ACS Catalysis
·
2019
·
IF 12.221
Yue Ma,Songqi Cheng,Xiaodong Wu,Yunzhou Shi,Li Cao,Liping Liu,Rui Ran,Zhichun Si,Jianbo Liu,Duan Weng
Solid-state ion-exchange (SSIE) is an effictive method to prepare Cu-SSZ-13, but usually requires high temperatures or assistance of NH3 for catalyst activation. Herein, an environmentally friendly low-temperature solid-state ion-exchange (LT-SSIE) method was developed. Cu salts that can decompose at temperatures lower than 300 °C (e.g., CuAc2 and Cu(NO3)2) were chosen as Cu precursors. An impregnation method was adopted to obtain high dispersion of the precursors inside the channels of SSZ-13, as confirmed by scanning transmission electron microscopy. A calcination in air at 300 °C for 30 min was found enough for catalyst activation. In situ X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy, thermogravimetry, ultraviolet–visible spectroscopy and H2 temperature-programmed reduction were performed to monitor the activation prcoess of CuAc2-impregnated SSZ-13. The ion-exchange sites of SSZ-13 are occupied by Cu2+ ions originating from CuAc2 at 250–300 °C, revealing the nature of the LT-SSIE process between CuAc2 and SSZ-13.
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
CHINESE JOURNAL OF CHEMICAL ENGINEERING
·
2021
·
IF 3.171
Xin Yong,Hong Chen,Huawang Zhao,Miao Wei,Yingnan Zhao,Yongdan Li
The effects of SO 2 on an one-pot synthesized Cu-SSZ-13 catalyst for selective reduction of NO x by NH 3 were examined. The addition of SO 2 inhibited NO x conversion significantly below 300 °C, while no effect on NO x conversion was observed above 300 °C. TGA, TPD , and XPS results showed that the deactivation was caused by the formation of (NH 4 ) 2 SO 4 , SO 2 chemisorption on the isolated Cu 2+ ion sites, as well as the formation of CuSO 4 -like species. Among them, the site-blocking effect of (NH 4 ) 2 SO 4 on Cu 2+ was the primary reason for deactivation. Fortunately, 89% of deNO x activity of the poisoned catalyst was recovered after thermal treatment at 500 °C in air, where (NH 4 ) 2 SO 4 was completely decomposed. The activity was further recovered with regeneration temperature increasing to 600 °C, removing the adsorbed SO 2 on the Cu 2+ sites. The regeneration at 600 °C could not recover the activity completely, because of the high stability of CuSO 4 -like species.
研究领域:
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
AICHE JOURNAL
·
2022
·Vol. 68
·期 11
·e17834
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IF 4.167
Wuyuan Liu,Zhaoying Wang,Ming Sun,Jiajian Gao,Lifeng Wang,Zihan Gao,Yingying Xu,Xiangyun Zhao,Cheng Zhang,Lin Yu
A series of CeO 2 modified Cu-SSZ-13 monolith catalysts were prepared by embedding CeO 2 into the washcoat of Cu-SSZ-13 monolith catalyst through solvent combustion method. These CexCu-SSZ-13 catalysts were studied in the selective catalytic reduction (SCR) of NO with NH 3 , among which the Ce2Cu-SSZ-13 catalyst exhibited the best low-temperature activity, hydrothermal stability, and sulfur resistance. The physicochemical properties of the catalysts were characterized using multiple methods. Results showed that the acidity, redox capacity, and ammonia adsorption capacity significantly enhanced after CeO 2 modification, thus leading to the high performance of Ce2Cu-SSZ-13 catalyst. Furthermore, the introduction of CeO 2 induced the fast SCR reaction by promoting the oxidation of NO to NO 2 . Analog calculation suggested that the porous structure generated via solvent combustion in the washcoat effectively increased the diffusion rate of reaction. In situ diffuse reflectance infrared Fourier transform spectroscopy ( in situ DRIFT) analysis showed that Brønsted acid sites were the main active center and the reaction followed Eley–Rideal mechanism.
研究领域:
催化化学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED MATERIALS
·
2023
·
IF 29.4
Yingzhen Wei,Shuang Wang,Mengyang Chen,Jinfeng Han,Guoju Yang,Qifei Wang,Jiancheng Di,Hongli Li,Wenzheng Wu,Jihong Yu
Core–shell catalysts with functional shells can increase the activity and stability of the catalysts in selective catalytic reduction of NO x with ammonia x . However, the conventional approaches based on multistep fabrication for core–shell structures encounter persistent restrictions regarding strict synthesis conditions and limited design flexibility. Herein, a facile coaxial 3D printing strategy is for the first time developed to construct zeolite-based core–shell monolithic catalysts with interconnected honeycomb structures, in which the hydrophilic noncompact silica serves as shell and Cu-SSZ-13 zeolite acts as core. Compared to a Cu-SSZ-13 monolith which suffers from the interfacial diffusion, the SiO 2 shell layer can increase the accessibility of active sites over Cu-SSZ-13@SiO 2 , resulting in a 10–20% higher NO conversion at200−550 °C under 300 000 cm 3 g −1 h −1 . Meanwhile, a thicker SiO 2 shell enhances the hydrothermal stability of the aged catalyst by inhibiting the dealumination and the formation of CuO x . Other representative monolithic catalysts with different topological zeolites as shell and diverse metal oxides as the core can be also realized by this coaxial 3D printing. This strategy allows multiple porous materials to be directly integrated, which allows for flexible design and fabrication of various core–shell monolithic catalysts with customized functionalities.
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
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2019
·
IF 14.229
Huawang Zhao,Yingnan Zhao,Mengke Liu,Xianghui Li,Yuhan Ma,Xin Yong,Hong Chen,Yongdan Li
Phosphorus is introduced to modify the Cu-SSZ-13 catalyst via incipient wetness impregnation, with P/Cu-SSZ-13 = 1 and 2 wt.%, and Si/Al = 4, for selective catalytic reduction of NOx with NH 3 . N 2 physisorption and XRD results show the incorporation of phosphorus as phosphate acid enhanced the hydrothermal stability of Cu-SSZ-13 significantly, during hydrothermal aging in 10 vol.% H 2 O/air at 750 °C for 16 h. NMR and Raman results suggest that phosphate ions migrate and coordinate with the framework-bonded Al species, forming a framework silicoaluminophosphate interface, thus impeding further dealumination and structure collapse. Before the hydrothermal aging, the isolated Cu 2+ ions partly interact with the phosphate ions, forming Cu-phosphate species and reducing the SCR performance. Nevertheless, the appropriate content of phosphate ions can prevent the structure collapse caused by the hydrothermal aging, remaining the isolated Cu 2+ ions as well as excellent SCR performance.
研究领域:
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
INORGANIC CHEMISTRY
·
2022
·
IF 5.436
Yichang Yang,Xiangyu Meng,Longfeng Zhu,Jinghuai Yang,Guoliang Zhang,Hongxia Shen,Xuebo Cao
Rapid synthesis of Si-rich (SiO2/Al2O3 > 100) SSZ-13 zeolite under fluoride-free conditions is highly desirable but still challenging. Herein, we for the first time report a rapid synthesis of all silica and aluminosilicate (SiO2/Al2O3 > 100) SSZ-13 zeolite without the addition of fluoride species. The crystallization could be fully completed at 160 °C for 4 h when the aging of the starting gel is 3 h at room temperature after the addition of a zeolite seed. The key to success is the formation of more basic building units (4- and 6-membered rings) in the initial gel with the aging time of 3 h after the addition of a zeolite seed, leading to the successful rapid synthesis of Si-rich SSZ-13 zeolite. The obtained Si-rich SSZ-13 zeolite displays high crystallinity, uniform cubic morphology with a nanoparticle feature, and a large surface area. More importantly, the obtained Si-rich SSZ-13 zeolite displays excellent performance in the adsorption of ethanol and methanol-to-olefin reaction.
研究领域:
材料科学
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化学工程
·
催化
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Physical Chemistry C
·
2021
·
IF 4.126
Shichao Han,Xiaomin Tang,Ye Ma,Qinming Wu,Jiaqi Shi,Jian Li,Xiangju Meng,Anmin Zheng,Feng-Shou Xiao
The selective catalytic reduction of nitrogen oxide with methane (CH4–SCR) has been considered as an alternative technology for the simultaneous removal of NOx and CH4, and one of the efficient catalysts for this reaction is Co-exchanged SSZ-13 (Co-SSZ-13) zeolite catalyst. However, the preparation of the Co-SSZ-13 zeolite catalyst is costly due to the use of an expensive organic template and Co exchange. We demonstrate here the design of a low-cost cobalt–amine complex (Co–DETA) as a novel structure-directing agent (SDA) for the one-pot synthesis of Co-SSZ-13 zeolite with the assistance of theoretical calculations. Physicochemical characterizations including X-ray diffraction, scanning electron microscopy, N2 sorption, and magic-angle spinning nuclear magnetic resonance show that the Co-SSZ-13 zeolite has good crystallinity, a cubic morphology, a high surface area, and four-coordinated aluminum species. Furthermore, thermogravimetry–differential thermal analysis, Fourier transform infrared spectroscopy, and diffuse reflectance ultraviolet–visible spectroscopy confirm that the Co–DETA complex acts as a SDA for the synthesis of Co-SSZ-13 zeolite. More importantly, the Co-SSZ-13 zeolite exhibits good catalytic performance in the CH4–SCR reaction with 10% H2O in the feed gas stream. The efficient and facile synthesis of Co-SSZ-13 zeolite plus its good catalytic performance might offer a good opportunity for its industrial applications in the future.
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
Journal of Environmental Chemical Engineering
·
2023
·
IF 7.7
Chenxi Wang,Gang Lv,Yunqiang Li,Ye Liu,Chonglin Song
The selective catalytic reduction of nitrogen oxides by methane (CH 4 /NO X -SCR) is a potential technique for the abatement of the NO X emissions from lean-burn GDI engines, due to the excellent thermal stability of CH 4 . This work focuses on the promotion of In/SSZ-13 catalysts by Ce modification for the CH 4 /NO X -SCR performance at high temperatures. A series of In/SSZ-13 and Ce-In/SSZ-13 catalysts were prepared using the wetness impregnation method. The effects of Ce modification on the catalytic performance were analysed in detail using the scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, ultraviolet-visible diffuse reflectance spectrum and temperature-programmed desorption/reduction techniques. The results show that the Ce modification significantly enhances the high-temperature activity of the In/SSZ-13 catalysts for the NO X -SCR reaction, especially for the 5 wt% Ce-15 wt% In/SSZ-13 sample which has more than 75% NO X conversion at 390–700 °C. In addition, the Ce modification enhances the water vapor tolerance of the catalyst sample. The Ce modification increases not only the concentration of surface chemisorption oxygen species, but also the relative amount of InO + species which serve as the main active sites for CH 4 activation. Furthermore, the incorporation of Ce into In/SSZ-13 greatly promotes NO X adsorption on the catalyst surface. Most importantly, the Ce modification makes In species well-dispersed on the catalyst surface and thus suppresses the formation of bulk In 2 O 3 species which are more active for the CH 4 non-selective oxidation. The combination of all these effects results in the Ce-In/SSZ-13 samples with the superior catalytic activity .
研究领域:
环境科学
·
催化化学
✓ 已验证
DOI
高影响因子
CHINESE JOURNAL OF CHEMICAL ENGINEERING
·
2025
·
IF 3.7
Dingding Liu,Yating Huang,Zhenguo Li,Guohua Jing,Yongdan Li,Huawang Zhao
The advancements in engine technology have led to a decrease in exhaust temperatures, hence enhancing the activity of Cu-SSZ-13 at low temperatures becomes crucial and challenging. This enhancement can be achieved using dual-phase metal oxide/Cu-SSZ-13 composite catalysts. In this work, we evaluated the comparative efficacy of Mn 3 O 4 and Mn 2 O 3 and discovered that Mn 3 O 4 exhibited a significantly superior enhancement in deNO x activity of Cu-SSZ-13 at low temperatures, achieving 95% NO x conversion at 200 °C. This is substantially higher than the conversions recorded by Mn 2 O 3 /Cu-SSZ-13 (78%) and Cu-SSZ-13 (40%). Kinetic and IR results demonstrate that Mn 3 O 4 /Cu-SSZ-13 and Mn 2 O 3 /Cu-SSZ-13 composite samples share a same low-temperature pathway, where bridged nitrates formed on the MnO x react with adsorbed on Brønsted acid sites in Cu-SSZ-13. In this reaction pathway, bridged nitrate formation is identified as the rate-determining step. The distinctive structure of Mn 3 O 4 triggers an increase in oxygen vacancies, creating a higher content of chemically adsorbed oxygen, compared to Mn 2 O 3 . Those adsorbed oxygen facilitates bridged nitrate formation. Consequently, due to the larger amount of bridged nitrate formed on Mn 3 O 4 compared to Mn 2 O 3 , the Mn 3 O 4 /Cu-SSZ-13 sample exhibits higher activity.
研究领域:
环境催化
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材料化学
·
大气污染控制
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化学工程
·
表面科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS TODAY
·
2019
·
IF 4.888
Yuhan Ma,Huawang Zhao,Cuijuan Zhang,Yingnan Zhao,Hong Chen,Yongdan Li
Cu-SSZ-13 is a highly active catalyst to remove NO x in the emission of diesel-powered engine. However, the enhancement of its stability in high-temperature (HT) hydrothermal conditions is a well-known challenge in application. This work presents a simple strategy to significantly improve its hydrothermal stability under HT hydrothermal condition by mechanically mixing another CHA type zeolite, Cu-SAPO-34. Both the two zeolites are synthesized via one-pot method, mixed in different ratios, and treated in 10% H 2 O/air at 750 °C for 16 h. The mixed samples are characterized before and after the hydrothermal treatment, and tested in NH 3 -SCR from 150 to 550 °C. The results show the activity of the hydrothermally treated catalysts increases with the increase of the amount of Cu-SAPO-34 up to 50 wt% in the mixed sample. The hydrothermal stability of Cu-SSZ-13 is obviously enhanced by mixing with Cu-SAPO-34. The dealumination is suppressed during the hydrothermal treatment; the framework and the isolated Cu 2+ sites are largely maintained in Cu-SSZ-13. This is attributed to the interaction between the two CHA zeolites during the hydrothermal treatment. We propose the delivery of extra-framework P species from Cu-SAPO-34 to Cu-SSZ-13 is critical to enhance the HT hydrothermal stability.
研究领域:
环境科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2019
·
IF 5.128
Han Jiang,Bin Guan,He Lin,Zhen Huang
This study focuses on investigating the influence of Si/Al ratio on the performance of hydrothermally aged Cu/SSZ-13 catalysts prepared by in situ hydrothermal synthesis method. It was found that NH 3 -SCR performance and hydrothermal stability of Cu/SSZ-13 decreased with increasing Si/Al ratio. Fresh and hydrothermally aged Cu/SSZ-13 with Si/Al ratio of 6.5 showed the best SCR activity and N 2 selectivity in a broad temperature of 200–500 °C, in which more than 90% NO x was reduced with superior N 2 selectivity above 95%. The effect of Si/Al ratio on the properties of the physicochemical structure, the change of acidity intensity, and Cu species migration or transformation of the fresh and aged Cu/SSZ-13 catalysts were comprehensively characterized by NH 3 -TPO, NH 3 -TPD, H 2 -TPR, N 2 physisorption, XRD, ICP-AES, and XPS. The increase of the surface CuO species, the decrease of the amount of Cu 2+ in active sites, the chemisorption NH 3 species, the specific surface area, the total pore volume, and the increase of average pore diameter, may be the main reasons for performance deterioration over high-Si/Al-ratio catalysts after hydrothermal aging. Furthermore, in situ DRIFTS indicate that, with the increasing Si/Al ratio, the zeolitic structure was easy to collapse, and that the surface acid sites, the active copper species, as well as the adsorbed surface nitrate, decreased after hydrothermally aged. After hydrothermal aging, the amount of isolated Cu 2+ decreased, and more CuO species were aggregated, mainly coming from the conversion of the unstable isolated Cu 2+ species in D6R or CHA cages. The decrease of isolated Cu 2+ and CuO species aggregation were significant in Cu/SSZ-13 with high Si/Al ratios. The CuO leaded to the instability of the SSZ-13 skeleton structure and NH 3 oxidation promotion, resulting in catalysts deactivation.
研究领域:
催化化学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
Reaction Kinetics Mechanisms and Catalysis
·
2021
·Vol. 134
·期 2
·837-849
·
IF 2.081
Zhao Xinhong,Niu Li,Hao Zongyi,Long Xuefeng,Wang Dongliang,Li Guixian
SSZ-13 has been widely used in catalysis and adsorption due to its excellent hydrothermal stability and large specific surface area. It was reported that the long crystallization time was one of the primary challenges limiting its industrial progress. In this paper, we reported a novel solid-state grinding route of synthesizing SSZ-13 zeolite, which was based on interzeolite transformation strategy and promoted by sodium persulfate (Na 2 S 2 O 8 ). The effects of the amount of Na 2 S 2 O 8 and crystallization time on the purity and crystallinity of SSZ-13 zeolite were studied by XRD measurements in detail. The results indicated that the crystallization time could be significantly shortened from 72 to 24 h when the molar ratio of Na 2 S 2 O 8 /SiO 2 was changed from 0 to 0.01, proving that Na 2 S 2 O 8 has the ability of accelerating the crystallization of SSZ-13 as a hydroxyl radical reagent. Three typical SSZ-13 materials and a reference sample were used as the catalysts for methanol-to-olefins reaction (MTO) and their physicochemical properties were analyzed by SEM, N 2 physisorption and NH 3 –TPD techniques. The SEM characterization results showed that the crystal size of SSZ-13 synthesized in the presence of Na 2 S 2 O 8 was larger than that of the one in the absence of it. The NH 3 –TPD results showed that the introduction of Na 2 S 2 O 8 could modulate the acid properties of SSZ-13 zeolites. The MTO tests revealed that the catalytic lifetime of one sample with Na 2 S 2 O 8 promoter (SSZ-13-0.01M-24h) was much longer than that of the other three samples. The observed difference in catalytic stability was mainly attributed to their various concentrations of medium strong acid sites.
研究领域:
化学工程
·
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）