Catalysts
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2022
·Vol. 12
·期 6
·606
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IF 4.501
Yadong Wang,Qing Hu,Ximing Wang,Yanpeng Huang,Yuanhao Wang,Fenghuan Wang
Methane reforming with carbon dioxide (DRM) is one promising way to achieve carbon neutrality and convert methane to syngas for high-value chemical production. Catalyst development with better performance is the key to its potential large-scale industrial application due to its deactivation caused by carbon deposition and metal sintering. Hence, a Ni/CeO2catalyst (Ni/CeO2-M) with higher CO2conversion and better stability is prepared, supported on CeO2precipitated via a novel microimpinging stream reactor. A series of ex-situ or in-situ characterizations, such as CO titration measurements, two-step transient surface reaction (two-step TSR), CO2and CH4temperature-programmed surface reaction (CO2-TPSR and CH4-TPSR), X-ray absorption fine structure (XAFS), and in-situ Raman spectroscopy study, were used to investigate its structure and mechanism. In contrast to Ni supported on commercial CeO2(Ni/CeO2-C), the Ni/CeO2-M catalyst with stronger lattice oxygen mobility and higher oxygen storage capacity enhances its CO2activation ability and carbon deposition. The Ni particle size of the Ni/CeO2-M catalyst decreased, and a higher oxidation state was obtained due to the strong metal–support interaction. Besides the reaction performance improvement of the Ni/CeO2-M catalyst, the novel microimpinging stream reactor could achieve catalyst continuous production with a high preparation efficiency. This work provides a novel method for the high-performance catalyst preparation for DRM reaction and its mechanism study gives a deep insight into high-performance catalyst development via bottom-up study.Keywords:dry reforming of methane;oxygen vacancy;Ni/CeO2catalyst
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2020
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IF 4.939
Yinghui Sun,Guojie Zhang,Haizhu Cheng,Jun Liu,Guoqiang Li
The mechanism and kinetic features of dry reforming with methane (DRM) over Ca promoted 1Co–1Ce/AC-N catalyst was investigated. The mechanistic pathway studies have conducted by FTIR and XPS analysis, structure-activity correlations demonstrated the CH 4 and CO 2 could adsorb on catalyst active sites and generate intermediate CH x , OH and CH x O, continue to generate CO and H 2 and then desorbed from active sites. Moreover, CH 4 could also oxidized by Ce 4+ and CO 2 reduced by Ce 3+ , the same content of Ce 4+ and Ce 3+ on promoted catalyst greatly improved the reaction rate. The kinetic of dry reforming with methane was examined for temperature between 650 and 850 at 800 °C. The research was carried out by changing the CH 4 /CO 2 ratios between 0.3 and 3.0. The obtained experiment data were fitted by three typical kinetic models (Power Law, Eley-Rideal and Langmuir-Hinshelwood), the fitting results demonstrated that the best prediction of reforming rates can provided by Langmuir-Hinshelwood model for the reaction temperatures between 650 and 800 °C. Moreover, activation energies of methane and carbon dioxide consumption were −117 and −47 kJ/mol, indicating that much higher energy barrier is needed for methane activation compared to carbon dioxide.
研究领域:
化学工程
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
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2025
·
IF 7.2
Jiming Wang,Min Ji,Jiaqi Lv,Min Wang
Photo-thermo-chemical dry reforming of methane (PTC-DRM) produces syngas has been a promising strategy to utilize abundant solar energy and alleviate greenhouse effect. Herein, we report an efficient PTC-DRM process on Ni-based catalyst with Zn doping and investigate the effect of Zn on the catalytic performance of catalysts. Zn promoted the generation of active sites on the surface of Ni-Al 2 O 3 , suppressed the accumulation of coke during the reaction process and enhanced the photocatalytic activity of the catalyst. Ni-ZnO-Al 2 O 3 catalyst exhibited highest thermal catalytic performance and the conversion of CH 4 and CO 2 are 50.2% and 58.1% at 650 ℃, respectively. All catalysts exhibited higher reaction rates of CH 4 and CO 2 and higher hydrogen selectivity under light conditions. Light also significantly enhanced the carbon deposition resistance and stability of the catalyst. And possible reaction mechanism of the Ni-ZnO-Al 2 O 3 was proposed during PTC-DRM process.
研究领域:
化学工程
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
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2019
·
IF 4.914
Jingqing Tian,Haocheng Li,Xin Zeng,Zichun Wang,Jun Huang,Chen Zhao
ABSTRACT Development of dry reforming of methane and carbon dioxide is an effective route to convert in-dustrial waste gases such as coke-oven gas and coal-to-oil gas into platform syngas. However, this process encounters severe problems of metal particle sintering and coke formation at high tem-peratures. In this work, we developed a new synthetic method for preparing confined Ni/MCM-41 catalysts, which impede the sintering of metal nanoparticles (NPs) and coke deposition at high temperatures, enabling them to be successfully applied to methane dry reforming . The method results in high activity and stability of the catalyst at 700 °C for 200 h. The Ni precursor is immersed in ethanol and impregnated into MCM-41 by the peculiar capillary action of hexagonal straight mesopores . By this method, 10 wt% Ni NPs (d = 2 nm) is equably confined to the mesoporous channels with strong metal-support interactions, as confirmed by HRTEM, TEM mapping, H2-TPR, and XRD measurements. Such a confined structure has a significant effect on the inhibition of metal NP agglomeration and carbon deposition during methane dry reforming, as evidenced by TEM, Raman, TGA, and TPO measurements of used Ni/MCM-41 catalysts. In contrast, unconfined Ni/MCM-41 catalysts, with Ni NPs located on the pore exteriors, are rapidly deactivated after 12 h due to the blocked contact between the active metal centers and the gas feedstock. Additionally, a fast increase in the Ni NP size and the formation of substantial carbon nanotubes on the unconfined catalyst surface are seen. This work offers a facile approach for the synthesis of anti-sintering, car-bon-resistant confined Ni catalysts that can operate at high temperatures
研究领域:
化学工程
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
ENERGY
·
2024
·
IF 9
Xu Ma,Wei-Wei Yang,Ju-Wen Su,Lan-Xin Liang,Wang-Xin Yang,Ya-Ling He
This study employed a novel one-pot method to encapsulate cerium species on the Ni–Al heterogeneous interface, aiming to achieve the capture and efficient utilization of greenhouse gas (CO 2 ). Characterization results revealed that nickel species experienced various forms such as oxides and carbon-nickel compounds at the heterogeneous interface. The presence of cerium groups within the catalytic system induces the precipitation of nickel grain monomers on the support, decomposing the CH 4 –CO 2 reforming process into a multistep reaction that breaks the thermodynamic barrier and kinetic limitation of the multicarbon coupling phenomenon, and greatly reduces the energy consumption of the reaction. Results showed that at a temperature of 800 °C and a Ni/Ce molar ratio of 0.2 in the catalyst, the activity was stable and the CO 2 conversion reached 81.69 %, which was a 15.33 % enhancement compared to the base catalyst. Additionally, the mutual conversion of Ce 3+ /Ce 4+ promoted the internal electron interaction process in the catalytic system, increasing the number of oxygen vacancies and reducing acidic sites, which facilitated reactant activation and carbon elimination. This work provides insights for the efficient utilization of greenhouse gases.
研究领域:
催化化学
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环境科学
✓ 已验证
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2023
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IF 4.2
Zongpeng Zou,Tao Zhang,Li Lv,Wenxiang Tang,Guoquan Zhang,Raju Kumar Gupta,Yan Wang,Shengwei Tang
Dry reforming of methane (DRM) presents a sustainable approach to convert greenhouse gases CO2 and CH4 into syngas. However, the industrialization of DRM is hindered by the short catalyst lifespan due to carbon deposition. Carbon deposition on Ni-catalysts is attributed to Ni step edges, which serve as carbon nucleation centers. We propose an innovative strategy to prevent carbon nucleation by modulating Ni size to eliminate Ni step edges. Ni was loaded on MCM-41, SBA-15, and DFNS (dendritic fibrous nanosilica) to prepare three distinct Ni catalysts. By altering the precursor concentration using the proposed microemulsion antisolvent coprecipitation method, we successfully adjusted the Ni size on DFNS. Ni particles with a diameter of ∼5 nm were obtained on DFNS, exhibiting excellent Ni dispersion and a physical spacing effect due to the specific preparation method and porous structure. Carbon deposition rates on Ni/MCM-41 and Ni/SBA-15 were 30.23 mgc·gcat·–1·h–1 and 16.33 mgc·gcat·–1·h–1, respectively. Remarkably, the carbon deposition rate on Ni/DFNS was only 0.15 mgc·gcat·–1·h–1. The gasification rate of deposited C to CO on the 5 nm Ni particles loaded on Ni/DFNS was five times that of the polyhedral Ni particles of Ni/MCM-41. This was attributed to the elimination of Ni step edges, which weakened C adsorption strength and enhanced the reaction of deposited C with O* to form CO. Our proposed catalyst preparation strategy is based on designing the catalyst microstructure to eliminate carbon nucleation sites. This research provides guidance for designing or preparing Ni-based catalysts for DRM with reduced carbon deposition.
研究领域:
催化化学
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
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2024
·Vol. 14
·期 52
·39061-39068
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IF 3.9
Han Xiao,Jiaming Dong,Yimin Zhang,Xiaohua Cao,Yanhong Li,Dedong He,Yongming Luo,Pingyan Wang,Hao Wang
The presence of abundant hydroxyl groups on the surface of Al2O3 can promote the dispersion of Ni species but produce an inactive NiAl2O4 phase at high temperatures. Moreover, the catalysts prepared by the conventional incipient wetness impregnation method lack the sites for the activation of CO2, which leads to coke deposition and thus affects the catalyst activity. The above restricts the utilization of Ni in conventional Ni/Al2O3 catalysts. In this paper, Al2O3 support was pre-treated by acetic acid to selectively remove hydroxyl groups without affecting the coordination environment of Al. Results revealed that the Al2O3 support after hydroxyl removal not only showed moderate metal–support interaction but also produced more sites for the adsorption and activation of the reactant, which significantly improves the utilization of nickel species and the stability of the catalyst. The conversion of CH4 and CO2 at 700 °C was as high as 88% and 90%, respectively, and has an excellent stability of 50 h. This study provides a feasible strategy for the design of highly active methane dry-reforming catalysts.
研究领域:
催化化学
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能源材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2019
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IF 4.084
Yinghui Sun,Guojie Zhang,Jiwei Liu,Ying Xu,Yongkang Lv
The dry reforming of methane (DRM) over Ni-MSC catalysts promoted by different Ce/Ca ratios was compared. The different Ce/Ca ratios proportions were introduced by coprecipitation . The catalysts with different content of promoter were characterized by N 2 adsorption, XRD , H 2 -TPR and TEM. XRD and TEM results demonstrated that Ni–4Ce1Ca-MSC catalyst modified with high Ce/Ca had the best dispersibility and the smallest Ni particle size, resulting in more surface active sites. The synergy between Ce and Ca made a great contribution to prohibiting the generation of carbon deposits and the sintering of active metal during DRM procession. In contrast, catalysts modified only with Ca or Ce exhibited poor catalytic performance, resulting in significant deposition of carbon on the surface of the Ni–5Ca-MSC catalyst. In addition, the high Ce concentration greatly increases the oxygen storage capacity, which helps to form oxygen vacancies by mutual conversion of Ce 4+ /Ce 3+ and Ni 2+ /Ni 0 .
研究领域:
化学工程
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催化材料
✓ 已验证
DOI
高影响因子
JOURNAL OF POWER SOURCES
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2014
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IF 5.211
Xiaogang Zheng,Shiyu Tan,Lichun Dong,Shaobo Li,Hongmei Chen
Spinel nickel ferrite nanoparticles (NiFe 2 O 4 NPs) embedded in silica (NiFe 2 O 4 #SiO 2 ) was prepared to enhance the reaction performance of the dry reforming of methane in a coaxial dielectric barrier discharge reactor. NiFe 2 O 4 NPs of around 10 nm were effectively embedded in porous SiO 2 NPs (∼100 nm in diameter). Compared to the supported Ni-based catalysts (Ni/γ-Al 2 O 3 , Ni–Fe/γ-Al 2 O 3 , Ni–Fe/SiO 2 , and NiFe 2 O 4 ), the NiFe 2 O 4 #SiO 2 catalyst placed at the discharge zone exhibited excellent catalytic performance and high resistance to carbon formation during dry reforming under ambient conditions without the involvement of extra heat. The synergetic effect between the non-thermal plasma and the NiFe 2 O 4 #SiO 2 catalyst favored the conversion of CH 4 and CO 2 into syngas . The results indicated that the special structure of the as-synthesized NiFe 2 O 4 #SiO 2 catalyst was capable of restraining the aggregation of Ni–Fe alloy and suppressing the carbon formation in the reforming process.
研究领域:
化学工程
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材料科学
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能源技术
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2024
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IF 20.2
Quanqi Zhang,Zhonghua Jiang,Yimin Zhang,Xinyu Xu,Ye Yang,Yucai Qin,Lijuan Song,Yi Mei,Yun Zu
Carbon deposition, an inevitable product operated at high temperatures, is a headache-inducing obstacle to enhance catalyst stability for methane dry reforming (MDR). Herein, we have ingeniously designed sintering-resistant Ni@S-1 nanosheet zeolites to purposefully induce common linear and non-linear deactivation of catalysts during MDR reaction for deciphering carbon footprint. Multiple evidences unveiled that "transient carbon", composed of multi-phenyl-rings via rapidly rearrangement of CH x * fragments, was a crucial vane for catalyst deactivation. Accordingly, we proposed a dynamic equilibrium theory for the generation and elimination of "transient carbon". Achieving this balance was dependent of the matching degree between Ni 0 nanoparticles and NiO x (OH) y , which both separately originated from the evolutions of 1:1 and 2:1 Ni phyllosilicates controlled by nanosheet thickness. Delightfully, synthetic Ni@S-1–60nm catalyst with an optimal ratio of Ni 0 /NiO x (OH) y contributed higher MDR activity and durability. These findings derived a new MDR reaction pathway and afforded value-filled information for developing high carbon-resistant MDR catalysts.
研究领域:
催化化学
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
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2024
·
IF 11.3
Jie Fan,Wen-Cui Li,Lei He,Bowen He,Fan Tang,Zhankai Liu,Dongqi Wang,Xi Liu,Liwei Chen,An-Hui Lu
Ni-based catalysts are the most promising candidates for methane dry reforming (MDR) reaction but still suffer from deactivation caused by coke-deposition. Herein, we reported a coke resistance MDR catalyst consisting of cationic Ni clusters (Niδ+, 0 < δ < 2) stabilized over oxygen-functionalized boron nitride. A simple method was developed for the fabrication of highly dispersed cationic Ni clusters on boron nitride. The local coordination modes between nickel and boron nitride determine the formation of cationic Ni clusters. We provided detailed spectroscopy and microscopy characterizations to reveal the structure features of these cationic Ni clusters. The average particle size of these clusters is ∼1.7 nm. There are abundant Nixδ+–O–B interfaces on the cationic Ni clusters, which serve as catalytically active sites. Compared to conventional metallic Ni nanoparticles, the cationic Ni clusters exhibited comparable apparent catalytic activity and reduced carbon deposition, particularly operated at 600 °C where unavoidable coke formation from CH4 cracking and the Boudouard reaction usually tends to occur thermodynamically and kinetically. Based on theoretical and experimental evidence, a dynamic synergistic conversion mechanism for CH4 and CO2 on the Nixδ+–O–B interface has been revealed. The oxygen within the Nixδ+–O–B interface could rapidly convert CHx*(x = 1–3) intermediates forming H2 and CO to avoid carbon deposition. CO2 is efficiently activated at boron sites of the Niδ+–O–B interface to regenerate active oxygen species, thereby boosting the conversion of CH4. These insights may shine light on the development of intrinsic coke-free Ni-based catalysts for methane dry reforming in the near future.
研究领域:
材料科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMISTRY OF MATERIALS
·
2022
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IF 10.508
Xiaojuan Cao,Le Ke,Kai Zhao,Xiaoyu Yan,Xiaoyu Wu,Ning Yan
The exsolution of metallic nanoparticles (NPs) from perovskite oxides is a promising strategy for synthesizing supported catalysts. The associated segregation of A-site cations on the surface is challenging to investigate experimentally and is often detrimental to the catalytic performance. In this work, we found that during the in situ exsolution of Ni-Co bimetallic nanoparticles from Pr0.45Ba0.45Mn1–x(Co1/3 Ni2/3)xO3±δ, A-site cation enrichment occurred on the surface when x is 0.1; yet, the perovskite surface decomposed when x reached 0.2, forming a thin layer comprising various nanocrystalline oxides, which partially blocked the active sites of the exsolved Ni-Co particles. A hydration and carbonation reaction facilitated the conversion of nanocrystalline BaO species into large and highly crystallized BaCO3 particles. This enabled the exposure of more Ni-Co active sites and offered a chance to quantify that the decomposed surface layer accounts for ∼7.2 wt % of the total perovskite. Because of this unique feature, the surface-decomposed catalyst showed higher activity in the dry methane reforming reaction with better stability. Importantly, the regeneration feature was not hampered as the complete exsolution-dissolution recyclability of the catalyst remained.
研究领域:
材料科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
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