3 phases. In such a composite, a synergistic effect for oxygen activation is realized via the effective manipulation of the photogenerated charge carrier separation and spatial transportation through the vibration-created piezopotential. A high piezoelectric coefficient (d 33 ) up to 826 pm V −1 and a superior H 2 O 2 yield of 403 µmol g −1 h −1 (in open air and pure water) are achieved on the optimized composite, outperforming most of the reported lead-free piezo-photocatalyst. The ultracompact composite is very robust without any decay in H 2 O 2 -delivering capability after many cyclic tests. This study provides a universal strategy for the rational design of high-performance piezo-photocatalysts.
研究领域:
材料科学
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环境科学
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化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2022
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IF 16.744
Weijie Yang,Kailong Sun,Jun Wan,Yang-Ai Ma,Yu Wang,Lin Liu,Bicheng Zhu,Feng Fu
Solar-driven activation of molecular oxygen (O 2 ) offers an appealing strategy to realize aerobic oxidation catalysis at room temperature, while the efficiency of photocatalytic O 2 activation is severely limited by lacking O 2 adsorption sites and poor carrier utilization. Herein, an efficient Ni 2 P/Bi 3 O 4 Br-OVs heterojunction is firstly proposed to overcome the limitation by the dual-site design of oxygen vacancies (OVs) and on Ni 2 P cocatalyst. By the joint observations from spectroscopic measurements and theoretical simulations, the introduction of OVs and Ni 2 P on Bi 3 O 4 Br nanosheets can not only optimize the light absorption, facilitate the separation and transfer of photogenerated charge carrier through the S-scheme mechanism, but also provide active sites for effective adsorption and activation of oxygen molecules, thereby contributing to highly efficient generation of •O 2 − radicals. Benefiting from the more oxidative active species of •O 2 − and h + , the Ni 2 P/Bi 3 O 4 Br-OVs photocatalyst achieves near-unity conversion rate and selectivity in aerobic oxidation of sulfide to sulfoxide, and it also exhibits outstanding photoactivity in the aerobic degradation of phenolic pollutants under visible light. This study showcases a feasible O 2 activation approach by defect and heterojunction engineering, and provides a new perspective for designing high-performance photocatalysts in the field of aerobic oxidation catalysis.
研究领域:
材料科学
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环境科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2023
·Vol. 13
·期 7
·4729-4745
·
IF 3.9
Kunyu Chen,Yiwei Huang,Meina Huang,Yanqiu Zhu,Ming Tang,Renjie Bi,Meiping Zhu
Photocatalytic oxidation (PCO) based on semiconductors offers a sustainable and promising way for environmental remediation. However, the photocatalytic performance currently suffers from weak light-harvesting ability, rapid charge combination and a lack of accessible reactive sites. Ultrathin two-dimensional (2D) materials are ideal candidates to overcome these problems and become hotpots in the research fields. Herein, we demonstrate an ultrathin (<4 nm thick) Na-doped BiOCl nanosheets with {001} facets (Na-BOC-001) fabricated via a facile bottom-up approach. Because of the synergistic effect of highly exposed active facets and optimal Na doping on the electronic and crystal structure, the Na-BOC-001 showed an upshifted conduction band (CB) with stronger reduction potential for O2 activation, more defective surface for enhanced O2 adsorption, as well as the highest visible-light driven charge separation and transfer ability. Compared with the bulk counterparts (BOC-010 and BOC-001), the largest amount of active species and the best photocatalytic performance for the tetracycline hydrochloride (TC) degradation were achieved for the Na-BOC-001 under visible-light irradiation, even though it had slightly weaker visible-light absorption ability. Moreover, the effect of the Na doping and crystal facet on the possible pathways for TC degradation was investigated. This work offers a feasible and economic strategy for the construction of highly efficient ultrathin 2D materials.
研究领域:
材料科学
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Yan Sun,Yue Jing,Zhicheng Wang,Mingjie Huang,Wen-Da Oh,Xiaohui Wu,Tao Zhou
Ubiquitous pyrite (FeS 2 ) in the earth’s crust features strong reducing capacity, presenting a promising alternative for molecular oxygen (O 2 ) activation to facilitate water purification, but the interfacial electron transfer efficiency was remarkably retarded due to the existed passivation layer and limited reactive sites on the surface of pristine pyrite. Herein, we proposed an effective mechanochemical approach to unlock the potential of pyrite for O 2 activation and refractory pollutant degradation. Compared to the inert pristine one, the ball milling-treated pyrite (BMPs) could achieve efficient sulfamethoxazole (SMX) degradation with a rate constant of 0.23 h −1 . By a combination of characterizations, batch experiments, and density function theory (DFT) calculations, a clear panorama delineated the consecutive O 2 adsorption and activation processes was established. Ball milling treatment could import rich sulfur vacancies (SVs) on pyrite, which unshifted the p -band center of adjacent S for improved O 2 adsorption, also narrowed the band gap of BMPs to promote the interfacial electron transfer rate for O 2 activation. Singlet oxygen ( 1 O 2 ) was identified as the dominant reactive species for SMX degradation , such non-radical oxidation feature rendered the system with remarkable activity and environmental robustness. Our work lay a foundation for constructing robust pyrite towards stable and efficient environmental remediation applications.
研究领域:
环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）