RSC Advances
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2023
·Vol. 13
·期 50
·35562-35568
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IF 3.9
Fenglong Wu,Jin Song
Herein, we synthesized a hydrophilic support formed from amorphous Cr2O3 and KIT-6 containing P123 using a simple solvent-free thermal method for Co species. The obtained catalyst (denoted as Co/Cr2O3-F-X) exhibits high activity for hydrogen production from ammonia borane (NH3BH3). The optimal Co/Cr2O3-F-0.5 exhibits the highest catalytic performance with the turnover frequency (TOF) value of 111.1 min−1. Advanced characterizations suggest the high catalytic performance is attributed to the synergistic effect of the strong interaction between amorphous Cr2O3 and KIT-6 containing P123 and improved wettability of the catalyst.
研究领域:
催化化学
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材料科学
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DOI
PubMed
高影响因子
CATALYSIS TODAY
·
2019
·
IF 4.888
Le Yang,Rui Ma,Hui Zeng,Zebao Rui,Yongdan Li
This work provides a facile strategy to prepare core-shell structured catalysts with MOF-templated metal active species embedded carbon matrix core and a functional metal oxide shell in a controllable way. The procedure features with the facile introduction of functional shell metal oxide and delivery of MOF morphology. Co(II/Ⅲ)@ZnO hexagonal prisms are fabricated with this procedure and ZIF-67 as the template. When being used in the selective oxidation of vanillyl alcohol to produce vanillin, ZnO shell plays an important role by faciliating redox of Co 3+ /Co 2+ for promoting vanillyl alcohol oxidation to vanillin and protecting the Co species against leaching into the reaction system. Co(II/Ⅲ)@ZnO exhibits a conversion of 20% with a selectivity of 80% after a 2 h reaction and shows stability after 3 catalytic cycles.
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
FUEL
·
2024
·
IF 6.7
Kaiwei Wang,Fumin Wang,Yi Zhai,Xubin Zhang,Mingshuai Sun,Jinjin Zhang,Xiaolu Fan,Changhao Bing
The metal species embedded in specific positions within the zeolite framework and their unique microenvironment exhibit fascinating effects on catalytic performance. Herein, we incorporated tetrahedrally coordinated Co 2+ into the framework of hollow silicate-1 zeolite and investigated the influence of halogen anions (Cl - , Br - and F - ) in the synthesized gel on the distribution of cobalt species in the channels. The addition of an appropriate amount of inorganic ammonium salts and seeds was found to be a necessary condition for cobalt incorporated into the framework. Notably, the Cl - anions present in the synthesis gel can induce more cobalt species located at the intersection cavity of silicate-1 (β-type). Comprehensive characterization results indicate that the tetrahedrally coordinated Co 2+ in the intersecting cavities of hollow zeolite appears to exhibit more efficient styrene epoxidation performance. This work presents a simple and cost-effective method to synthesize hollow cobalt-based zeolite with adjustable metal distribution in channels. By regulating the spatial distribution of cobalt species with halogens, the CS-0.1–0.5-Cl catalyst enhanced activity and selectivity in the epoxidation reaction of styrene to styrene oxide. Specifically, at a temperature of 80 °C after a reaction time of 6 h, the catalyst demonstrated a styrene oxide yield of 42.47 % and a excellent styrene oxide selectivity of 82.29 %.
研究领域:
催化化学
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材料科学
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产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2024
·
IF 9.4
Zidan Chen,Guanghao Meng,Zenghui Han,Hongjiang Li,Shaoming Chi,Guangzhi Hu,Xue Zhao
The development of highly catalytic activity, low-cost and environmentally friendly catalysts is crucial for the use of advanced oxidation processes (AOPs) to treat organic pollutants. In this study, to reduce costs, enhance catalytic activity and avoid secondary pollution form metal ions, pomelo peel was used as raw material, combined with surface crystallization, carbon layer protection and heat treatment technology to effectively construct AOPs catalyst that can efficiently activate peroxymonosulfate (PMS) to degrade harmful organic pollutants. Under the optimal conditions, the Co/BC-PMS system can degrade about 100 % of tetracycline (TC, a spectral antibiotic) within 5 min, and the degradation rate of TC can still reach 100 % even if Co/BC (cobalt anchored on biochar) was reused for 6 times. The Co/BC-PMS system can resist complex environmental conditions, including acidic solution, alkaline solution, coexisting ions, different water quality, and is universal for the degradation of most organic pollutants. The integrated purification column with Co/BC as the core realizes the continuous and complete degradation of organic pollutants and has the ability of practical application. Radical capture and monitoring combined with density-functional-theory calculations confirmed that the Co(111) and amorphous CoO sites in Co/BC are the key to driving PMS to degrade organic pollutants, Co/BC can efficiently adsorb PMS and promote the dissociation of PMS into highly active OH, SO 4 − and 1 O 2 , and these reactive oxygen species jointly promote the degradation of organic pollutants. This study provides experimental support and theoretical insights for the design of efficient AOPs catalysts, and plays an important role in promoting the development of AOPs.
研究领域:
环境科学
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催化化学
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产品关联
DOI
PubMed
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
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2022
·
IF 5.876
Zhonghui Zheng,Jichao Wang,Meng Liu,Bibimaryam Mousavi,Ning Liu,Somboon Chaemchuen
A facile and green method is developed to synthesize cobalt species embedded in a nitrogen-doped carbon matrix (P–Co@NCs). The materials are synthesized using hard template precursors via single-step in-situ thermal treatment under free solvent conditions. The optimal P–Co@NC composite prepared through rational synthesis and synergic composition shows an efficient electrocatalytic performance for oxygen evolution reduction (OER). The P–Co@NC exhibits the OER overpotential of 350 mv at 10 mA cm −2 and low Tafel 73 mv·dec −1 in 0.1 M KOH electrolyte. The advantage of catalyst is the dispersion of Co species, which are in close interaction with nitrogen-doped carbon matrix. The Co-Nx plays a dominating role among Co species in P–Co@NC and is well protected by the nitrogen-doped carbon matrix layer. That resulted in efficient electron transport on CNTs (high conductivity) that improves the OER performance of P–Co@NC compared to the reference catalysts (IrO 2 and B–Co@NC). The P–Co@NC also showed excellent cycling performance from long-term chronoamperometry testing. Interestingly, the P–Co@NC catalyst could be synthesized straightforward via a short solvent-free single-step process that introduced it as a green and environmental friendly method, which can be potential to develop catalyst based on metal embedded N-doped carbon.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
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2022
·
IF 14.224
Zelin Wu,Zhaokun Xiong,Rui Liu,Chuanshu He,Yang Liu,Zhicheng Pan,Gang Yao,Bo Lai
Metal leaching and catalytic stability are the key issues in Fenton-like reaction. Herein, a hollow yolk-shell nanoreactor (HYSCN) with shell confined Co species was fabricated for peroxymonosulfate (PMS) activation to degrade carbamazepine (CBZ). The uniform Co nanoparticles were completely anchored in a hollow void, further confined by a porous N-doped carbon shell. The unique construction significantly reduces Co species leaching in PMS activation and enhances catalytic stability. Co leaching came from HYSCN dropped by almost fourfold compared to CN-8 without shell confined (0.403 mg/L to 0.120 mg/L). The catalytic stability is also greatly improved, confirming the dominant role of heterogeneous catalysis in the HYSCN/PMS system. HYSCN exhibits excellent catalytic performance compared to a solid structure (SCSCN), demonstrating the significance of hollow structures. Mechanism study found that HO • , SO 4 • – and 1 O 2 induced in HYSCN/PMS system and the relative contributions were distinguished and quantified by stoichiometric methods. The UPLC-Q-TOF-MS/MS was used to identify the CBZ degraded intermediate products and the possible degradation pathway was proposed. This study will provide theoretical guidance for reducing metal leaching and improving catalytic stability in the PMS activation.
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
MICROPOROUS AND MESOPOROUS MATERIALS
·
2023
·
IF 5.2
Dingmei Han,Meiyu Liu,Chengming Huang,Xinyu Sun,Linjie Guan,Binbin He,Yi Mei,Yun Zu
Co-based catalysts are promising alternatives to replace expensive Pt- and toxic Cr-based catalysts for propane dehydrogenation (PDH), while the catalytic stability and propylene selectivity have been subjected to the diversity of Co speciations. Given the situation, uniformly stable hydroxylated Co 2+ silicate sites (depicted as {OH–Si–(OH)–Co–O–Si-(OH) 3 }) are successfully embedded into the silicalite-1 zeolite framework located in the straight and intersection channels (Co@S-1) with the assistance of Co precursors and geminal silanols via a facile hydrothermal synthesis , as revealed by detail characterizations. Under comparable conditions, a superior catalytic PDH performance with attractive propylene formation rate of 14.6 mmol·g cat −1 ·h −1 , propylene selectivity higher than 93% and very low deactivation rate of 0.0206 h −1 after 7 h is achieved over the Co@S-1(EDA) catalyst. Furthermore, the catalytic performance can be restored to the same as that of the fresh catalyst after 3 successive regenerations. In situ FTIR spectra analysis further reveals the dynamic changes in the characteristic absorption bands associated with the hydroxylated Co 2+ silicate sites and the intermediate product (2-propyl) during the PDH reaction and a reaction mechanism is proposed accordingly. This work provides a new insight for designing high-efficiency nonprecious metal PDH catalysts.
研究领域:
化学工程
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
ANALYTICAL CHEMISTRY
·
2024
·
IF 6.7
Runkun Zhang,Yanhui Zhong,Yufei Hu,Yi Chen,Ling Xia,Gongke Li
Accurate discrimination of metal species is a significant analytical challenge. Herein, we propose a novel methodology based on liquid-phase cyclic chemiluminescence (CCL) for the identification of cobalt speciation. The CCL multistage signals (In) of the luminol–H2O2 reaction catalyzed by different cobalt species have different decay coefficients k. Thereby, we can facilely identify various cobalt species according to the distinguishable k values, including the complicated and structurally similar cobalt complexes, such as analogues of [Co(NH3)5X]n+ (X = Cl–, H2O, and NH3), Co(II) porphyrins, and bis(2,4-pentanedione) cobalt(II) derivatives. Especially, the number of substituent atoms also influences the k value greatly, which allows excellent discrimination between complexes that only have a subtle difference in the substituent group. In addition, linear discriminant analysis based on In provides a complementary solution to improve the differentiating ability. We performed density functional theory calculations to investigate the interaction mode of H2O2 over cobalt species. A close negative correlation between the adsorption energy and the k value is observed. Moreover, the calculation of energy evolutions of H2O2 decomposition into a double hydroxide radical shows that a high level of consistency exists between the activation energy barrier and the k value. The results further demonstrate that the decay coefficient of the CCL multistage signal is associated with the catalytic reactivity of the cobalt species. Our work not only broadens the application of chemiluminescence but also provides a complementary technology for speciation analysis.
研究领域:
分析化学
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催化化学
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理论化学
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DOI
PubMed
高影响因子
ACS Catalysis
·
2022
·
IF 13.7
Wei Qu,Zhuoyun Tang,Hailin Wen,Manhui Luo,Tao Zhong,Qiyu Lian,Lingling Hu,Shuanghong Tian,Chun He,Dong Shu
High-performance and robust catalysts act as core drivers for catalytic ozonation to eliminate gaseous sulfur-containing volatile organic compounds (VOCs). Herein, nitrogen-doped carbon nanotubes embedded with Co species (Co@NCNT) are synthesized by thermolysis of a ZIF-67/melamine mixture. The carbon-confinement effects in Co@NCNT not only improve the stability of Co species but also regulate the electronic structure of Co─C bonds, consequently synergistically improving the catalytic ozonation performance. The experimental results indicate that the Co@NCNT catalyst could still remove ∼86% of odorous methyl mercaptan (CH3SH) after running for 60 h at 25 °C under an initial concentration of 50 ppm CH3SH and 40 ppm ozone, relative humidity of 60%, and space velocity of 600,000 mL h–1 g–1, outdistancing reported values under comparable reaction conditions. Detailed characterization and theoretical simulations reveal that the electronic metal–support interaction of Co─C bonds in Co@NCNT significantly adjusts the electronic structure of Co species, thereby promoting ozone-specific adsorption/activation to convert the surface atomic oxygen (*Oad) and ·OH/1O2/·O2–. Also, the electrons obtained from CH3SH in the electron-poor center transferred through the C─Co bond bridge to maintain the redox cycle of ≡Co0/2+ → ≡Co3+ → ≡Co0/2+ and realize the efficient and stable removal of CH3SH into CO2/SO42–/H2O. This work demonstrates that MOF-derived materials with tunable electronic structures achieve the stable removal efficiency for gaseous sulfur-containing VOCs via electron transfer trade-offs and provide potential candidate catalysts for the application of air purification.
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 Water Process Engineering
·
2025
·
IF 6.7
Ya Zeng,Lingfeng Qin,Sijie Tian,Caicheng Long,Taiping Qing,Peng Zhang,Bo Feng
Cobalt-based multiphase catalysts can effectively activate peroxymonosulfate (PMS) and degrade organic pollutants. However, their practical application faces critical challenges, including insufficient exposure of active sites, slow reaction kinetics, and cobalt ion leaching, which collectively reduce catalytic efficiency and sustainability. Although there have been attempts to improve the catalytic efficiency through structural modifications such as core-shell structure or porous design, these strategies are still difficult to optimize the active site exposure and cobalt ion stability simultaneously. To overcome these limitations, here we propose a novel triple-shell yolk@shell architecture (3YS-Co@NC) constructed via a stepwise strategy involving crystal extension growth, selective etching, and calcination. The optimized nanoreactor degraded 100 % of bisphenol S (BPS) within 12 min with a rate constant (0.342 min −1 ) 9.5-, 2.34-, and 1.49-fold higher than solid nanoparticles (Co@NC), single-shell (1YS-Co@NC), and double-shell (2YS-Co@NC) counterparts, respectively. Notably, the TOC removal rate of 3YS-Co@NC reached 71 %, surpassing those of 1YS-Co@NC (53 %), 2YS-Co@NC (65 %), and Co@NC (21 %). The enhanced performance results from (i) the yolk@shell structure providing nanoreaction cavities and abundant active sites, and (ii) the robust Co 0 /Co 2+ /Co 3+ redox cycling. Quenching experiments and EPR analysis revealed that SO 4 •- and •OH dominated PMS activation, while O 2 •- played an auxiliary role. In contrast, 1 O 2 exhibited negligible contribution. LC/MS analysis identified key degradation intermediates, and the ECOSAR model predicted reduced biotoxicity of these products. This study not only promotes the development of advanced oxidation processes, but also provides a new insight into the design of cobalt-based catalysts.
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
CHINESE JOURNAL OF CATALYSIS
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2025
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IF 17.7
Liang Zhang,Jialiang Rui,Yiqian Li,Zhizhi Yang,Shiro Kubuki,Junhu Wang,Bofan Zhang
Precise manipulation of the catalytic spin configuration and delineation of the relationship between spin related properties and oxidation pathways remain significant challenges in Fenton-like processes. Herein, encapsulated cobalt nanoparticles and cobalt-nitrogen-doped carbon moieties, endowed with confinement effects and variations in shell curvature were constructed via straightforward pyrolysis strategies, inducing alterations in magnetic anisotropy, electronic energy levels and spin polarization. The enhanced spin polarization at cobalt sites leads to a reduction in crystal field splitting energy and an increase in electronic spin density. This phenomenon facilitated electron transfer from cobalt orbitals to p z orbitals of oxygen species within peroxymonosulfate molecules, thereby promoting the formation of high-valent cobalt species. The encapsulation effectively stabilized cobalt nanoparticles, mitigating their dissolution or deactivation during reactions, which in turn enhances stability and durability in continuous flow processes. The high-valent cobalt species within the shell exhibit increased exposure and generate localized high concentrations, thereby intensifying interactions with migrating pollutants and enabling efficient and selective oxidation of emerging compounds with elevated redox potentials. This work underscores the profound impact of confined encapsulation curvature and spin polarization characteristics of metal sites on catalytic oxidation pathways and performance, opening novel avenues for spin engineering in practical environmental catalysis.
研究领域:
环境催化
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材料化学
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物理化学
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纳米催化
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污染控制化学
✓ 已验证
产品关联
DOI
高影响因子
Catalysis Science & Technology
·
2025
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IF 4.2
Fuwei Gan,Wen Liu,Xinbao Zhang,Maochen Qian,Shaoguo Li,Yuzhong Wang,Junjie Li,Xiangxue Zhu,Xiujie Li
Primary amines, exemplified by n-butylamine, serve as critical intermediates in the synthesis of pharmaceuticals and agrochemicals. Amination of n-butanol with ammonia over supported cobalt catalysts represents a promising synthetic route. To enhance the catalytic performance of Co-based amination catalysts, we reported an acid-treated strategy that allows for precise regulation of cobalt speciation. Among the evaluated supports, silicalite-1 demonstrated superior amination performance, attributed to its unique ability to enhance cobalt dispersion and suppress acid-induced side reactions. Through acid treatment, oversized Co3O4 nanoparticles are selectively removed, thereby preserving highly dispersed cobalt species. Under rigorous reaction conditions (WHSV = 2.5 h-1), the acid-treated catalyst achieved 90% selectivity toward n-butylamine, accompanied by improved stability compared to untreated counterparts. Mechanistic investigations revealed that well-dispersed metallic Co0 nanoparticles promoted selective C-N bond formation via efficient coupling, whereas larger cobalt domains facilitated dehydrogenation-driven carbon deposition pathways. This work establishes a clear structure-performance relationship for cobalt-based amination catalysts, offering a blueprint for sustainable amine production.
研究领域:
催化
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化学合成
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材料科学
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反应工程
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有机化学
✓ 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）