HYDROMETALLURGY
·
2023
·
IF 4.7
Haitao Zhou,Kun Huang
In conventional liquid-liquid extraction, Pt(IV) and Pd(II) chloride complex anions PtCl 6 2− and PdCl 4 2− in concentrated hydrochloric acid cannot be separated using simple amine extractants according to the ion association mechanism based on the thermodynamic difference in the interaction of their inner sphere coordinated chloride ions with protonated amine. This study exhibits a novel strategy for enhancing the separation of PtCl 6 2− and PdCl 4 2− anions using thin-layer organic membrane-based laminar flow (TOMLF) extraction by controlling the acidified primary amine N1923 (A-N1923) molecular orientation on the surface of concentrated hydrochloric acid with a laminar shear flow. Experiments revealed that the separation selectivity is primarily determined by the interaction of A-N1923 molecules with the outer sphere-bound water molecules around PtCl 6 2− and PdCl 4 2− anions, and is easily controlled by regulating the A-N1923 molecular orientation on the surface of laminar flow. It is a new phenomenon that has not been previously documented. The evolution of A-N1923 molecular orientation and complexation sites induced by laminar shear flow would result in a controllable spatial geometry recognition, therefore promoting or inhibiting the separation of PtCl 6 2− and PdCl 4 2− anions in concentrated hydrochloric acid. This work is expected to provide new insight into the development of hydration-sphere coordination strategies based upon shear-switch laminar flow for controllable host-guest molecule recognition at a flowing liquid-liquid interface.
研究领域:
化学工程
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材料科学
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分析化学
·
物理化学
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DOI
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
·
2020
·
IF 2.463
Shaoping Feng,Kun Huang,Zhangjie Huang,Guiyang Liu,Guowei Zhang,Gaozhang Gou
ABSTRACT In view of the separation and recycling of Pd(II) from multi-metal aqueous solution, a functionalized extractant of 2-[(2-ethylhexyl)thio]benzoxazole (EHBXS) with excellent selectivity for Pd(II) was synthesized and used to extract Pd(II) for the first time. The effects of EHBXS concentration, HCl concentration, organic/aqueous (O/A) phase ratio, contact time, and regeneration of EHBXS were investigated in detail. The extraction efficiency of Pd(II) was almost 100 % while the co-extraction efficiencies of Pt(IV), Rh(III), Cu(II), Fe(III) and Ni(II) existed in the aqueous solution were less than 10 %, which indicates that EHBXS is an effective extractant and can effectively remove Pd(II) from other metals at desired extraction conditions. Thiourea ((NH 2 ) 2 CS) solution (1.0 mol/L) could be used as an effective Pd(II) stripping agent and the one-step stripping efficiency of Pd(II) was higher than 98 %. EHBXS has excellent regeneration ability and the extraction efficiency of Pd(II) with regenerated EHBXS reaches to 87% even after 7 cycles. Moreover, the coordination mechanism between EHBXS and Pd(II) has been proven via the slope method, FT-IR spectra, 1 H NMR, 13 C NMR and single X-ray diffraction. Pd(II) and EHBXS formed a 1:2 complex of Pd(EHBXS) 2 Cl 2 during extraction. Pd(II) was coordinated with two Cl atoms and two EHBXS, and thus formed Pd(EHBXS) 2 Cl 2 molecule, in which EHBXS was coordinated with Pd(II) via the N atom in the benzoxazole ring as neutral unidentate ligand.
研究领域:
化学
·
环境科学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2018
·
IF 6.735
Yong Gao,Shu-Qi Deng,Xia Jin,Song-Liang Cai,Sheng-Run Zheng,Wei-Guang Zhang
For the first time, an amorphous solid contains large cationic M 12 L 24 metal–organic cage (MOC) based on Pd(II) and 3,5-di-pyridin-4-yl-benzaldehyde ( L ), namely a MOC-1 , was constructed and characterized. Although it is an amorphous structure, regular cavity that created by MOC still exists in the solid and performs excellent dye adsorption and separation ability in water. The a MOC-1 can rapidly adsorb the anionic dyes including methyl orange (MO), fluorescein disodium salt (FS), acid fuchsin (AF) and methyl blue (MB) only in several minutes to about 30 min. The adsorption capacities for them are 359, 464, 116 and 150 mg/g, respectively. On the contrary, the adsorption rate of a MOC-1 towards cationic dyes is significantly slower than that of anionic dyes. The adsorption of cationic dyes shows a size-selectively behavior, in which the adsorption of rhodamine B (RhB) is more favorable than the other selected smaller or bigger cationic dyes. The adsorption capacity of RhB is up to 454 mg/g. According to the differences in the adsorption rates and capacities for different charged dyes, a MOC-1 displays diverse dye separation behaviors. It can selectively adsorb RhB from a mixed solution of MLB and RhB by size selectivity. Moreover, the selective separation of anionic and cationic dyes shows an interesting new time-dependence mode that the anionic dye can be selectively adsorbed from a mixed solution of anionic and cationic dyes by controlling the adsorption time. The good adsorption and separation performance of a MOC-1 is caused by the large cavity and the high positive Zeta potential of the material, which are created by the Pd 12 L 24 metal-organic cages.
研究领域:
材料科学
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环境科学
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产品关联
DOI
高影响因子
HYDROMETALLURGY
·
2023
·
IF 4.7
Shaoping Feng,Kun Huang
Dialkylsulfide is considered as the most promising extractant for separating Pd(II) and Pt(IV) in industrial processes. However, the slow kinetics for Pd(II) extraction limits its extensive application. The development of new extractants with faster kinetics, high extraction efficiency, and exceptional Pd(II) separation selectivity has been a persisting goal over the past few decades. In this study, a new functionalized extractant, 1-methyl-2-(nonylthio)-1H-imidazole (MNI) containing both N and S atoms, was synthesized and employed to separate Pd(II) from mixed hydrochloric acid solutions with different initial Pd(II)/Pt(IV) concentration ratios. Experimental results revealed that MNI not only has a high selectivity for Pd(II) over Pt(IV) but also has faster kinetics for Pd(II) extraction than diisopentylsulfide (S201) under similar extraction conditions. In contrast to traditional dialkylsulfide extractants, MNI coordinates with Pd(II) ions via the N(5) atom in its imidazole ring to form Pd(MNI) 2 Cl 2 complexes, instead of using the S atom as with dialkylsulfide. The extraction mechanism involving the coordination between Pd(II) and MNI was demonstrated using the slope analysis method and ultraviolet (UV), Fourier-transform infrared (FT-IR), 1 H NMR, and 13 C NMR spectroscopic methods. The fast extraction kinetics between MNI and Pd(II) was possibly attributed to the high charge density of the N(5) atom in the imidazole ring, whereas the outstanding separation selectivity for Pd(II) was due to the strong affinity of the N(5) atom. The facile synthesis, high saturation capacity, excellent Pd(II) selectivity, and remarkable reusability endow MNI with potential applications in Pd(II) recovery from leach solutions of waste automotive catalysts and other secondary resources.
研究领域:
化学工程
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材料科学
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产品关联
DOI
高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
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2018
·
IF 2.829
Ting Zou,You Han,Xinxue Li,Wei Li,Jinli Zhang,Yan Fu
Controlled synthesis of noble metal nanocatalysts with desirable catalytic activities remains a great challenge. Inspired by electron-rich functional groups and supramolecular assembly properties of natural nucleotides, herein we propose a versatile approach to construct Pd nanocatalysts through employing seven nucleotides as both electron donors and stabilizers . The catalytic performance of nucleotide-Pd complexes are greatly associated with the chemical structures of nucleobases as well as the number of phosphate groups . Guanosine 5′-triphosphate-Pd complexes possess high activities in the hydrogenation reduction of 4-nitrophenol assisted by NaBH 4 , with the relative rate constant of 7770 min −1 mM −1 at 25 °C. Pd(II)-coordinated nucleotides are also promising in NaBH 4 -mediated degradation of organic dyes. This work demonstrates a green and facile process to construct Pd nanocatalysts containing abundant active sites under the assistance by natural nucleotides.
研究领域:
化学
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材料科学
·
催化
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产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2026
·
IF 7.6
Yaxu Liu,Ziyi Quan,Zheng Wang,Lixing Zhao,Jifu Sun,Lei Guo,Bo Wang
The Suzuki-Miyaura cross-coupling is a pivotal method for constructing C–C bonds in biaryl synthesis. Conventional palladium-catalyzed solution-phase reactions are hampered by high catalyst loadings, complex catalyst compositions, toxic solvents, and requirements for inert atmospheres and elevated temperatures. Here, we report the first mechanochemical Suzuki-Miyaura coupling employing well-defined, air-stable dimeric Pd(II)-NHC precatalysts. This solvent-free strategy efficiently couples aryl bromides with boronic acids at low Pd loadings (0.1–0.5 mol %) within 60 min, surpassing both Pd(OAc)2 and phosphine-based mechanochemical systems. The system demonstrates broad chemoselectivity across 102 substrates, stemming from the superior σ-donation and steric tunability of the NHC ligands. DFT calculations reveal a reduced energy barrier for Pd-SIMes in the rate-determining step and a narrower HOMO–LUMO gap relative to phosphine-based analogues, consistent with their enhanced catalytic efficiency and selectivity.
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DOI
高影响因子
RESEARCH ON CHEMICAL INTERMEDIATES
·
2013
·Vol. 40
·期 4
·1633-1636
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IF 0.88
Qin Qi-xue,Yang Jian,Yang Bo
Abstract A facile and simple procedure for the synthesis of norathyriol using Pd(II) as a catalyst via two steps under mild conditions is described. The major advantages of this method are the use of a commercially available catalyst, short reaction times, and the simplicity of the reaction and work-up. The overall yield of 36.6 % is acceptable. Graphical Abstract All reactions were monitored by TLC . The UV-Vis spectra of the product and the intermediate are as follows:
研究领域:
有机化学
·
药物化学
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DOI
高影响因子
Nanomaterials
·
2024
·Vol. 14
·期 6
·512
·
IF 4.4
Yuan Chen,Jiaxing Wang,Daidi Chen,Boxi Wang,Jinchuan Wu,Rongrong Liu,Qingxin Li
Many studies have been conducted on the microbial reduction of Pd (II) to palladium nanoparticles (Pd-NPs) due to the environmental friendliness, low cost, and the decreased toxicity of Pd (II) ions. In this study, we investigate the reduction mechanism of Pd (II) byBacillus megateriumY-4 through proteomics. The data are available via ProteomeXchange with identifier PXD049711. Our results revealed thatB. megateriumY-4 may use the endogenous electron donor (NAD(P)H) generated by nirB, tdh, and fabG and reductase to reduce Pd (II) to Pd-NPs. The expression levels of fabG, tdh, gudB, and rocG that generate NAD(P)H were further increased, and the number of reduced Pd-NPs was further increased with the exogenous electron donor sodium formate. Endogenous electron mediators such as quinones and flavins inB. megateriumY-4 can further enhance Pd (II) reduction. The findings provided invaluable information regarding the reduction mechanism of Pd (II) byB. megateriumY-4 at the proteome level.
研究领域:
微生物学
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环境科学
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产品关联
DOI
PubMed
高影响因子
ChemSusChem
·
2024
·
IF 7.5
Borong Liao,Junhao Gao,Pei Weng,Linya He,Yusheng Zhang,Qiuhua Liu,Zaichun Zhou
Graphical A semiconductor effect from 4d x 2 − y 2 (Pd) to a 2u (π) orbitals in Pd(II) porphyrin was discovered and a domino relationship from ring distortion, core deformation, band gap variation to photocatalytic activity was established and confirmed. In this work, four saddled Pd(II) porphyrins were developed as photocatalyst for N-dealkylation of triethyl Rhodamine (TER) under visible light, and their catalytic ability was found to be negatively related to the out-of-plane of their macrocycles. Two important relationships involving the metalloporphyrins as catalyst were revealed: (1) a photoexcitative semiconductor effect between the 4d x 2 − γ 2 (Pd) and a 2u (π) orbitals of Pd(II) porphyrin on the dealkylation. (2) a domino process from strap length, ring geometry, core deformation, d-π gap variation, to photocatalytic activity. Two revelations imply a unidirectional electron transfer route from axial ligand, to central metal, to porphyrin ring based on photoexcitation and guide the design and development of complex photocatalysts, and their revelation is attributed to the acquisition of a series of Pd(II) porphyrins with continuous ring distortion. The findings help to understand the photocatalytic single electron transfer (SET)-first mechanism based on metallic complex.
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产品关联
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
·
2020
·
IF 8.758
Jianguo Liu,Nan Wang,Jianan Liu,Ming Li,Ying Xu,Chenguang Wang,Yanzhi Wang,Haoquan Zheng,Longlong Ma
Highly selective catalytic hydrogenation of alkynes to alkenes is a highly important reaction owing to its industrial and commercial application. Specifically, semihydrogenation of terminal alkynes has been more challenging than internal alkenes even using Lindlar catalysts. Also, the high reduction degree state metal-supported catalysts like Pd0/C, Pt0/C, and Ru0/C have been well-known to be used widely in hydrogenation due to their super activity. However, charcoal can absorb a large amount of water; Pd/C with 50% water is convenient on a large-scale synthesis. Charcoal generally bears oxygen groups on its surface, which are responsible for low selectivity and undesired products. Even typically, only 10–60% of the Pd metal atoms are exposed, they still suffer from poor stability in acids owing to leaching. Herein, we intend to design active and stable metal catalysts with features as the following to avoid leaching: having strong interaction with the support and coordinatively unsaturated metal sites or low valence state metals physically isolated from the acid environment. Herein, a highly efficient semihydrogenation of terminal alkynes to produce alkenes has been realized using a heterogeneous Pd(II)/POP-GIEC catalyst, imine-linked, crystalline, and porous organic polymer supporter modified by coordination of Pd(OAc)2 to its walls under mild conditions. Surprisingly, for the first time, modified POP-supported low reduction degree PdII catalysts were synthesized efficiently, and they were successfully used in semihydrogenation of terminal alkynes. The substrate scope was studied and included both unfunctionalized as well as functionalized substituents on the para, ortho, and meta position of aromatic alkynes. The substrate having a substituent with the functionality of fluoro protected at the meta position was semihydrogenated with a high alkyne conversion of 100% and olefin selectivity (up to 99%).
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
PubMed
高影响因子
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
·
2022
·Vol. 2022
·期 33
·e202200316
·
IF 3.261
Yong Wang,Hui Wang,Qifan Yang,Shihua Xie,Hongjun Zhu
Graphical Herein, palladium(II)-catalyzed halogenation of 2-phenylquinazolines using N -halosuccinimides as halogen sources was described via C−H activation under mild reaction conditions. A series of halogen-substituted 2-arylquinazolines were synthesized through C−H functionalization. An efficient quinazoline-assisted ortho -halogenation of 2-arylquinazolines has been developed using N -halosuccinimides as halogen sources with Pd(II)-catalyzed C−H bond activation. No additional ligand and oxidant are required. This protocol is highly regioselective and applicable to a broad range of quinazoline substrates bearing different functional groups, giving yields of up to 98 %. The mechanism of the quinazoline ortho -halogenation was investigated by comprehensive experimentation.
研究领域:
有机化学
·
合成化学
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2019
·
IF 5.107
Jian Lu,Yingying Qin,Chao Yu,Xinyu Lin,Minjia Meng,Yongsheng Yan,Hougang Fan,Yilin Wu,Chunxiang Li
Pd (II) from release-unbridled electroplating wastewater is causing great challenges, which is unfavourable either to human health or resource reutilization. Ion-imprinted membranes (IIMs) have recently drawn attentions for selective separation of specific ions from analogues. In this context, we have developed a facile strategy for fabrication of Pd (II)-imprinted membranes (Pd-IIMs) for the selective separation of Pd (II). The enhanced flux was obtained by three-dimensional macroporous structure on polydimethylsiloxane (PDMS). Then the Pd-IIMs were synthesized by a modification-imprinting strategy based on PDMS substrates. With the existence of Co (II), Cu (II), Cd (II) and Ni (II), the as-obtained Pd-IIMs showed superior adsorptive selectivity (3.32–5.06) and perm-selectivity (2.34–4.04) towards Pd (II), as well as the satisfactory regeneration performance (more than 92% of the initial rebinding capacities after 5 cycles of adsorption/desorption). Moreover, the as-prepared Pd-IIMs also displayed stability on separation factors even under ultrasonic treatment. Notably, the overused Pd-IIMs after applications for selective separation of Pd (II) showed a satisfactory performance for the treatment of methylene blue (99.87%), which displayed potentials for the “further applications”. The Pd-IIMs and preparation strategy developed in this work have shown a positive opportunity for the efficient treatment of electroplating wastewater and organic dyes.
研究领域:
环境科学
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材料科学
·
化学工程
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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）