Molecular Catalysis
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2026
·
IF 4.3
Bo Liu,Jiating Li,Chunyan Xiang,Hongyue Pan,Zemin An,Yuanjie Xu,Lizhi Wu,Li Tan,Yu Tang
The direct conversion of methane into valuable chemicals under mild conditions represents a promising technological pathway, yet achieving both high efficiency and selectivity remains a major challenge in catalysis. In this work, we report a rhodium catalyst atomically dispersed on ZSM-5 for catalytic conversion of methane to oxygenates using H 2 O 2 as oxidant under mild conditions. With carbon monoxide (CO) as a promoter, the catalyst achieved an oxygenates productivity of 46.8 mmol·g cat −1 ·h −1 (equivalent to 9360 mmol·g Rh −1 ·h −1 or 964.1 mol·mol Rh −1 ·h −1 ) with approximately 90.7 % overall selectivity (including liquid products and gaseous CO 2 ). The catalyst retained high activity over five recycling experiments. A combined investigation by HAADF-STEM, XAFS, and DRIFTS-CO analyses confirms that the active sites consist of atomically dispersed Rh species in a Rh 1 O 5 configuration anchored within the ZSM-5 micropores. Mechanistic studies, including controlled experiments, EPR, and in situ infrared spectroscopy, reveal that CO plays a dual role. It promotes the formation of ·OH radicals from H 2 O 2 and facilitates the activation of methane, leading to the generation of ·CH 3 species. Oxygenate products are produced via the direct coupling of ·CH 3 , ·OH, and CO molecules. This work highlights the potential of tailoring atomically dispersed metal catalysts and using CO as reactant and promoter to enable efficient methane transformation into valuable oxygenates.
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高影响因子
Separations
·
2026
·Vol. 13
·期 5
·148
·
IF 3.5
Siyu Wang,Junyang Du,Junsu Jin,Jianguo Mi
Metal–organic frameworks (MOFs) show great potential for post-combustion carbon capture, yet their practical application is often constrained by challenges such as powder handling difficulties, limited structural stability during shaping processes, and performance degradation under high-humidity conditions. In this study, Mg-gallate was structured into millimeter-sized Mg-gallate/CA composite beads via the ionotropic gelation method, and then a hydrophobic layer of vinyltrimethoxysilane (VTMS) was constructed on the bead surface by chemical vapor deposition. The synthesized Mg-gallate/CA and V-Mg-gallate/CA are characterized by XRD, FT-IR, and other techniques, and their CO2adsorption behavior, adsorption–desorption kinetics, breakthrough performance, and cyclic stability are systematically evaluated. At 298 K and 0.1 bar, the CO2adsorption capacity of Mg-gallate/CA reached 94.2% of that of Mg-gallate powder. The microporous–microporous hierarchical structure constructed by the ionotropic gelation method improved the CO2capture efficiency of the composite beads by 16.7% at 0.1 bar. V-Mg-gallate/CA maintained a high dynamic CO2adsorption capacity of 2.87 mmol/g for a 10 vol.% CO2/90 vol.% N2gas mixture at 298 K under 80% RH, corresponding to 2.04 times the capacity of Mg-gallate/CA, and retained 98.8% of its initial adsorption capacity at 0.1 bar after 10 cycles. Combining ionotropic gelation shaping with surface hydrophobic modification represents an effective strategy for developing MOF-based adsorbents suitable for post-combustion CO2capture.
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JOURNAL OF CATALYSIS
·
2022
·
IF 8.047
Xiao-Chao Chen,Tian Lan,Kai-Chun Zhao,Lin Guo,Yong Lu,Ye Liu
Tandem hydroaminomethylation (HAM) represents one of the most important catalytic protocols for the one-pot synthesis of amines using low-cost and widely available olefins, syngas and amines as starting materials. In this work, the applied P,O-hybrid ligand containing phosphino-fragment and carboxylic group [ L1 , 2-(diphenylphosphino)benzoic acid] could stoichiometrically react with Rh(acac)(CO) 2 to afford a stable Rh-complex of Z [dicarbonyl-2-(diphenylphosphino)benzoato rhodium(I)], wherein the more substantial P,O-chelation derived from L1 as a bidental pincer upon deprotonation as well as the thermodynamically favored six-membered ring structure warranted its stability. It was found that Z could serve as a highly active catalyst to accelerate the reaction rate of each individual step in the HAM, advantageous with the completely inhibited side-reaction of olefin-hydrogenation. The in situ high-pressure FT-IR spectral analysis demonstrated, for the first time, that the involvement of L1 greatly facilitated the formation of two kinds of the active Rh-H intermediates ( A′ and A , v 2012 and 2043 cm −1 ) with well-maintained longevity. And the DFT calculations further confirmed that the Rh-complex of Z exhibited exclusive ability to activate H 2 , resulting in the efficient formation of Rh-H intermediates of A′ and A , the later ( A ) was responsible for rapid olefin-hydroformylation, and the former ( A′ ) was in charge of imine-hydrogenation.
研究领域:
催化化学
·
有机合成
·
理论计算
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高影响因子
JOURNAL OF MATERIALS CHEMISTRY
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2012
·Vol. 22
·期 18
·9117-9122
·
IF 5.968
Sha Chen,Hongye Zhang,Lingyan Wu,Yanfei Zhao,Changliang Huang,Maofa Ge,Zhimin Liu
Based on the galvanic replacement reaction between Cu nanoparticles and noble metal ions, a simple and efficient strategy was developed for the preparation of supported Cu–M (M = Pt, Pd, Ru, Rh) bimetallic nanoparticles under intense ultrasonication irradiation at ambient environment. A series of Cu–M/TiO2 bimetal catalysts with controllable composition, metal particle size less than 2 nm and narrow size distribution were obtained, and characterized by transmission electron microscopy (TEM), high resolution transmission electron microscope (HRTEM) with scanning TEM (STEM) mode, energy-dispersive X-ray spectrometers (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and ICP-AES analysis. It was demonstrated that most of the metal particles were present in the form of bimetallic state. The mechanism of this strategy was discussed. The resultant Cu–Pd/TiO2 was used to reduce nitrate at room temperature, and it exhibited extremely high activity.
研究领域:
催化化学
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环境科学
·
材料科学
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高影响因子
RSC Advances
·
2019
·Vol. 9
·期 26
·15033-15041
·
IF 3.049
Ya Gao,Yongjie Zheng,Jixing Chai,Jingzhi Tian,Tao Jing,Deqing Zhang,Junye Cheng,Huiqing Peng,Bin Liu,Guangping Zheng
Effective separation and rapid transfer of photogenerated electron–hole pairs are key features of photocatalytic materials with high catalytic activity, which could be achieved in co-catalysts. It is reported that the two-dimensional (2D) MoS2 is a promising co-catalyst due to its unique semi-conductive properties and graphene-like layered structure. However, the application of MoS2 as a co-catalyst is limited by its poor electrical conductivity. On the other hand, it is worth noting that TiO2 possesses reactive crystal facets, which is one of the dominant mechanisms for the separation of photogenerated electron–hole pairs. In this work, we prepared MoS2/RGO hybrids as co-catalysts which were doped to TiO2 with highly reactive {001} planes via the hydrothermal method. It was found that the {001}-TiO2/MoS2/RGO photocatalysts with 7 wt% MoS2/RGO co-catalyst show the highest photodegradation activity for the degradation of Rh B under visible light irradiation (λ > 400 nm), which could result from the synergy of the effective separation of electron–hole pairs by the {001} facets in TiO2 and the rapid transfer of electron–hole pairs in MoS2/RGO. The results show that the {001}-TiO2/MoS2/RGO hybrid is a low-cost and stable photocatalyst for the effective degradation of Rh B under visible light.
研究领域:
材料科学
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环境科学
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PubMed
高影响因子
ChemCatChem
·
2019
·Vol. 11
·期 22
·5543-5552
·
IF 4.495
Haimeng Tian,Junjie Zhou,Yunong Li,Yiming Wang,Lei Liu,Yongjian Ai,Ze-Nan Hu,Jifan Li,Rongxiu Guo,Zhibo Liu,Hong-bin Sun,Qionglin Liang
Graphical Functionalized surfaces : Rh nanoparticles supported on magnetic silica spheres with various functional groups were tested in the catalytic hydrogenation of nitroarenes under mild conditions. Electron-donating groups can effectively increase the electron density of catalytic sites and the ratio of Rh 0 /Rh 3+ , which results in the promotion of the selectivity of the catalyst for hydrogenation at room temperature under atmospheric conditions. Modifying the surface of metal catalyst is a crucial subject for improving the heterogeneous metal catalysts. It is still a great challenge to understand the structure-activity relationship (SAR) between the surface supporting groups and the metal particles. Herein, Rh NPs supported on the magnetic silica sphere with various functional groups (−NH 2 , −SH, −SO 3 H, −N=CH 2 , −Cl, −NHCOCH 3 and −NHCH 2 Ph) have been prepared for catalytic hydrogenation of nitroarenes under atmospheric pressure at room temperature. We discover that the chemical state of Rh NPs depends on the supporting groups significantly. The electron-donating functionalities can effectively elevate the Rh 0 /Rh 3+ ratio, which increase the catalytic performance both in conversion and selectivity. The amino group decorated catalyst has such a good selectivity that no dechlorination reaction is observable in the hydrogenation of 2-chloro-3-nitropyridine. What's more, by introducing magnetic Fe 3 O 4 nuclei and mesoporous silica encapsulating layer, the catalyst can be recovered conveniently by an external magnet, and can be reused 10 cycles without any loss of activity.
研究领域:
催化化学
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材料科学
·
纳米技术
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高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2016
·
IF 3.205
Bao-Xia Dong,Hui Tian,Yi-Chen Wu,Fan-Yan Bu,Wen-Long Liu,Yun-Lei Teng,Guo-Wang Diao
Liquid ammonia electrolysis is conducted out at ambient temperature using different ammonium salt electrolytes with and without the reference electrode. It is determined that electrolytes containing NH 4 + increase the current density and reduce the solution resistance. Moreover, ammonium salts of NH 4 Br, NH 4 NO 3 and NH 4 Cl preserve >80% current efficiency and a 0.6–0.8 mL min −1 average rate of H 2 generation during chronopotentiometry tests at 120 mA cm −2 for 3 h. A minimum electrolysis voltage ( E min ) of ca . 1.2 V is required for the NH 4 Cl electrolyte when using Pt-foil as the anode and cathode . To decrease the overpotential of the anode reaction, five types of electrocatalysts were prepared and characterized: Pt-black, Rh, Pt–Ir, Rh–Pt and Ph–Pt–Ir alloys. Trimetallic Rh–Pt–Ir and bimetallic Pt–Ir, Rh–Pt (1:1) alloy electrodes exhibit a combined benefit of better activity and minimized deactivation. The ternary Rh–Pt–Ir alloy anode shows the best electrocatalytic activity with the lowest E min of ca . 0.47 V and highest current density of 46.9 mA cm −2 at 2.0 V. In comparison with the Pt-foil anode, the E min is reduced by two-thirds, and the current density is increased two-fold.
研究领域:
化学工程
·
能源科学
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高影响因子
Nano Research
·
2017
·Vol. 10
·期 5
·1749-1755
·
IF 7.354
Jiang Binbin,Yang Lulu,Liao Fan,Sheng Minqi,Zhao Haozhe,Lin Haiping,Shao Mingwang
Hydrogen evolution by electrocatalysis is an attractive method of supplying clean energy. However, it is challenging to find cheap and efficient alternatives to rare and expensive platinum based catalysts. Pt provides the best hydrogen evolution performance, because it optimally balances the free energies of adsorption and desorption. Appropriate control of these quantities is essential for producing an efficient electrocatalyst. We demonstrate, based on first principles calculations, a stepwise designed Rh-Au-Si ternary catalyst, in which adsorption (the Volmer reaction) and desorption (the Heyrovsky reaction) take place on Rh and Si surfaces, respectively. The intermediate Au surface plays a vital role by promoting hydrogen diffusion from the Rh to the Si surface. Theoretical predictions have been explored extensively and verified by experimental observations. The optimized catalyst (Rh-Au-SiNW-2) has a composition of 2.2:28.5:69.3 (Rh:Au:Si mass ratio) and exhibits a Tafel slope of 24.0 mV·dec –1 . Its electrocatalytic activity surpasses that of a commercial 40 wt.% Pt/C catalyst at overpotentials above 0.19 V by exhibiting a current density of greater than 108 mA·cm –2 . At 0.3 V overpotential, the turnover frequency of Rh-Au-SiNW-2 is 10.8 times greater than that of 40 wt.% Pt/C. These properties may open new directions in the stepwise design of highly efficient catalysts for the hydrogen evolution reaction (HER).
研究领域:
材料科学
·
能源化学
·
催化科学
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高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2023
·
IF 19
Jiali Mu,Guifa Long,Xiangen Song,Siquan Feng,Xingju Li,Qiao Yuan,Bin Li,Zheng Jiang,Li Yan,Yunjie Ding
The local coordination environment of central active sites plays a critical role in tuning the catalytic properties of heterogeneous single-metal-site catalysts (HSMSCs). However, carbon supports with inert surface properties provide weak interaction with the active sites, which hamper the effective modulation of the coordination structure of HSMSCs. Herein, this work shows that introducing N and S atoms into carbon support can modify the coordination environment of single-Rh-site and effectively improves the catalytic activity for the methanol carbonylation reaction. The synthesized Rh/AC-NS with single-Rh-site exhibits a high methanol conversion of 88% and a stable acetyl production rate of 2812 h −1 , in contrast with 1285 h −1 of Rh/AC without N- and S- functional groups, and meanwhile remarkably higher than those of Rh/AC-N and Rh/AC-S with only N- or S- functional group under the same mild reaction conditions. As revealed by the experimental result and density functional theory (DFT) calculations, the special combination of N- and S- functional groups offers favorable coordination configuration and also beneficial electronic structure for facilitated CH 3 I oxidative addition and CO insertion steps of single-Rh-site. This work offers new opportunities for rationally tuning the coordination structure of HSMSCs for heterogeneous catalysis.
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高影响因子
Nanoscale
·
2022
·Vol. 15
·期 3
·1422-1430
·
IF 8.307
Haisheng Wei,Zhaohua Gao,Liru Cao,Kairui Li,Xiaorui Yan,Tiantian Liu,Mingyuan Zhu,Fei Huang,Xu Fang,Jian Lin
Chemoselective hydrogenation of quinoline and its derivatives under mild reaction conditions still remains a challenging topic, which requires a suitable interaction between reactants and a catalyst to achieve high performance and stability. Herein, FePO4-supported Rh single atoms, subnano clusters and nanoparticle catalysts were synthesized and evaluated in the chemoselective hydrogenation of quinoline. The results show that the Rh subnano cluster catalyst with a size of ∼1 nm gives a specific reaction rate of 353 molquinoline molRh−1 h−1 and a selectivity of >99% for 1,2,3,4-tetrahydroquinoline under mild conditions of 50 °C and 5 bar H2, presenting better performance compared with the Rh single atoms and nanoparticle counterparts. Moreover, the Rh subnano cluster catalyst exhibits good stability and substrate universality for the hydrogenation of various functionalized quinolines. A series of characterization studies demonstrate that the acidic properties of the FePO4 support favors the adsorption of quinoline while the Rh subnano clusters promote the dissociation of H2 molecules, and then contribute to the enhanced hydrogenation performance. This work provides an important implication to design efficient Rh-based catalysts for chemoselective hydrogenation under mild conditions.
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PubMed
高影响因子
ACS Applied Nano Materials
·
2023
·
IF 5.9
Xin Ning,Heming Wang,Ganghua Zhou,Longyun Zhang,Yanju Yang,Jingya Sun,Xiaozhi Wang
Ni catalysts decorated with trace Rh supported on γ-Al2O3 were prepared by the co-impregnation method. To obtain the Ni–Rh nanoparticles with different nanostructures and chemical compositions, bimetallic catalysts with varied Ni/Rh molar ratios were prepared. For comparison, monometallic Ni/γ-Al2O3 and Rh/γ-Al2O3 catalysts were also prepared by the impregnation method. The selective gas phase catalytic hydrodechlorination of 1,2-dichloroethane to ethylene was used to evaluate catalytic performances of the catalysts. The catalysts were characterized by X-ray diffraction, N2 adsorption, X-ray photoelectron spectroscopy, H2 temperature-programmed reduction, transmission electron microscopy–energy-dispersive X-ray, and CO chemisorption. It was found that the introduction of Rh to Ni catalyst facilitated the generation of spillover hydrogen which could enhance the ability of the Ni catalyst for H2 activation. In bimetallic catalysts, there was an intimate interaction between Ni and Rh, and isolated Rh sites were formed due to the dilution effect of Ni. Accordingly, compared with the monometallic Ni catalyst for gas phase catalytic hydrodechlorination of 1,2-dichloroethane, the bimetallic Ni–Rh(800)/γ-Al2O3 catalyst exhibited markedly higher 1,2-dichloroethane conversion (37%) and comparable selectivity to ethylene (95%). The findings in this study indicate that Ni–Rh/γ-Al2O3 with trace Rh can be used as a promising catalyst for highly effective and selective catalytic hydrodechlorination of chlorinated hydrocarbons.
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高影响因子
ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Guangjun Ji,CunYao Li,Xiangsong Lin,Xiao-Feng Wu,Li Yan,Yunjie Ding
To enhance the catalytic performance of single-metal-site catalysts (SMSCs), regulating the interaction between the active site and substrate is crucial but challenging. Herein, a series of Rh-based SMSCs (Rh/m-3vPAr3-POLs) were designed and synthesized on P-abundant porous organic polymers (POPs) with different electronegativities of frame phosphine. The Rh–P active sites on various POPs were modified by functional groups (−F, −H, −Me, or −OMe). Both the formation of HRh(CO)2(P)2 active species and the insertion of CO were promoted via the electron-accepting property of fluorine, which endowed Rh/m-3vPAr3-POL-F with the best activity (TOF = 3000 h–1), selectivity (>88.1%), l/b ratio (>6.8), and stability (1000 h) for 1-octene hydroformylation in a fixed-bed reactor. Multiple characterization techniques (extended X-ray absorption fine structure, scanning transmission electron microscopy, in situ Fourier-transform infrared spectroscopy, etc.) and density functional theory calculations were employed to get further insights into the microenvironment and active structure of Rh-based SMSCs. This work offers a promising avenue for designing efficient and stable SMSCs in heterogeneous catalysis.
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