APPLIED SURFACE SCIENCE
·
2025
·
IF 6.9
Yakai Chen,Xinya Feng,Xiaohan Yu,Xingliang Xu,Jing Xu
Catalytic aldol condensation of biomass-derived furfural (FAL) with acetone (AC) into the single-condensation product 4-(2-furyl)-3-buten-2-one (FAC) is a potential and promising strategy for biomass improvement process and still challenging. Metal oxides exposed different crystal facets can regulate their surface structure and adsorption activation ability, which can provide an opportunity to enhance aldol condensation performance. Here, nanoparticles-CeO 2 (P-CeO 2 ), nanorods-CeO 2 (R-CeO 2 ) and nanocubes-CeO 2 (C-CeO 2 ) with (111), (110) and (100) plane predominant exposure was prepared to explore their catalytic performance for the aldol condensation of FAL with AC to obtain FAC. The serial detailed characterizations, experimental results and density functional theory calculation revealed that R-CeO 2 with a dominant (110) facet possesses appropriate surface adsorption energy, abundant oxygen vacancy (Ov) and excellent acid-base properties, which can effectively boost the adsorption and activation of FAL and AC and reduce the barrier of aldol condensation reaction based on the acid-base catalysis mechanism. The work would reveal the influence of CeO 2 crystal facet on the aldol condensation and provide a broad potential for the rational design of metal oxide catalysts for other acid-base catalytic reactions.
研究领域:
催化化学
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生物质能
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Energy Material Advances
·
2022
·
IF 0
Abraham Adenle,Ming Shi,Xiaoping Tao,Yue Zhao,Bin Zeng,Na Ta,Rengui Li
The development of photocatalysts with wide spectral absorption and high charge separation efficiency has always been a pursued objective for photocatalytic solar energy conversion. Herein, we reported a wide-range visible-light-active Bi4TaO8Cl (BTOC) single crystal nanoplate with dominating {110} and {001} facets for enhancing the intrinsic charge separation efficiency. Insitu selective photodeposition of metals and metal oxides provides evidences of photogenerated electrons and holes spatially separated on {110} and {001} coexposed facets of BTOC, respectively. The intrinsic charge separation efficiency was demonstrated to be closely dependent on the crystal facets, which can be modulated by tuning the coexposed crystal facet ratio. Further surface modification of BTOC with suitable dual cocatalyst Ag and RuOx enables remarkable improvement of charge separation efficiency and photocatalytic water oxidation performance. Investigation by comparison between well-defined BTOC nanoplate and BTOC nanoparticles confirmed the significance of coexposed crystal facets for efficient spatial charge separation and the blocking of reverse reaction from Fe2+ to Fe3+ ions during water oxidation reaction, indicating that rational modulation of exposed crystal facets is significant for controlling the intrinsic charge separation efficiency on Bi4TaO8Cl photocatalyst for efficient photocatalytic water splitting.
研究领域:
材料科学
·
能源化学
✓ 已验证
DOI
Materials Science and Engineering B-Advanced Functional Solid-State Materials
·
2025
·
IF 4.6
Muhammad Kamran,Muhammad Sajjad,Salman Qadir,Changle Wang,Runtong Zhang,Baode Ma,Shao-Tao Bai
Crystal facet engineering is an important concept in material science but is yet to be explored direction of fabricating catalysts with improved selectivity. In this study, we prepared pure TiO 2 brookite nanorod catalysts exposed with a variation of (120), (111), and (110) active crystal domains for photocatalytic NOx (nitrogen oxides) abatement using TALH (C 6 H 18 N 2 O 8 Ti) titania precursor via a variation of sodium lactate (C 3 H 5 NaO 3 ) and urea (NH 4 CNO) addition. The different characterization such as XRD, SEM, and TEM proved the high availability of (111) crystal facet and approximate equal presence of (120), (111), and (110) crystal domains in TALH-6U-SL resulting in up to 4.9-fold higher selectivity than commercial TiO 2 -P25 as well as other brookite nanorod catalysts. TGA, FTIR, and XPS results demonstrated that compared to other catalysts, TALH-6U-SL nanorod catalyst adsorbs more water and contains more oxygen vacancies and crystal defects, thus boosting the photocatalytic selectivity for NOx conversion to NO 3 − ions.
研究领域:
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
SENSORS AND ACTUATORS B-CHEMICAL
·
2024
·
IF 8
Shenman Yao,Dehua Wang,Jiahao Li,Jianxian You,Yulin Zhu,Wufei Gong,Keng Xu,Yan Liang,Yanxing Yang,Yong Yang
Crystal facets engineering emerges as a potent strategy for modulating the surface properties and gas sensing performance of semiconductor metal oxides. However, related studies have primarily focused on conventional binary metal oxides gas sensing materials, while few studies have investigated the crystal facets-dependent gas sensing activity of recently developed ternary metal oxides. Herein, the effect of crystal facets on the gas sensing activity of Aurivillius-type layered perovskite structure material Bi 2 MoO 6 was studied. It was shown that Bi 2 MoO 6 nanosheets with {001} crystal facets exhibited significantly enhanced gas sensing activity with a high response value of 72 (R a /R g ) towards 100 ppm of triethylamine at relatively low working temperature of 250 °C, which was about 10 times higher than that of Bi 2 MoO 6 nanosheets with {010} crystal facets. The gas mechanism was elucidated at the atomic and electronic levels through first principles calculation combined with experimental characterization. On the one hand, the synergistic effect of Mo/Bi bimetallic sites makes the adsorption/charge transfer between {001} facets and triethylamine much stronger. On the other hand, {001} facets have abundant chemically adsorbed oxygen and oxygen vacancy on the surface, which act as the active species in gas sensing. These results not only significantly broaden the application scope of Aurivillius-type layered perovskite structure materials in the realm of gas sensing, but also provide important guidance for the study of gas sensing mechanism in ternary metal oxides.
研究领域:
材料科学
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气体传感技术
✓ 已验证
产品关联
DOI
高影响因子
ChemSusChem
·
2021
·Vol. 15
·期 13
·e202101983
·
IF 8.928
Yanan Wei,Yunlei Zhang,Yao Chen,Fang Wang,Yu Cao,Wen Guan,Xin Li
Graphical Saving face : Catalytic performance of Au/CeO 2 with different exposed CeO 2 crystal faces for oxidation of 5-hydroxymethlfurural to 2,5-furandicarboxylic acid is dependent on the oxygen vacancy (V O ) concentration. Higher V O concentration of Au/rod-CeO 2 (110) is more beneficial for adsorption of oxygen and formation of active oxygen species than Au/cube-CeO 2 (100) and Au/oct-CeO 2 (111). Developing an efficient catalyst to upgrade 5-hydroxymethylfurfural (HMF) to high-value-added downstream chemicals is of great significance in biomass conversion. Nanorod (110)-, nanocube (100)-, and nanooctaheron (111)-CeO 2 -supported Au nanoparticles were prepared to investigate the intrinsic effect of CeO 2 crystal faces on the oxidation of HMF to 2,5-furandicarboxylic acid (FDCA). The experimental results and density functional theory calculation revealed that the concentration of oxygen vacancy (V O ) for exposed specific crystal faces was crucial to the oxygen adsorption ability, and Au/nanorod-CeO 2 with the highest V O concentration promoted the formation of more oxygen active species (superoxide radical) on CeO 2 (110) crystal face than (100) and (111) crystal faces. Besides, the higher V O concentration could provide a strong adsorption ability of HMF, greatly boosting the activation of HMF. Thus, these results led to a superior catalytic activity for HMF oxidation over Au/nanorod-CeO 2 (FDCA yield of 96.5 %). In-situ Fourier-transform (FT)IR spectroscopy uncovered the HMF oxidation pathway, and the possible catalytic mechanism was proposed. The deep insight into the role of regulation for crystal faces provides a basis for the rational design of highly active facets for the oxidation of HMF and related reactions.
研究领域:
催化化学
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材料科学
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生物质转化
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Zunqing Wen,Xiaoguo Shi,Huiying Sui,Minglu Zhang,Longquan Zhang,Yawei Gu,Qing Feng,Ke Ma,Na Zhang,Mingzhe Wang,Ruiyan Zhang,Chongqing Xu,Zengjin Li,Rong Xue
Numerous studies have revealed that air oxidation behavior profoundly impacts pyrite properties. Whereas its influence on pyrite Fenton performance remains controversial. Herein, pyrite FeS 2 nanoparticles synthesized by facile wet-mechanochemical method was employed as oxidation model and its oxidation degree was evaluated by XPS depth profiling technique. Based on theoretical calculation and experimental evidence, the properties and Fenton performance of surface oxidized pyrite (SOP x ) were comprehensively assessed. With oxidation degree increase, free radical generation selectivity was alternated from •O 2 – to •OH, and the selectivity to •OH showed strong correlations with {210} facet ratio, Fe(Ⅱ)-O and sulfur vacancies (SVs) contents. The oxidation degree dependence in •OH selective production primarily stemmed from different electron-donating and Fe 2+ releasing capacity. Moderately oxidized pyrite (SOP 4 ) with high {210} facet ratio, SVs and Fe(Ⅱ)-O contents could donate electrons for H 2 O 2 barrierless dissociation and Fe 2+ /Fe 3+ redox-cycle, and cause more Fe 2+ releasing to enhance homogeneous Fenton reaction. As the oxidation degree increased (from SOP 0 to SOP 4 ), the Fenton systems demonstrated a significant enhancement in sulfadiazine (SDZ) degradation kinetics, with the rate constant increasing from 0.02039 to 0.06904 min −1 . The superior SDZ removal efficiency in SOP 4 system at wide pH range (5–9) indicated moderate oxidation significantly improved its decontamination and practical application ability. However, the amorphous iron oxide layer generated in the over-oxidized pyrite (SOP 6 ) impaired its catalytic activity, resulting in a decrease of the rate constant (0.0485 min −1 ). These findings unveiled the mystery of Fenton performance regulated by FeS 2 oxidation via {210} facet, SVs and Fe(Ⅱ)-O, and offered fresh insights into developing targeted structures for tunable performance.
研究领域:
环境科学
·
材料科学
✓ 已验证
DOI
高影响因子
ACS Catalysis
·
2020
·
IF 12.35
Feng Jiang,Shanshan Wang,Bing Liu,Jie Liu,Li Wang,Yang Xiao,Yuebing Xu,Xiaohao Liu
CeO2 is an excellent potential material for CO2 hydrogenation attributed to the highly tunable properties including metal–support interaction and abundant oxygen vacancy. In this work, four CeO2 supports with structurally well-defined different shapes and crystal facets are hydrothermally prepared, and their effects on the composition of Pd species and oxygen vacancy over Pd/CeO2 catalysts have been intensively investigated in the reduction of CO2 to methanol. The 2Pd/CeO2-R (rods) shows the highest concentration and number of oxygen vacancies, where the (110) facet with high surface oxygen mobility and low oxygen vacancy formation energy is exposed over the CeO2-R surface. The oxygen mobility at the interface of (111) and (100) facets mainly observed on 2Pd/CeO2-P (polyhedrons) is higher than the single (111) and (100) facets mainly observed on 2Pd/CeO2-O (octahedrons) and 2Pd/CeO2-C (cubs), respectively. The presence of Pd highly promotes the formation of oxygen vacancies by providing dissociated H atoms to facilitate the removal of surface O in ceria support under a H2 atmosphere. Both the PdxCe1–xOδ solid solution dominated on CeO2-R and the PdO species dominated on CeO2-O are reduced to metallic Pd after reduction with 6–10 nm average particle size. As revealed by density functional theory (DFT) calculations, in contrast to the single Pd0 atom on CeO2 and the thermodynamically most unstable PdxCe1−xOδ solid solution, the Pd0 nanoparticles are the most stable species under the realistic reaction conditions. The 2Pd/CeO2-R shows the highest catalytic activity as the abundantly available oxygen vacancies function as CO2 adsorption and activation sites. Moreover, oxygen vacancy reactivity is correlated with its formation energy. The lower formation energy facilitates the formation of oxygen vacancy; however, the reactivity of each oxygen vacancy is lower as the TOFoxygen vacancy of 2Pd/CeO2-O is 15 times as that of 2Pd/CeO2-R. Thus, a suitable oxygen vacancy formation energy is likely favorable for enhancing CO2 reactivity. DFT calculations indicate that the CH3OH formation is most probably from the formate (HCOO*) pathway via the C–O bond cleavage in H2COOH*, with the reduction of HCOO* to HCOOH* as the rate-limiting step. These results would provide experimental and theoretical insights into the rational design of an effective catalyst for CO2 hydrogenation.
研究领域:
催化化学
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材料科学
·
理论计算
✓ 已验证
产品关联
DOI
高影响因子
Journal of CO2 Utilization
·
2019
·
IF 5.189
Shanshan Chai,Yong Men,Jinguo Wang,Shuang Liu,Qiaoling Song,Wei An,Gunther Kolb
Catalytic reduction of CO 2 to methane has been recognized as one of the most important strategic reactions to produce highly valuable chemicals and for storage of renewable energy (power-to-gas). This study demonstrates a crystal facet-dependent catalytic reduction of CO 2 to CH 4 on ruthenium nanoparticles deposited over TiO 2 nanocrystal with exposed (001) and (101) facets. Compared with TiO 2 (101) nanocrystal with the same Ru loading, Ru nanoparticles supported by TiO 2 (001) exhibited a highly enhanced CO 2 conversion rate and significantly improved methanation reactivity, along with a considerable durability. The physicochemical properties of the samples were characterized by HR-TEM, XRD, BET, FT-IR, UV–vis, Raman, ICP, and temperature-programmed reaction with CO 2 , and CO 2 + H 2 . In view of the difference in catalytic activity and the physicochemical properties of the supported Ru/TiO 2 catalysts, the results uncovered that the nature of the catalyst support of Ru/TiO 2 strongly affected the dispersion of Ru species and the synergistic effect between Ru and underlying TiO 2 supporting materials due to the strong metal-support interaction, and thus affected their capability to activate CO 2 and determined the catalytic activity for CO 2 methanation. Our work demonstrated the important role of the exposed crystal facets of the underlying support and the resulting Ru particle which had a large effect on CO 2 methanation.
研究领域:
催化化学
·
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Dehao Kong,Weirong Zhou,Jiayin Han,Yubing Gao,Yuan Gao,Liupeng Zhao,Peng Sun,Geyu Lu
Crystal facet engineering strategy is an effective way to regulate the exposed facets, which affect the ability of the surface to adsorb and react with gas molecules, ultimately enhancing the gas-sensing properties. In this work, Co 3 O 4 mesoporous nanosheets with dominant exposed {1 1 1} facets (Co 3 O 4 -60) or {1 1 2} facets (Co 3 O 4 -100) were synthesized by simply adjusting the condensation-reflux temperature. The sensing results toward toluene show that Co 3 O 4 -60 exhibited superior performance. According to the crystal structure analysis and work function calculations, the (1 1 1) facet composed of Co 2+ would adsorb more oxygen molecules, which have been proved by experimental characterization, facilitating the sensing efficiency. The results of X-ray photoelectron spectroscopy indicated that Co 3 O 4 -60 possesses a higher Co 2+ content and chemisorbed oxygen ratio (52.9%). Furthermore, Co 3 O 4 -60 has a high electrical conductivity and a minor apparent activation energy for toluene (38.75 kJ/mol). The gas sensor based on Co 3 O 4 -60 exhibited a response of 20.6 for 100 ppm toluene with rapid recovery and a detection limit of 1 ppm. Besides, other properties such as selectivity, repeatability, and humidity resistance were evaluated. This work evidences that crystal facet engineering is a practical approach to improving the gas-sensing properties of pure-phase Co 3 O 4 .
研究领域:
材料科学
·
传感器技术
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Hongrui Zhu,Chun Zhang,Kefeng Xie,Xingang Li,Guangfu Liao
Defect engineering, exposed crystal facets, and Z-scheme mechanism are promising strategies to greatly promote photocatalytic performance. Herein, the ZnFe 2 O 4 (ZFO) with Ag-doping, oxygen vacancies and different exposed crystal facets was firstly prepared by a facile hydrothermal strategy. Subsequently, the MoS 2 flowers were in-situ grown on the surface of the prepared Ag-doping ZFO (Ag-ZFO) for fabricating MoS 2 /Ag-ZFO Z-scheme heterojunction by hydrothermal strategy. Due to the synergistic effects of defect engineering (Ag-doping and oxygen vacancies), exposed crystal facets, and Z-scheme mechanism, the photocatalytic activity for tetracycline degradation was evidently improved. More importantly, the prepared MoS 2 /Ag-ZFO (T) also show excellent photocatalytic performance under real environment water. This work offers a new insight for future design and development of highly active photocatalysts.
研究领域:
环境科学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2024
·
IF 18.5
Mengting Li,Huiying Mu,Ran Su,Ruihong Liu,Ying Liu,Yilei Li,Fa-tang Li
Although crystal facet engineering is extensively studied in energy and environmental technologies, the in-depth understanding of intrinsic mechanisms governing crystal facet heterojunctions in tuning band alignments is still limited. Here, novel Bi 5 O 7 NO 3 crystals exposing tailor {080} facets are synthesized via NH 4 + -assisted self-confined construction. It has been confirmed that NH 4 + ions selectively adsorb on the {141} facets, inversely inducing the growth of desired {080} crystal facets, while the tailored {080} facets facilitate the generation of oxygen vacancies. The controllable concentration of oxygen vacancies, influenced by different exposed facets, can optimize the relative positions of Fermi levels and shift the photoelectron transfer route between the {141} and {080}-OV facets from type-II to S-scheme, thus triggering rapid charge transport channels and effectively suppressing electron-hole recombination. DFT calculation verifies that the energy barrier for the *COOH formation on Bi 5 O 7 NO 3 -{080}-OV is the lowest, thereby promoting the generation of CO. The well-designed Bi 5 O 7 NO 3 crystals with the optimal {080}/{141} facet ratio exhibit a 3.8-fold enhancement in photocatalytic CO 2 reduction, compared to traditional Bi 5 O 7 NO 3 dominated by the {141} facets. This work offers new insights into the regulation of band alignments at heterointerfaces and the design of high-efficiency photocatalysts.
研究领域:
材料科学
·
环境科学
·
能源技术
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2015
·
IF 3.942
Jun Chen,Shuanghong Tian,Jiang Lu,Ya Xiong
This study aims to provide a direction to tailor catalytic activity of catalyst by selectively exposing a crystal facet. Herein three sheet-like MgO materials with the primarily exposed crystal facet of (1 1 1), (1 1 0), (2 0 0) were prepared, respectively. Results show that the catalytic ozonation on each MgO substantially enhanced the removal of 4-chlorophenol and total organic carbon when compared with ozonation alone or that on traditional MgO. The pseudo first-order reaction constant of 4-chlorophenol removal in ozonation catalyzed by MgO(1 1 1), MgO(1 1 0), MgO(2 0 0) is 4.8, 2.5, 3.1 times higher than that in the single ozonation, respectively. When different dosage but the same surface area of MgO was applied, their catalytic activities changed as MgO(1 1 1) > MgO(1 1 0) > MgO(2 0 0). It indicates that the catalytic activity significantly depends on the crystal facet besides the surface area. That is because the drawbacks, such as edges, steps, and kinks, on each facet decreased in the order of (1 1 1) > (1 1 0) > (2 0 0). CO 2 -TPD and zeta potential measurement show that the drawbacks caused more and stronger surface basic groups in the form of hydroxyl and isolated oxygen due to the availability of more unsaturated coordination sites. These active basic centers make the easy formation of basic microenvironment near MgO particles and thus favor the ozonation. Finally, the catalytic mechanism was explored and compared by evaluating the ozone decomposition, qualitatively and quantitatively identifying hydroxyl radicals, and determining the ozone utilization efficiency. It reveals that MgO with more surface basic groups can enhance the transformation rate of ozone to hydroxyl radicals more efficiently. All these results show that MgO is a very potential ozonation catalyst and the catalytic activity can be tailored by exposing crystal facet with more drawbacks.
研究领域:
环境科学
·
材料科学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）