4.8 Article

Ligand-Sharing-Mediated Synthesis of Intermetallic FeM Clusters Embedded in Ultrathin γ-Fe2O3 Nanosheets


Volume 30, Issue 5, Pages -


DOI: 10.1002/adfm.201906995


coordination structures; heterometallic ions; nanocatalysts; precious metal nanoclusters; Raman spectra


  1. National Key R&D Program of China [2016YFA0203102]
  2. National Natural Science Foundation of China [21577157, 21777177, 21822608]
  3. Youth Innovation Promotion Association of CAS

Ask authors/readers for more resources

Precious metal intermetallic nanoclusters (IMNCs) are promising nanocatalysts for practical industrial applications. However, to date, the preparation of these nanoclusters has been restricted to harsh conditions, and only succeeds for a limited number of elements. This study developed a simple and efficient strategy that enables the synthesis of supported IMNCs under ambient conditions via inorganometallic coordination chemistry, specifically, by donating the Cl- ligand, a noble metal chloride (MClab-) forms a heterobimetallic ion (MxFeyClzn-) with the coordination-unsaturated FeCl3. Upon reduction, the ordered heterobimetallic ions are simultaneously transformed into IMNCs and embedded into gamma-Fe2O3 nanosheets, which form from excess FeCl3. In addition to providing convincing spectral evidence for the structure of the heterobimetallic ions, magnetic measurements, atomic-resolution electron microscopy, X-ray absorption spectroscopy, and Fourier transform infrared spectroscopy of chemisorbed CO collectively confirm the successful preparation of the L1(0)-phased Pd3Fe IMNCs. Furthermore, this versatile method can be extended to synthesize other IMNCs, such as AuFe and PtFe, and seems to be applicable to IrFe, RhFe, RuFe, and MCo. When utilized as a heterogeneous catalyst in a Heck coupling reaction, the prepared Pd3Fe IMNCs display satisfactory activity and stability, highlighting their potential applications as advantageous catalysts.


I am an author on this paper
Click your name to claim this paper and add it to your profile.


Primary Rating

Not enough ratings

Secondary Ratings

Scientific rigor
Rate this paper


Review Instruments & Instrumentation

Flow field-flow fractionation hyphenated with inductively coupled plasma mass spectrometry: a robust technique for characterization of engineered elemental metal nanoparticles in the environment

Qingsheng Bai, Yongguang Yin, Yanwanjing Liu, Haowen Jiang, Mengxin Wu, Weidong Wang, Zhiqiang Tan, Jingfu Liu, Myeong Hee Moon, Baoshan Xing

Summary: Due to the increased applications of engineered elemental metal nanoparticles (EMNPs) in recent years, their release into the environment has gained attention. The on-line coupling of flow field-flow fractionation with inductively coupled plasma mass spectrometry (F4-ICPMS) has been well established for the characterization of EMNPs in complex matrices of environmental samples. This review focuses on the specific advantages of the F4 method and recent advances in the application of F4-ICPMS techniques in examining the occurrence and transformation of EMNPs in the environment.


Article Environmental Sciences

Removal of iodide anions in water by silver nanoparticles supported on polystyrene anion exchanger

Li Li, Su-Juan Yu, Rong-Gang Zheng, Peng Li, Qing-Cun Li, Jing-Fu Liu

Summary: The synthesized nanocomposite Ag-D201 showed high efficiency in removing iodide from water, and its adsorption capacity was influenced by pH and water matrix. The synergistic mechanism for iodide adsorption by Ag-D201 was proposed, including the Donnan membrane effect caused by D201 resin, chemisorption of iodide by AgNPs, and catalytic effect of AgNPs.


Article Environmental Sciences

Blockage of ATPase-mediated energy supply inducing metabolic disturbances in algal cells under silver nanoparticles stress

Ruohua Qu, Mi Chen, Jingfu Liu, Qiting Xie, Na Liu, Fei Ge

Summary: Studies have shown that silver nanoparticles (AgNPs) have a negative impact on ATP generation of aquatic organisms, leading to decreased ATP content and metabolic disturbances. AgNPs compete with adenosine diphosphate and inorganic phosphate for binding sites on chloroplast ATPase, reducing substrate binding efficiency. Additionally, AgNPs significantly inhibit multiple ATP-related metabolic pathways. These findings are of great significance for understanding the mechanism of energy supply and metabolic regulation in aquatic organisms under nanoparticle stress.


Article Environmental Sciences

Aggregation and stability of selenium nanoparticles: Complex roles of surface coating, electrolytes and natural organic matter

Sujuan Yu, Hao Liu, Rui Yang, Wenjing Zhou, Jingfu Liu

Summary: This study systematically investigated the aggregation and stability of selenium nanoparticles (SeNPs) under various water conditions using alginate-coated SeNPs (Alg-SeNPs) and polyvinyl alcohol-coated SeNPs (PVA-SeNPs) as models. The results showed that Alg-SeNPs underwent apparent aggregation in the presence of calcium and lanthanum ions, while PVA-SeNPs remained highly stable. Natural organic matter enhanced the stability of Alg-SeNPs in monovalent electrolytes but accelerated their attachment in polyvalent electrolytes. The long-term stability experiments demonstrated that both Alg-SeNPs and PVA-SeNPs increased in aggregation size over time, indicating their potential suspension or settling in water.


Article Chemistry, Multidisciplinary

AuFe3@Pd/?-Fe2O3 Nanosheets as an In Situ Regenerable and Highly Efficient Hydrogenation Catalyst

Zongshan Zhao, Yanhen Wu, Wei Ran, Huachao Zhao, Xiaotian Yu, Jie-fang Sun, Guangzhi He, Jingfu Liu, Rui Liu, Guibin Jiang

Summary: In this study, AuFe3@Pd/gamma-Fe2O3 nanosheets were developed as an in situ regenerable and highly active hydrogenation catalyst. The Pd monolayer sites could be fully regenerated under ambient conditions, initiated by center dot OH radicals from gamma-Fe2O3 nanosheets. The nanosheets exhibited high activity in hydrogenating the carbon-halogen bond and withstand ten rounds of regeneration.

ACS NANO (2023)

Article Engineering, Environmental

Determination of the Particle Number Concentration, Size Distribution, and Species of Dominant Silver-Containing Nanoparticles in Soils by Single-Particle ICP-MS

Qingsheng Bai, Qingcun Li, Jingfu Liu

Summary: We developed an effective method for determining the particle number, size, and species of dominant AgCNPs in soils. AgCNPs were extracted efficiently from soils using ultrasonication wand-assisted tetrasodium pyrophosphate extraction. Multistep selective dissolution of Ag NPs, AgCl NPs, and whole Ag NPs/AgCl NPs/Ag2S NPs was achieved by different reagents. The concentrations and sizes of AgCNPs in the extracts were determined, and Ag2S NPs were found to be the main form of AgCNPs in the soils.


Article Engineering, Environmental

Regulating the reaction pathway of nZVI to improve the decontamination performance through magnetic spatial confinement effect

Hai -Yuan Chi, Xiao-Xia Zhou, Min-Rong Wu, Wan-yu Shan, Jing-fu Liu, Jin-quan Wan, Bing Yan, Rui Liu

Summary: This study investigates the effect of constructing a magnetic mesoporous SiO2 shell on the surface of nanoscale zero-valent iron (nZVI). The results show that this structure can regulate the electron transfer pattern, avoid the formation of iron oxide layers, and improve the efficiency of active hydrogen production.


Article Chemistry, Physical

Dynamic Monitoring of the Structural Evolution of Au@Pd under Electrochemistry

Xiaoyu Zhao, Wei Ran, Zixuan Wang, Jiefang Sun, Rui Liu, Jingfu Liu

Summary: This article investigated the structural transformation of Pd shells on Au nanocubes in different electrolytes at various electrochemical windows. It was found that Pd sites are stable under basic and neutral conditions but experience severe structure evolution under acidic conditions. Pd atoms react with H+ under acidic conditions to form Pd ions, which are easily coreduced with Au ions into surface alloys.


Article Chemistry, Multidisciplinary

Promoting Effect of Nitride as Support for Pd Hydrodechlorination Catalyst

Xiaotian Hua, Wenxuan Wang, Wei Ran, Guangzhi He, Jingfu Liu, Rui Liu

Summary: Metal nitrides, especially TiN, can effectively modulate the electronic states of Pd sites and enhance their catalytic performance in hydrodechlorination reactions, making them promising supports for highly efficient Pd catalysts.


Review Biochemistry & Molecular Biology

Total organic halogen (TOX) analysis in waters: A short review

Jing Wu, Yunwen Wang, Xuexin Gong, Mei He, Xiaoli Wang, Rusong Zhao, Zhineng Hao, Jingfu Liu

Summary: Halogenated organic compounds (HOCs) are widely found in environmental waters, but current analytical techniques cannot identify and quantify all individual HOCs. Total organic halogen (TOX) is proposed as a total quantity index for HOCs in waters, and significant progress has been made. This review presents an overview of TOX analysis, including detection and pretreatment methods, separation methods with and without enrichment, and key factors. It emphasizes the need for more efficient TOX measurement approaches in the future.


Article Engineering, Environmental

Extraction of Common Small Microplastics and Nanoplastics Embedded in Environmental Solid Matrices by Tetramethylammonium Hydroxide Digestion and Dichloromethane Dissolution for Py-GC-MS Determination

Peng Li, Yujian Lai, Rong-gang Zheng, Qing-cun Li, Xueying Sheng, Sujuan Yu, Zhineng Hao, Ya-qi Cai, Jingfu Liu

Summary: A novel method combining TMAH digestion and DCM dissolution has been developed to extract small microplastics and nanoplastics embedded in soils, sediments, and sludges. The feasibility of this method has been verified and it shows promise for evaluating small solid-embedded microplastic and nanoplastic pollution.


Article Engineering, Environmental

Quantitation of Atmospheric Suspended Polystyrene Nanoplastics by Active Sampling Prior to Pyrolysis-Gas Chromatography-Mass Spectrometry

Xue-ying Sheng, Yu-jian Lai, Su-juan Yu, Qing-cun Li, Qing-xiang Zhou, Jing-fu Liu

Summary: Plastic has been shown to release nanoparticles (NPs) into the atmosphere when exposed to sunlight, which poses a continuous health risk to the respiratory system. This study presents a simple and reliable method for quantifying atmospheric polystyrene (PS) NPs using pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS). The method demonstrated excellent reproducibility and high sensitivity, with a detection limit as low as 15 pg/m(3) for PS NPs. The method can be used for routine monitoring of atmospheric PS NPs and assessing their risk to human health.


Article Chemistry, Physical

SERS for Probing Highly Reactive Pd Sites with Elongated Pd-Pd Bonds on the Au Surface

Huachao Zhao, Wei Ran, Guangzhi He, Hongxin Wei, Jiefang Sun, Xiaoxia Zhou, Shiwei Li, Jingfu Liu, Bing Yan, Rui Liu, Guibin Jiang

Summary: Bond length is an important structural parameter that can affect the activity of catalysts. In core-shell gold-palladium (Au@Pd) nanocatalysts, elongated Pd-Pd bonds resulting from lattice mismatches between Au and Pd are found to exhibit distinct catalytic activity. Surface-enhanced Raman scattering (SERS) spectra of chemisorbed 2,6-dimethylphenyl isocyanide (2,6-DMPI) were used to investigate the elongated Pd-Pd bonds on Au@Pd. The study revealed that strained sites with elongated Pd bonds are more than 100 times more active in a catalyzed Suzuki-Miyaura coupling reaction.


Article Engineering, Environmental

Active Center Size-Dependent Fenton-Like Chemistry for Sustainable Water Decontamination

Zelin Wu, Zhaokun Xiong, Wen Liu, Rui Liu, Xuezhen Feng, Bingkun Huang, Xinhao Wang, Yixuan Gao, Hong Chen, Gang Yao, Bo Lai

Summary: Accurate control of catalytic activity and mechanism, as well as understanding the correlation between structure, activity, and selectivity in Fenton-like chemistry, is crucial for designing efficient catalysts for sustainable water decontamination. In this study, size-dependent catalysts with single cobalt atoms, atomic clusters, and nanoparticles were prepared to investigate the change in catalytic activity and mechanism in peroxymonosulfate-based Fenton-like chemistry. The results showed that the catalytic activity and durability varied with the size of the metal active centers, and the contributions of radical and nonradical mechanisms were modulated by reducing the metal size. Density functional theory calculations revealed the evolution of catalytic mechanisms in size-dependent systems at different Gibbs free energies for reactive oxygen species generation. The findings of this study provide an in-depth understanding of the effects of metal size in Fenton-like chemistry and can guide the design of intelligent catalysts for specific water purification applications.


Article Chemistry, Physical

Optimising PtFe nanoparticle structure to enhance catalytic activity and stability for propane oxidation

Zhenpeng Huang, Jihang Yu, Wenbo Li, Xuan Tang, Yanglong Guo, Yun Guo, Li Wang, Sheng Dai, Rui Liu, Wangcheng Zhan

Summary: This study focuses on the surface structure of PtFe nanoparticles on PtFe/CeO2-x catalysts and its impact on the activity and water resistance for propane oxidation. The PtFe/CeO2-O catalyst exhibited superior performance due to the cooperation among metallic Pt sites, active oxygen species, and FeOx nanoclusters. The findings of this study provide valuable insights for the development of efficient bimetallic catalysts to eliminate volatile organic compound pollutants.


No Data Available