CHEMICAL ENGINEERING SCIENCE
·
2021
·
IF 4.311
Zhongliang Huang,Yujia Yuan,Miaomiao Song,Zhimian Hao,Jingran Xiao,Dongren Cai,Abdul-Rauf Ibrahim,Guowu Zhan
Herein, we fabricated a series of bimetallic Pt-Ni catalysts supported on mesoporous silica nanorods ( m SNR, specific BET surface area of 1802 m 2 g −1 ) to study the effect of Ni/Pt ratio on the product selectivity in CO 2 hydrogenation. Both monometallic Pt/ m SNR and Ni 50 Pt 50 / m SNR catalysts revealed negligible methane selectivity. However, methane became the major product only when increasing the Ni/Pt ratio up to 9. X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) characterizations showed that the Pt/Ni ratio on the catalyst surface was appreciably higher than the bulk composition, suggesting the enrichment of Pt on the surface ( e.g. , Pt/Ni of 61/39 for Ni 50 Pt 50 / m SNR catalyst). The Pt/Ni ratio was crucial in determining the CH 4 /CO selectivity, and the addition of a tiny amount of Pt could improve the catalytic performance and stability of Ni/ m SNR. Among the different catalysts, Ni 98 Pt 2 / m SNR showed the best CO 2 conversion (59%) and CH 4 selectivity (96%) at 400 °C, 0.1 MPa, 9600 mL h −1 g cat −1 , and H 2 /CO 2 of 3. In-situ DRIFTS and temperature-programmed surface experiments suggested that the dissociated adsorption of CO 2 on the Pt site led to CO*, but the strongly adsorbed CO* cannot be further hydrogenated to CH 4 over the Pt site. In contrast, CO* could be further hydrogenated into CH 4 via CH x O* intermediates on adjacent Ni sites.
研究领域:
催化
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材料科学
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化学工程
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Chenghong Wu,Xiaopeng Chen,Jiezhen Liang,Jiawei Fu,Zhongyao Zhang,Xiaojie Wei,Linlin Wang
The catalytic hydrogenation of dicyclopentadiene (DCPD) is one of the pivotal processes in the production of green high-energy-density liquid hydrocarbon fuels, jet propellent-10 (JP-10). However, the high dependency of the current catalysts on high temperature and pressure, whether the non-noble (>120 ℃, >15 bar) or even the noble catalyst (80 ℃, >7.6 bar), leads to enormous energy consumption and technical challenges in environment and sustainable development. Herein, we prepared a carbon layer wrapped Ni nanoparticles/g-C 3 N 4 catalyst (Ni@C/g-C 3 N 4 ) derived from the in-situ-formed Ni-MOF/g-C 3 N 4 composite. Benefiting from the 53.2 wt% small-sized Ni nanoparticles and nanosheet structure, resulting in high-density accessible active sites (5.38 × 10 20 sites g −1 ) and the mass transfer enhancement, Ni@C/g-C 3 N 4 achieved DCPD hydrogenation under ambient conditions. > 99.9 % DCPD conversion and 98.1 % endo -tetrahydrodicyclopentadiene yield was obtained at 30 ℃, 1 bar, significantly outperforming the benchmark 5 % Pd/C. To the best of our knowledge, it’s the mildest condition for DCPD hydrogenation. Further, comprehensive mechanistic insights were gained from combining means of kinetic investigations, in situ characterization, and theoretical calculations. The discrimination result of 27 kinetic models indicated that DCPD hydrogenation followed the Langmuir-Hinshelwood-Haugen-Watson formulism regarding the reaction between the chemisorbed dihydrodicyclopentadiene (DHDCPD) and dissociatively adsorbed hydrogen as the rate-determining step. In-situ DRIFTS confirm that the norbornene ring is preferentially adsorbed and hydrogenated. The DFT calculations further substantiate the hydrogenation pathway. The present work provides guidance for the development of highly efficient non-noble metal catalysts and opens up an environmental-friendly and economically viable avenue for DCPD hydrogenation.
研究领域:
催化
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材料科学
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化学工程
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物理化学
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产品关联
DOI
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
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2023
·
IF 13.6
Xin Yang,Kaijie Liu,Xinyu Han,Jianheng Xu,Mengyao Bian,Daying Zheng,Haijiao Xie,Yibo Zhang,Xiangguang Yang
It is essential to develop the catalyst for NH 3 -SCR with excellent performance at ultra-low temperature (≤150 °C), and resource recycling is another important part of environmental protection. Based on the principle of environmental friendliness, the LiMn 2 O 4 , one of the waste battery cathode materials, was successfully modified into a novel high-value catalyst for ultra-low temperature NH 3 -SCR through hydrogen ion exchange and two-dimensional vanadic oxide modification. The optimized LiMn 2 O 4 -0.5V-10H catalyst performed the best balance of NO x conversion and N 2 selectivity , with activity reaching 96 % at 150 °C and N 2 selectivity exceeding 70 % at ultra-low temperature. Due to the unique three-dimensional network structural characteristics of LiMn 2 O 4 spinel, hydrogen exchange could exchange Li + from the lattice and increase surface acidity; and a small amount of two-dimensional vanadic oxide loading could appropriately regulate redox ability and increase acidic sites. The in-situ DRIFTS results still showed that the L-H and E-R mechanisms coexisted during the reaction. Moreover, combining first-principles calculations and in-situ DRIFTS, the dual modification of H and V could enhance the adsorption of NH 3 on the surface of LiMn 2 O 4 but weaken the adsorption of NO, and promote the decomposition of nitrites while inhibit the formation of surface nitrate species, which was the core reason for the improvement of N 2 selectivity. The modification mode in this work was simple and inexpensive, which provided a new idea for the high-value utilization of waste batteries and the design of NO x purification catalyst at ultra-low temperature.
研究领域:
环境科学
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催化
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材料科学
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化学工程
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产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2021
·
IF 13.273
Wei Bi,Ling Zhang,Hao Jiang,Chunzhong Li,Yanjie Hu
The precise regulation of the nano-catalyst structure is a big challenge that limits the application of photocatalytic technology in CO 2 reduction. Herein, to improve the utilization of sunlight, the separation and transfer efficiency of photogenerated electron-hole pairs, and the surface catalytic reaction process, CuInS 2 /C/TiO 2 (CIS/C/T) hierarchical tandem heterostructure have been rationally designed. Multiple in-situ characterizations and DFT simulations show that CQDs not only act as a co-catalyst, but also act as a bridge between TiO 2 (T) and CuInS 2 (CIS), which further attribute to the efficient separation and enrichment of photogenerated electron-hole pairs while effectively avoiding the recombination. In consideration of the excellent broad-spectrum absorption, the CO 2 -to-CO photoreduction performance of the optimal CIS/C/T reaches up to 7.73 μmol g -1 h −1 , about 3.16 times enhancement of C/T. Combined with in-situ DRIFTs, the intrinsic structure–activity relationship is pointed out, and extended to other similar TiO 2 -based catalytic systems (In 2 S 3 /C/TiO 2 ). This work will provide a new universal strategy for the design and synthesis of high-performance nano-photocatalysts.
研究领域:
光催化
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材料科学
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环境科学
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化学工程
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产品关联
DOI
高影响因子
GREEN CHEMISTRY
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2023
·
IF 9.8
Tan Li,Jing Su,Linjia Yin,Xiangkun Zhang,Cong Wang,Xinbao Li,Jing Zhang,Kaige Wang
A Cu-based catalyst was developed for one-step solvent-free synthesis of aviation biofuel from biomass-derived ketones, including acetone, cyclopentanone, cyclohexanone, and 2-pentanone. Under the optimal working conditions, the conversion rate of acetone, cyclopentanone, cyclohexanone and 2-pentanone of 100% can be achieved by using Cu/Al2O3. 79.7 c% maximum carbon yield of liquid hydrocarbons with 89.5% selectivity of aviation biofuel was obtained under the conditions of 1.0 MPa H2, 280 °C, and 2 h−1 WHSV. The effects of the calcination temperature on the acidity and basicity of the catalyst, as well as the valence and dispersion of Cu species, were investigated. Based on DFT calculations and in situ DRIFTS results, the preferred adsorption of carbonyl groups and efficient dissociation of hydrogen on Cu+ increased the local concentration of H and feedstock on the catalyst surface, accelerating the rate-determining step that predominated on Cu0. The synergistic effect of Cu0 and Cu+ enhanced the formation of aviation biofuel.
研究领域:
催化
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化学工程
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可再生能源
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材料科学
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产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2020
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IF 7.489
Xuanxuan Jia,Hao Liu,Yu Zhang,Wei Chen,Qing Tong,Guangxia Piao,Chuanzhi Sun,Lin Dong
In recent years, Fe-based catalysts for the selective catalytic reduction of NO with NH 3 (NH 3 -SCR) have been attracting more attention. In this work, a novel Fe-Sb binary metal oxide catalyst was synthesized using the ethylene glycol assisted co-precipitation method and was characterized using a series of techniques. It was found that the catalyst with a molar ratio of 7:3 (Fe:Sb) displayed the best NH 3 -SCR activity with 100% conversion of NO x (nitrogen oxides) over a wide temperature window and with good resistance to H 2 O + SO 2 at 250 °C. The X-ray photoelectron spectroscopy (XPS) and in situ diffused reflectance infrared Fourier transform spectroscopy ( in situ DRIFTS) of NO x adsorption results suggested that strong electron interactions between Fe and Sb in Fe-O-Sb species existed and electrons of Sb could be transferred to Fe through the 2Fe 3+ + Sb 3+ ↔ 2Fe 2+ + Sb 5+ redox cycle. The introduction of Sb significantly improved the adsorption behaviour of NO x species on the Fe 0.7 Sb 0.3 O x surface, which benefitted the adsorption/transformation of NO x , thereby facilitating the NH 3 -SCR reaction. In addition, the Fe 0.7 Sb 0.3 O x catalyst demonstrated a good tolerance of H 2 O and SO 2 , since the decomposition of NH 4 HSO 4 on the catalyst surface was promoted by the introduction of Sb.
研究领域:
催化
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环境科学
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材料科学
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DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
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2023
·
IF 5.5
Jiacheng Xu,Tiantian Zhang,Yan Sun,Shiyu Fang,Zuliang Wu,Jiali Zhu,Lianxin Dai,Weihua Liu,Buhe Zhang,Junwei Zhang,Shuiliang Yao,Erhao Gao,Jing Li
MnO 2 is a promising catalyst due to its abundant metal valence and good redox ability. Different crystal phases of MnO 2 have different oxygen species, but the relationship between their catalytic activity and crystal structures is unclear. In this study, four MnO 2 catalysts with crystal structures ( α -, β -, γ -, and δ -MnO 2 ) were selected to unveil the roles of terminal-type (Mn O), superoxide-type Mn(-O-) 2 Mn, and bridge-type (Mn-O-Mn) oxygen species in CO oxidation . γ -MnO 2 has the best CO oxidation performance. Density functional theory calculation results show that Mn O on γ- MnO 2 can adsorb CO easier than other two types of oxygen species. Operando TPR-DRIFTS-MS results show that Mn O on the surface of γ- MnO 2 can react with CO to form terminal-type oxygen vacancies (M 2+ =□ 2– ) at low temperatures. Meanwhiles, Mn(-□-)(-O-)Mn and Mn-□-Mn can dissociate O 2 to form Mn O under certain conditions to promote CO oxidation. MnO 2 catalysts with more Mn O oxygen species are of great significance for CO oxidation at a low temperature.
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DOI
高影响因子
FUEL
·
2025
·
IF 7.5
Lina Dai,Qiang Li,Xianglan Dong,Enqi Zhang,Yufeng Hu,Xin Guo,Yanduo Liu
Photocatalysis exhibits great potential for applications in solving energy and environmental problems, and has received widespread attention. This article constructs a new type of Mn-Fe Prussian blue analogues S-scheme mechanism photocatalytic material. The material is composed of oxidized photocatalysts (Ag 2 MoO 4 ) and reduced photocatalysts (Mn-Fe PBAs). The composite photocatalyst constructed in this way shows advantages such as a wide spectral response range, high charge carrier separation efficiency, and strong oxidation–reduction ability, which can significantly enhance photocatalytic efficiency. By studying the construction method and CO 2 reduction performance of the photocatalyst, the structure-performance relationship can be clarified. The CO production rate is 43.3 μmol/g/h, and the selectivity can reach 94.9 %, which is far superior to the current mainstream photocatalytic system. The electron transfer kinetics and S-scheme charge separation mechanism between the Mn-Fe PBAs and Ag 2 MoO 4 interfaces are explained by steady-state surface photovoltage spectroscopy (SS-SPS) and near ambient pressure XPS (NAP-XPS). In-situ DRIFTS techniques are used to monitor the changes of transition intermediates, and combined with theoretical calculations, the activation mechanism of CO 2 by the Mn-Fe catalytic site is deeply revealed at the atomic level. This study provides new theoretical guidance and profound insights for the construction of Prussian blue analogues photocatalysts.
研究领域:
材料科学
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环境科学
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物理化学
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纳米技术
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催化
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能量转换
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2025
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IF 21.1
Shufan Yu,Zhao Sun,Zhiqiang Sun
Methanol steam reforming is a promising approach for real-time hydrogen production, while its practical application is hindered by catalyst deactivation and undesired CO byproduct formation. In this study, we propose a self-activation approach to anchoring a series of x CuO/YCrO 4 catalysts by employing methanol and steam as reductants. The self-activated 0.8CuO/YCrO 4 catalyst achieves a high hydrogen production rate of 22.3 μmol H 2 ·g −1 cat ·s −1 and demonstrates exceptional stability over 3000 min at 220°C. TEM-EDS, XPS, EPR, and XAS collectively reveal the promotion of generating Cu δ + /Y-O v -Cr interfacial sites and oxygen vacancies via self-activation, and in situ Raman spectroscopy confirms the structural stability of the Y-O v -Cr framework. In situ DRIFTS analysis further confirms that Cu δ + /Y-O v -Cr interfacial sites effectively anchor and promote the hydrogenation of bidentate formate intermediates, mitigating active site blockage by byproduct species and enhancing catalytic efficiency. This work provides new insights into the self-activation mechanism of Cu-based catalysts and offers a promising strategy for developing highly active and durable catalysts.
研究领域:
催化化学
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制氢技术
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材料科学
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表面化学
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化学工程
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纳米技术
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产品关联
DOI
高影响因子
JOURNAL OF POROUS MATERIALS
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2021
·Vol. 28
·期 6
·1737-1747
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IF 2.496
Jiang Haoxi,Zhao Yingying,Lin Jing,Chen Yifei,Wang Sheng
Highly dispersed palladium nanoparticles (NPs) supported on UiO-66 as catalyst for CO 2 methanation were prepared by supercritical fluid deposition (SFD). As a result, the most suitable Pd precursor salt and co-solvent are Na 2 PdCl 4 and ethanol/DMF, respectively. The best SFD process condition to deposit the Pd precursor on UiO-66 is 40 °C, 10 MPa and 2 h. Under the above condition, 4% Pd/UiO-66 exhibits the highest activity with 53% of CO 2 conversion and 95% of CH 4 selectivity while the turnover frequency (TOF) value is 3669.4 h −1 . The catalysts were characterized by XRD, BET, TEM, XPS, TGA, CO-DRIFTS and ICP-OES to investigate the structure–activity relationship. The 4% Pd/UiO-66 with the average size of 2.2 nm of Pd prepared in assistance of supercritical fluid behaved the similar activity as the 6%Pd/UiO-66 with average size of 9.7 nm of Pd prepared by sol–gel method. It is showed prospect of technique for reducing noble metal loading resulting from high dispersion effect.
研究领域:
催化
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材料科学
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化学工程
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环境科学
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产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
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2021
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IF 7.92
Yonglong Li,Senyou Yang,Honggen Peng,Wenming Liu,Yangyang Mi,Zheng Wang,Changjin Tang,Daishe Wu,Taicheng An
Manganese (Mn)-based mixed oxides are considered the most efficient catalysts for low-temperature ammonia selective catalytic reduction of nitrogen oxides (NO x ) (NH 3 -SCR of NO x ). Water resistance and sulfur tolerance, especially the SO 2 tolerance of Mn-based catalysts, are the main obstacles preventing their practical application. Therefore, in this study, a series of cobalt (Co)-doped MnFeO x ternary mixed oxides catalysts with a hierarchically ordered structure (Hierc-MnFe 1-δ Co δ O x , δ = 0.2, 0.4 and 0.6) were developed and applied for NH 3 -SCR of NO x at low temperature. Compared with Hierc-MnFeO x , Hierc-MnFe 1-δ Co δ O x catalyst exhibited enhanced low-temperature activity and a broadened temperature window (NO x conversion above 80% was between 90 and 343 °C over Hierc-MnFe 0.6 Co 0.4 O x ), as well as better H 2 O resistance and SO 2 tolerance. The enhanced low-temperature activity was attributed to a larger amount of active oxygen species, a higher proportion of Mn 4+ , Fe 3+ and Co 3+ content, and the improvement of surface acidity, which can facilitate the adsorption and activation of NO and NH 3 . Additionally, the Hierc-MnFe 0.6 Co 0.4 O x catalyst exhibited superior soot tolerance due to its special hierarchically ordered architecture. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) revealed that the Co-modified Hierc-MnFe 1-δ Co δ O x ternary oxide catalyst could efficiently protect nitrate species on Hierc-MnFe 0.6 Co 0.4 O x from the poisoning effect of SO 2 , thereby boosting its SO 2 tolerance. This study provides a good candidate for low-temperature de NO x application with enhanced SO 2 and soot tolerance.
研究领域:
催化
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环境科学
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材料科学
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化学工程
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产品关联
DOI
高影响因子
ACS Earth and Space Chemistry
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2021
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IF 3.475
Xiaozhong Fang,Yangyang Liu,Kejian Li,Tao Wang,Yue Deng,Yiqing Feng,Yang Yang,Hanyun Cheng,Jianmin Chen,Liwu Zhang
The carbonate radical (CO3•–) has been proved to be of great significance in the water environment. However, a few studies concerned with its contribution to atmospheric heterogeneous chemistry. Here, we report the pathway for the first time for CO3•– generation by interfacial photogenerated hole/hydroxyl radical (•OH) transfer between the photoactive component and (bi)carbonate (CO32–/HCO3–) of mineral dust under atmospherically relevant actinic irradiation. By combining laboratory simulation, nanosecond transient absorption spectroscopy (NTAS), and field observation, we demonstrate that (bi)carbonate in the atmosphere not only has a pH buffering effect in the uptake of NO2 but more importantly directly participates in the photochemical reactions by generating CO3•– under irradiation. CO3•– can play an important role by facilitating nitrite transformation to nitrate, especially under a lower light intensity (15 mW/cm2) and a higher humidity (60% RH). Diffuse reflectance infrared Fourier transform spectrometry (DRIFTS) was used to detect the surface species generated on simulated mineral dust. Under irradiation, the time-dependent reactive uptake coefficient for the first-order reaction of NO2 uptake on simulated mineral dust was found to be 2.817 × 10–8 × e–t/6559. These results highlight the important role of CO3•– in atmospheric photochemistry, which could act as a reactive radical and influence secondary aerosol formation.
研究领域:
大气化学
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环境科学
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光化学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）