New heteroleptic and homoleptic complexes of the type[Pd(4,5-dmbipy)C12], [Pd(4,5-dmbipy)L2], and [Pd(4,5-dimebipy)2]2+ (L = Pyridine or 4-methylpyridine(4-picoline), bipy = 2,2'-bipyridine, and 4,5-dimebip...New heteroleptic and homoleptic complexes of the type[Pd(4,5-dmbipy)C12], [Pd(4,5-dmbipy)L2], and [Pd(4,5-dimebipy)2]2+ (L = Pyridine or 4-methylpyridine(4-picoline), bipy = 2,2'-bipyridine, and 4,5-dimebipy = 4,5-dimethyl-2,2'-bipyridine) were synthesized and characterized by IH NMR and elemental analysis. The crystal structure of bis(4-methylpyridine)-4,5- dimethyl-2,2'-bipyridinepalladium(II)perchlorate [Pd(4,5-dmbipy)(4-pic)2](CIO4)2 was also determined by single crystal X-ray diffraction. This complex crystallized in the triclinic crystal system and space group PI with a = 9.562 (2), b = 11.326 (4), c = 15.0120 (10) A°; α = 70.940°, β= 77.60 (2), γ= 67.86 (2) and z = 4. The Pd (II) in square planar environment showed a small distortion towards tetrahedral through one coordinated bipyridine ring twisting with respect to the other.展开更多
With the development of hydrogen energy,palladium-based membranes have been widely used in hydrogen separation and purification.However,the poor chemical stability of palladium composite membranes limits their commerc...With the development of hydrogen energy,palladium-based membranes have been widely used in hydrogen separation and purification.However,the poor chemical stability of palladium composite membranes limits their commercial applications.In this study,a zeolite-palladium composite membrane with a sandwich-like structure was obtained by using a TS-1 zeolite film grown on the surface of palladium membrane.The membrane microstructure was characterized by SEM and EDX.The effects of the TS-1 film on the hydrogen permeability and stability of palladium composite membrane were investigated in details.Benefited from the protection of the TS-1 zeolite film,the stability of palladium composite membrane was enhanced.The results indicate that the TS-1-Pd composite membrane was stable after eight cycles of the temperature exchange cycles between 773 K and 623 K.Especially,the loss of hydrogen permeance for TS-1-Pd composite membrane was much smaller than that of the pure palladium membrane when the membrane was tested in the presence of C3H6atmosphere.It indicated that the TS-1-Pd composite membrane had better chemical stability in comparison with pure palladium membrane,owing to its sandwich-like structure.This work provides an efficient way for the deposition of zeolite film on palladium membrane to enhance the membrane stability.展开更多
The selective removal of trace acetylene in ethylene feed gas is of great significance in the petrochemicalindustry;however, there are still challenges in designing and developing high-performance catalysts. Here, a M...The selective removal of trace acetylene in ethylene feed gas is of great significance in the petrochemicalindustry;however, there are still challenges in designing and developing high-performance catalysts. Here, a MOFassistedencapsulation strategy was adopted for the precise synthesis of diatomic Pd2 sites on a ZnO support. When usedfor the acetylene semi-hydrogenation reaction, the dual-atom Pd2-ZnO catalyst exhibited improved catalytic performance,achieving complete conversion of acetylene at 125 °C with an 89% selectivity to ethene, as compared to Pd single-atom andnanoparticles. This enhancement was mainly attributed to the catalyst’s ability to dissociate H2 and facilitate the desorptionof intermediate C2H4. Moreover, the strong interaction between the support and the diatomic Pd sites was responsible for thecatalyst’s excellent stability during the long-term reaction.展开更多
In practical applications,noble metal doping is often used to prepare high performance gas sensors,but more noble metal doping will lead to higher preparation costs.In this study,CeO_(2)/ZnO-Pd with low palladium cont...In practical applications,noble metal doping is often used to prepare high performance gas sensors,but more noble metal doping will lead to higher preparation costs.In this study,CeO_(2)/ZnO-Pd with low palladium content was prepared by ultrasonic method with fast response and high selectivity for acetone sensing.With the same amount of palladium added,the selectivity coefficient of CeO_(2)/ZnO-Pd is 1.88 times higher than that of the stirred sensor.Compared with the pure PdO-doped CeO_(2)/ZnO-PdO material,the content of Pd in CeO_(2)/ZnO-PdO is about 30%of that in CeO_(2)/ZnO-PdO,but the selectivity coefficient for acetone is 2.56 times higher.The CeO_(2)/ZnO-Pd sensor has a higher response(22.54)to 50×10^(−6) acetone at 300℃and the selectivity coefficient is 2.57 times that of the CeO_(2)/ZnO sensor.The sensor has a sub-second response time(0.6 s)and still has a 2.36 response to 330×10^(−9) of acetone.Ultrasonic doping makes Pd particles smaller and increases the contact area with gas.Meanwhile,the composition of n-p-n heterojunction and the synergistic effect of Pd/PdO improve the sensor performance.It shows that ultrasonic Pd doping provides a way to improve the utilization rate of doped metals and prepare highly selective gas sensors.展开更多
Carbonylation reactions,crucial for carbonyl group incorporation,struggle with the inherent complexity of achieving selective mono-or double-carbonylation on single substrates,often due to competing reaction pathways....Carbonylation reactions,crucial for carbonyl group incorporation,struggle with the inherent complexity of achieving selective mono-or double-carbonylation on single substrates,often due to competing reaction pathways.Herein,our study introduces a strategy employing palladium amides,harnessing their unique reactivity control,to direct the selective carbonylation of amines for the targeted synthesis of urea and oxamide derivatives.The palladium amide structure was elucidated using single-crystal X-ray diffraction.Controlled experiments and cyclic voltammetry studies further elucidate that the oxidation of palladium amide or its insertion into a carbonyl group diverges into distinct pathways.By employing sodium percarbonate as an eco-friendly oxidant and base,we have successfully constructed a switchable carbonylation system co-catalyzed by palladium and iodide under room temperature.The utilizing strategy in this study not only facilitates effective control over reaction selectivity but also mitigates the risk of explosions,a critical safety concern in traditional carbonylation methods.展开更多
Supported Pd catalyst is an important noble metal material in recent years due to its high catalytic performance in CO_(2)hydrogenation.A fluidized-bed plasma assisted atomic layer deposition(FP-ALD) process is report...Supported Pd catalyst is an important noble metal material in recent years due to its high catalytic performance in CO_(2)hydrogenation.A fluidized-bed plasma assisted atomic layer deposition(FP-ALD) process is reported to fabricate Pd nanoparticle catalyst over γ-Al_(2)O_(3)or Fe_(2)O_(3)/γ-Al_(2)O_(3)support,using palladium hexafluoroacetylacetonate as the Pd precursor and H_(2)plasma as counter-reactant.Scanning transmission electron microscopy exhibits that highdensity Pd nanoparticles are uniformly dispersed over Fe_(2)O_(3)/γ-Al_(2)O_(3)support with an average diameter of 4.4 nm.The deposited Pd-Fe_(2)O_(3)/γ-Al_(2)O_(3)shows excellent catalytic performance for CO_(2)hydrogenation in a dielectric barrier discharge reactor.Under a typical condition of H_(2)to CO_(2)ratio of 4 in the feed gas,the discharge power of 19.6 W,and gas hourly space velocity of10000 h^(-1),the conversion of CO_(2)is as high as 16.3% with CH_(3)OH and CH4selectivities of 26.5%and 3.9%,respectively.展开更多
Covalent organic frameworks(COFs)have emerged as a class of promising supports for electrocatalysis because of their advantages including good crystallinity,highly ordered pores,and structural diversity.However,their ...Covalent organic frameworks(COFs)have emerged as a class of promising supports for electrocatalysis because of their advantages including good crystallinity,highly ordered pores,and structural diversity.However,their poor conductivity represents the main obstruction to their practical application.Here,we reported a novel synthesis strategy for synergistically endowing a triphenylamine-based COFs with improved electrical conductivity and excellent catalytic activity for oxygen reduction,via the in-situ redox deposition and confined growth of palladium nanoparticles inside the porous structure of COFs using reductive triphenylamine frameworks as reducing agent;meanwhile,the triphenylamine unit was oxidized to radical cation structure and affords radical cation COFs with conductivity as high as3.2*10^(-1) S m^(-1).Such a uniform confine palladium nanoparticle on highly conductive COFs makes it an efficient electrocatalyst for four-electron oxygen reduction reaction(4e-ORR),showing excellent activities and fast kinetics with a remarkable half-wave potential(E_(1/2))of 0.865 V and an ultralow Tafel slope of 39.7 mV dec^(-1) in alkaline media even in the absence of extra commercial conductive fillers.The generality of this strategy was proved by preparing the different metal and metal alloy nanoparticles supported on COFs(Au@COF,Pt@COF,AuPd@COF,AgPd@COF,and PtPd@COF)using reductive triphenylamine frameworks as reducing agent.This work not only provides a facile strategy for the fabrication of highly conductive COF supported ORR electrocatalysts,but also sheds new light on the practical application of Zn-air battery.展开更多
Suzuki-Miyaura reaction of aryl halides with phenylboronic acid using a heterogeneous palladium catalyst based on activated carbons(AC) was systematically investigated in this work. Two different reaction modes(batch ...Suzuki-Miyaura reaction of aryl halides with phenylboronic acid using a heterogeneous palladium catalyst based on activated carbons(AC) was systematically investigated in this work. Two different reaction modes(batch procedure and continuous-flow procedure) were used to study the variations of reaction processing. The heterogeneous catalysts presented excellent reactivity and recyclability for iodobenzene and bromobenzene substrates in batch mode, which can be attributed to stabilization of Pd nanoparticles by the thiol and amino groups on the AC supports. However, significant dehalogenation in the reaction mixture and Pd leaching from the heterogeneous catalysts were observed in continuous-flow mode.This unique phenomenon in continuous-flow mode resulted in a dramatic decline in reaction selectivity and durability of heterogeneous catalysts comparing with that of batch mode. In addition, the heterogeneous Pd catalysts with thiol-and amino-modified AC supports exhibited different reactivity and durability in batch and continuous-flow mode owing to the difference of interaction between Pd species and AC supports.展开更多
【目的】以葡萄汁为原料,植物乳杆菌Zhang-LL及马克斯克鲁维酵母M3为发酵菌株,优化葡萄汁酵素的发酵工艺条件。【方法】比较植物乳杆菌Zhang-LL和马克斯克鲁维酵母M3在葡萄汁中的不同接种方式对益生菌活菌数和DPPH清除率的影响,筛选葡...【目的】以葡萄汁为原料,植物乳杆菌Zhang-LL及马克斯克鲁维酵母M3为发酵菌株,优化葡萄汁酵素的发酵工艺条件。【方法】比较植物乳杆菌Zhang-LL和马克斯克鲁维酵母M3在葡萄汁中的不同接种方式对益生菌活菌数和DPPH清除率的影响,筛选葡萄汁酵素最优接种发酵方式。进一步通过单因素试验及响应面试验,优化葡萄汁酵素最佳发酵工艺条件。【结果】植物乳杆菌Zhang-LL和马克斯克鲁维酵母M3共发酵可以显著提高葡萄汁酵素中益生菌活菌数和DPPH清除率;植物乳杆菌Zhang-LL和马克斯克鲁维酵母M3共发酵的最佳工艺条件为:按照1∶1比例接种,初始接种量5.00 lg CFU/mL、大豆蛋白胨添加量0.46%、34℃发酵18 h,植物乳杆菌Zhang-LL活菌数达6.60×10^(8)CFU/mL,马克斯克鲁维酵母M3活菌数达8.20×10^(7)CFU/mL,酵素DPPH清除率85.25%。【结论】乳酸菌与酵母菌协同发酵,在缩短发酵时间的同时还能达到较高的活菌数和DPPH清除率,可为葡萄汁酵素的工业化制备及后续多功能产品研发提供理论依据。展开更多
Palladium nanoparticles supported on cross-linked polyaniline with bulky phosphorus ligands were developed.These catalysts showed high efficiency in the Suzuki-Miyaura reaction of aryl chlorides and bromides with phen...Palladium nanoparticles supported on cross-linked polyaniline with bulky phosphorus ligands were developed.These catalysts showed high efficiency in the Suzuki-Miyaura reaction of aryl chlorides and bromides with phenylboronic acids.Aryl chlorides and bromides with functional groups,such as CN,MeO,CHO,MeCO and NO_2,were converted to the corresponding biphenyls in high yields with catalyst loading.Additionally,the catalysts combined high activity with good reusability;they could be used at least five times for the Suzuki-Miyaura coupling reaction.展开更多
The neutral palladium(Ⅱ) complex bis-[1-(5'-diphenylphosphinothiazol-2'-yl)-imidazolyl]dichloropalladium(Ⅱ)(1A) ligated by thiazolylimidazolyl-based phosphine(L1) in which thiazolylimidazolyl acted as an...The neutral palladium(Ⅱ) complex bis-[1-(5'-diphenylphosphinothiazol-2'-yl)-imidazolyl]dichloropalladium(Ⅱ)(1A) ligated by thiazolylimidazolyl-based phosphine(L1) in which thiazolylimidazolyl acted as an S- and N-donor provider with weak coordinating nature,and the ionic complex bis-[1-(5'-diphenylphosphinothiazol-2'-yl)-3-methylimidazolium]dichloropalladium(Ⅱ) trifluoromethanesulfonate(2A) ligated by thiazolylimidazolium-based phosphine(L2) after quaternization of L1 using methyl trifluoromethanesulphonate were synthesized.It was found that the introduced positive charges and strong electron-withdrawing effect in 2A not only led to changes in the configuration and structural stability of the complex,but also lowered its catalytic performance in carbonylative Sonogashira reactions.These effects reveal the important role of the N-donor in 1A.In addition,as an ionic palladium complex,2A combined with the room-temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate could be recycled eight times as the catalyst in carbonylative Sonogashira reactions without detectable metal leaching.展开更多
An important area of research in nanotechnology deals with the synthesis of nanoparticles of different chemical compositions,sizes and controlled monodispersity.Currently,there is a growing need to develop environment...An important area of research in nanotechnology deals with the synthesis of nanoparticles of different chemical compositions,sizes and controlled monodispersity.Currently,there is a growing need to develop environmentally benign nanoparticle synthesis in which no toxic chemicals are used in the synthesis protocol.Palladium nanoparticles(Pd Np) are of interest because of their catalytic properties and affinity for hydrogen.Our protocol for the phyto-synthesis of Pd Np under moderate p H and room temperature offers a new means to develop environmentally benign nanoparticles.Solanum trilobatum is enlightened in our present study as it is enriched with phytochemicals to reduce palladium chloride ions.Poly MVA a dietary supplement based on the nontoxic chemotherapeutic lipoic acid-palladium complex(LA-Pd) is been hypothesized as the new paradigm of cancer therapy.Hence forth we successfully conjugated lipoic acid(S-Pd Np-LA) and vitamins(S-Pd Np-Vitamin-LA) to palladium nanoparticles synthesised from Solanum trilobatum leaf extract.These nanoparticles(S-Pd Np,S-Pd Np-LA,S-Pd Np-Vitamin-LA) were characterized with UV-Vis Spectroscopy,SEM and FTIR analysis,which revealed that S-Pd Np are polydisperse and of different morphologies ranging from 60?70 nm(S-Pd Np),65?80 nm(S-Pd Np-LA) and 75?100 nm(S-Pd Np-Vitamin-LA) in size.展开更多
Dislocation structures in polycrystalline Ni 3Al alloy doped with palladium deformed at room temperature have been investigated by transmission electron microscopy. The structure consists mainly of dislocations dissoc...Dislocation structures in polycrystalline Ni 3Al alloy doped with palladium deformed at room temperature have been investigated by transmission electron microscopy. The structure consists mainly of dislocations dissociated into a /2〈011〉 super partials bounding an anti phase boundary (APB). Dislocations dissociated into a /3〈112〉 super Shockley partials bounding a superlattice intrinsic stacking fault (SISF) are also common debris. The majority of the SISFs are truncated loops, i.e. the partials bounding the SISF are of similar Burgers vector. These faulted loops are generated from APB coupled dislocations, according to a mechanism for formation of SISFs proposed by Suzuki et al , and recently modified by Chiba et al . The APB energies for {111} and {010} slip planes are measured to be 144±20 mJ/m 2 and 102±11 mJ/m 2 respectively, and the SISF energy has been estimated to be 12 mJ/m 2 in this alloy. It is concluded that the dislocation structure in Ni 74.5 Pd 2Al 23.5 alloy deformed at room temperature is similar to that in binary Ni 3Al, and the difference in fault energies between these two alloys is small. Thus, it seems unlikely that the enhancement of ductility of Ni 74.5 Pd 2Al 23.5 results from only such a small decrease of the ordering energy of the alloy. SISF bounding dislocations also have no apparent influence on the ductilization of Ni 74.5 Pd 2Al 23.5 alloy.展开更多
Pd/YZ-Al2O3 (Y and Zr modified Al2O3, and hereafter, labelled as A1) catalysts with 4 wt% additive CeO2 and/or La2O3 were prepared and characterized by X-ray photoelectron spectroscopy (XPS), NO-temperature progra...Pd/YZ-Al2O3 (Y and Zr modified Al2O3, and hereafter, labelled as A1) catalysts with 4 wt% additive CeO2 and/or La2O3 were prepared and characterized by X-ray photoelectron spectroscopy (XPS), NO-temperature programmed desorption (NO-TPD), Nz-adsorption/desorption (Branauer-Emmet-Teller BET method), X-ray diffraction (XRD) and CO-chemisorption. Catalytic activities for CH4, CO and NO conversion were tested in a gas mixture simulated the emissions from natural gas vehicles (NGVs) operated under stoichiometric conditions. The results indicated that all catalysts exhibited excellent catalytic performances for CH4 and CO oxidation and the promoting effect of CeO2 or La2O3 was significant for NO conversion. XPS results showed that the electron density around Pd was increased by CeO2 and/or La2O3, the binding energy of Pd 3d decreased as the order: Pd/Al 〉 Pd/Ce/Al 〉 Pd/La/Al 〉 Pd/CeLa/Al. The electron-rich Pd showed Rh-like catalytic properties which exhibited good activity for the reduction of NO. NO-TPD results showed that the addition of CeO2 and/or La2O3 increased NO adsorption on surface, and promoted the conversion of NO.展开更多
A series of solvent-stabilized palladium colloidal nanoparticles were prepared via thermal decomposition of palladium acetate methylisobutylketone (MIBK) solution in the presence of alkali and alcohol with microwave i...A series of solvent-stabilized palladium colloidal nanoparticles were prepared via thermal decomposition of palladium acetate methylisobutylketone (MIBK) solution in the presence of alkali and alcohol with microwave irradiation. The colloidal nanoparticles were characterized with TEM, XPS and XRD. The average diameters of nanoparticles increase from 30 to 40 nm with the increase in concentration of palladium acetate. TEM and XRD observation demonstrated that the palladium colloidal nanoparticles were clusters agglomerated from hundreds of smaller palladium crystallines with size of 3-4 nm. The influence of the concentrations of alkali and alcohol to the particle size was also discussed.展开更多
The rare earths of ytterbium, lanthanum, praseodymium, neodymium and their binary mixtures were respectively added into the traditional electroless plating solution to prepare thin palladium film on the inner surface ...The rare earths of ytterbium, lanthanum, praseodymium, neodymium and their binary mixtures were respectively added into the traditional electroless plating solution to prepare thin palladium film on the inner surface of porous ceramic tube. The experimental results shows that the addition of rare earths increases palladium deposition rates and the binary mixtures are superior to the single rare earths and the mixture of ytterbium-lanthanum is the most efficient. Adding the mixture of ytterbium-lanthanum can also reduce the plating temperature by 10 ~ 20℃, shrink the metal crystal size and improve the film densification compared to those by traditional electroless plating. A thin palladium film with 5μm was prepared and the film made a highly pure hydrogen with a molar fraction of more than 99.97% from a H2-N2 gas mixture. More attentions were paid to analyze the physical and chemical behaviors of the rare earths in palladium film preparation.展开更多
The Fengshan porphyry-skarn copper-molybdenum (Cu-Mo) deposit is located in the south-eastern Hubei Province in east China. Cu-Mo mineralization is hosted in the Fengshan granodiorite porphyry stock that intruded th...The Fengshan porphyry-skarn copper-molybdenum (Cu-Mo) deposit is located in the south-eastern Hubei Province in east China. Cu-Mo mineralization is hosted in the Fengshan granodiorite porphyry stock that intruded the Triassic Daye Formation carbonate rocks in the early Cretaceous (-140 Ma), as well as the contact zone between granodiorite porphyry stock and carbonate rocks, forming the porphyry-type and skaru-type association. The Fengshan granodiorite stock and the immediate country rocks are strongly fractured and intensely altered by hydrothermal fluids. In addition to intense skarn alteration, the prominent alteration types are potassic, phyllic, and propylitic, whereas argiilation is less common. Mineralization occurs as veins, stock works, and disseminations, and the main ore minerals are chalcopyrite, pyrite, molybdenite, bornite, and magnetite. The contents of palladium, platinum and gold (Pd, Pt and Au) are determined in nine samples from fresh and mineralized granodiorite and different types of altered rocks. The results show that the Pd content is systematically higher than Pt, which is typical for porphyry ore deposits worldwide. The Pt content ranges from 0.037 tol.765 ppb, and the Pd content ranges between 0.165 and 17.979 ppb. Pd and Pt are more concentrated in porphyry mineralization than skarn mineralization, and have negative correlations with Au. The reconnaissance study presented here confirms the existence of Pd and Pt in the Fengshan porphyry-skarn Cu-Mo deposit. When compared with intracontinent and island arc geotectonic settings, the Pd, Pt, and Au contents in the Fengshan porphyry Cu-Mo deposit in the intracontinent is lower than the continental margin types and island are types. A combination of available data indicates that Pd and Pt were derived from oxidized alkaline magmas generated by the partial melting of an enriched mantle source.展开更多
文摘New heteroleptic and homoleptic complexes of the type[Pd(4,5-dmbipy)C12], [Pd(4,5-dmbipy)L2], and [Pd(4,5-dimebipy)2]2+ (L = Pyridine or 4-methylpyridine(4-picoline), bipy = 2,2'-bipyridine, and 4,5-dimebipy = 4,5-dimethyl-2,2'-bipyridine) were synthesized and characterized by IH NMR and elemental analysis. The crystal structure of bis(4-methylpyridine)-4,5- dimethyl-2,2'-bipyridinepalladium(II)perchlorate [Pd(4,5-dmbipy)(4-pic)2](CIO4)2 was also determined by single crystal X-ray diffraction. This complex crystallized in the triclinic crystal system and space group PI with a = 9.562 (2), b = 11.326 (4), c = 15.0120 (10) A°; α = 70.940°, β= 77.60 (2), γ= 67.86 (2) and z = 4. The Pd (II) in square planar environment showed a small distortion towards tetrahedral through one coordinated bipyridine ring twisting with respect to the other.
基金financial support provided by Liaoning Revitalization Talents Program(XLYC2007171)the Natural Science Foundation of Liaoning Province(2021-MS-321)Research funding project of Liaoning Provincial Education Department(LJKZZ20220086)。
文摘With the development of hydrogen energy,palladium-based membranes have been widely used in hydrogen separation and purification.However,the poor chemical stability of palladium composite membranes limits their commercial applications.In this study,a zeolite-palladium composite membrane with a sandwich-like structure was obtained by using a TS-1 zeolite film grown on the surface of palladium membrane.The membrane microstructure was characterized by SEM and EDX.The effects of the TS-1 film on the hydrogen permeability and stability of palladium composite membrane were investigated in details.Benefited from the protection of the TS-1 zeolite film,the stability of palladium composite membrane was enhanced.The results indicate that the TS-1-Pd composite membrane was stable after eight cycles of the temperature exchange cycles between 773 K and 623 K.Especially,the loss of hydrogen permeance for TS-1-Pd composite membrane was much smaller than that of the pure palladium membrane when the membrane was tested in the presence of C3H6atmosphere.It indicated that the TS-1-Pd composite membrane had better chemical stability in comparison with pure palladium membrane,owing to its sandwich-like structure.This work provides an efficient way for the deposition of zeolite film on palladium membrane to enhance the membrane stability.
基金the National Natural Science foundation of China(22379053 and 21878127)China Postdoctoral Science Foundation(2022M711358).We also thank Xu Fangping for assistance in HRTEM characterization from the Central Laboratory of School of Chemical and Material Engineering of Jiangnan University.
文摘The selective removal of trace acetylene in ethylene feed gas is of great significance in the petrochemicalindustry;however, there are still challenges in designing and developing high-performance catalysts. Here, a MOFassistedencapsulation strategy was adopted for the precise synthesis of diatomic Pd2 sites on a ZnO support. When usedfor the acetylene semi-hydrogenation reaction, the dual-atom Pd2-ZnO catalyst exhibited improved catalytic performance,achieving complete conversion of acetylene at 125 °C with an 89% selectivity to ethene, as compared to Pd single-atom andnanoparticles. This enhancement was mainly attributed to the catalyst’s ability to dissociate H2 and facilitate the desorptionof intermediate C2H4. Moreover, the strong interaction between the support and the diatomic Pd sites was responsible for thecatalyst’s excellent stability during the long-term reaction.
基金Project(2023JJ10005)supported by the Natural Science Foundation of Hunan Province,ChinaProjects(51772082,51804106)supported by the National Natural Science Foundation of China。
文摘In practical applications,noble metal doping is often used to prepare high performance gas sensors,but more noble metal doping will lead to higher preparation costs.In this study,CeO_(2)/ZnO-Pd with low palladium content was prepared by ultrasonic method with fast response and high selectivity for acetone sensing.With the same amount of palladium added,the selectivity coefficient of CeO_(2)/ZnO-Pd is 1.88 times higher than that of the stirred sensor.Compared with the pure PdO-doped CeO_(2)/ZnO-PdO material,the content of Pd in CeO_(2)/ZnO-PdO is about 30%of that in CeO_(2)/ZnO-PdO,but the selectivity coefficient for acetone is 2.56 times higher.The CeO_(2)/ZnO-Pd sensor has a higher response(22.54)to 50×10^(−6) acetone at 300℃and the selectivity coefficient is 2.57 times that of the CeO_(2)/ZnO sensor.The sensor has a sub-second response time(0.6 s)and still has a 2.36 response to 330×10^(−9) of acetone.Ultrasonic doping makes Pd particles smaller and increases the contact area with gas.Meanwhile,the composition of n-p-n heterojunction and the synergistic effect of Pd/PdO improve the sensor performance.It shows that ultrasonic Pd doping provides a way to improve the utilization rate of doped metals and prepare highly selective gas sensors.
基金The National Key Research and Development Program of Ministry of Science and Technology(No.2022YFA1504602)Natural Science Foundation of Jiangsu Province(No.BK20211094)National Natural Science Foundation of China(No.22302214,21972152,U22B20137).
文摘Carbonylation reactions,crucial for carbonyl group incorporation,struggle with the inherent complexity of achieving selective mono-or double-carbonylation on single substrates,often due to competing reaction pathways.Herein,our study introduces a strategy employing palladium amides,harnessing their unique reactivity control,to direct the selective carbonylation of amines for the targeted synthesis of urea and oxamide derivatives.The palladium amide structure was elucidated using single-crystal X-ray diffraction.Controlled experiments and cyclic voltammetry studies further elucidate that the oxidation of palladium amide or its insertion into a carbonyl group diverges into distinct pathways.By employing sodium percarbonate as an eco-friendly oxidant and base,we have successfully constructed a switchable carbonylation system co-catalyzed by palladium and iodide under room temperature.The utilizing strategy in this study not only facilitates effective control over reaction selectivity but also mitigates the risk of explosions,a critical safety concern in traditional carbonylation methods.
基金financially supported by National Natural Science Foundation of China (Nos. 12075032 and 12105021)Beijing Municipal Natural Science Foundation (Nos.8222055 and 2232061)+1 种基金Yunnan Police College Project (No. YJKF002)Beijing Institute of Graphic Communication Project (No. Ec202207)。
文摘Supported Pd catalyst is an important noble metal material in recent years due to its high catalytic performance in CO_(2)hydrogenation.A fluidized-bed plasma assisted atomic layer deposition(FP-ALD) process is reported to fabricate Pd nanoparticle catalyst over γ-Al_(2)O_(3)or Fe_(2)O_(3)/γ-Al_(2)O_(3)support,using palladium hexafluoroacetylacetonate as the Pd precursor and H_(2)plasma as counter-reactant.Scanning transmission electron microscopy exhibits that highdensity Pd nanoparticles are uniformly dispersed over Fe_(2)O_(3)/γ-Al_(2)O_(3)support with an average diameter of 4.4 nm.The deposited Pd-Fe_(2)O_(3)/γ-Al_(2)O_(3)shows excellent catalytic performance for CO_(2)hydrogenation in a dielectric barrier discharge reactor.Under a typical condition of H_(2)to CO_(2)ratio of 4 in the feed gas,the discharge power of 19.6 W,and gas hourly space velocity of10000 h^(-1),the conversion of CO_(2)is as high as 16.3% with CH_(3)OH and CH4selectivities of 26.5%and 3.9%,respectively.
基金financially supported by the National Natural Science Foundation of China(21674068,52173133,52161145402)the Sichuan Science and Technology Department(2021YFH0180)。
文摘Covalent organic frameworks(COFs)have emerged as a class of promising supports for electrocatalysis because of their advantages including good crystallinity,highly ordered pores,and structural diversity.However,their poor conductivity represents the main obstruction to their practical application.Here,we reported a novel synthesis strategy for synergistically endowing a triphenylamine-based COFs with improved electrical conductivity and excellent catalytic activity for oxygen reduction,via the in-situ redox deposition and confined growth of palladium nanoparticles inside the porous structure of COFs using reductive triphenylamine frameworks as reducing agent;meanwhile,the triphenylamine unit was oxidized to radical cation structure and affords radical cation COFs with conductivity as high as3.2*10^(-1) S m^(-1).Such a uniform confine palladium nanoparticle on highly conductive COFs makes it an efficient electrocatalyst for four-electron oxygen reduction reaction(4e-ORR),showing excellent activities and fast kinetics with a remarkable half-wave potential(E_(1/2))of 0.865 V and an ultralow Tafel slope of 39.7 mV dec^(-1) in alkaline media even in the absence of extra commercial conductive fillers.The generality of this strategy was proved by preparing the different metal and metal alloy nanoparticles supported on COFs(Au@COF,Pt@COF,AuPd@COF,AgPd@COF,and PtPd@COF)using reductive triphenylamine frameworks as reducing agent.This work not only provides a facile strategy for the fabrication of highly conductive COF supported ORR electrocatalysts,but also sheds new light on the practical application of Zn-air battery.
基金the support of the National Natural Science Foundation of China (20222809, 21978146)TsinghuaFoshan Innovation Special Fund (2021THFS0214)。
文摘Suzuki-Miyaura reaction of aryl halides with phenylboronic acid using a heterogeneous palladium catalyst based on activated carbons(AC) was systematically investigated in this work. Two different reaction modes(batch procedure and continuous-flow procedure) were used to study the variations of reaction processing. The heterogeneous catalysts presented excellent reactivity and recyclability for iodobenzene and bromobenzene substrates in batch mode, which can be attributed to stabilization of Pd nanoparticles by the thiol and amino groups on the AC supports. However, significant dehalogenation in the reaction mixture and Pd leaching from the heterogeneous catalysts were observed in continuous-flow mode.This unique phenomenon in continuous-flow mode resulted in a dramatic decline in reaction selectivity and durability of heterogeneous catalysts comparing with that of batch mode. In addition, the heterogeneous Pd catalysts with thiol-and amino-modified AC supports exhibited different reactivity and durability in batch and continuous-flow mode owing to the difference of interaction between Pd species and AC supports.
文摘【目的】以葡萄汁为原料,植物乳杆菌Zhang-LL及马克斯克鲁维酵母M3为发酵菌株,优化葡萄汁酵素的发酵工艺条件。【方法】比较植物乳杆菌Zhang-LL和马克斯克鲁维酵母M3在葡萄汁中的不同接种方式对益生菌活菌数和DPPH清除率的影响,筛选葡萄汁酵素最优接种发酵方式。进一步通过单因素试验及响应面试验,优化葡萄汁酵素最佳发酵工艺条件。【结果】植物乳杆菌Zhang-LL和马克斯克鲁维酵母M3共发酵可以显著提高葡萄汁酵素中益生菌活菌数和DPPH清除率;植物乳杆菌Zhang-LL和马克斯克鲁维酵母M3共发酵的最佳工艺条件为:按照1∶1比例接种,初始接种量5.00 lg CFU/mL、大豆蛋白胨添加量0.46%、34℃发酵18 h,植物乳杆菌Zhang-LL活菌数达6.60×10^(8)CFU/mL,马克斯克鲁维酵母M3活菌数达8.20×10^(7)CFU/mL,酵素DPPH清除率85.25%。【结论】乳酸菌与酵母菌协同发酵,在缩短发酵时间的同时还能达到较高的活菌数和DPPH清除率,可为葡萄汁酵素的工业化制备及后续多功能产品研发提供理论依据。
基金supported by the National Natural Science of Foundation of China(21676140)the fund from the State Key Laboratory of Materials-Oriented Chemical Engineering(ZK201402)the Project of Priority Academic Program Development(PAPD) of Jiangsu Higher Education Institutions~~
文摘Palladium nanoparticles supported on cross-linked polyaniline with bulky phosphorus ligands were developed.These catalysts showed high efficiency in the Suzuki-Miyaura reaction of aryl chlorides and bromides with phenylboronic acids.Aryl chlorides and bromides with functional groups,such as CN,MeO,CHO,MeCO and NO_2,were converted to the corresponding biphenyls in high yields with catalyst loading.Additionally,the catalysts combined high activity with good reusability;they could be used at least five times for the Suzuki-Miyaura coupling reaction.
基金supported by the National Natural Science Foundation of China(21473058,21273077)~~
文摘The neutral palladium(Ⅱ) complex bis-[1-(5'-diphenylphosphinothiazol-2'-yl)-imidazolyl]dichloropalladium(Ⅱ)(1A) ligated by thiazolylimidazolyl-based phosphine(L1) in which thiazolylimidazolyl acted as an S- and N-donor provider with weak coordinating nature,and the ionic complex bis-[1-(5'-diphenylphosphinothiazol-2'-yl)-3-methylimidazolium]dichloropalladium(Ⅱ) trifluoromethanesulfonate(2A) ligated by thiazolylimidazolium-based phosphine(L2) after quaternization of L1 using methyl trifluoromethanesulphonate were synthesized.It was found that the introduced positive charges and strong electron-withdrawing effect in 2A not only led to changes in the configuration and structural stability of the complex,but also lowered its catalytic performance in carbonylative Sonogashira reactions.These effects reveal the important role of the N-donor in 1A.In addition,as an ionic palladium complex,2A combined with the room-temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate could be recycled eight times as the catalyst in carbonylative Sonogashira reactions without detectable metal leaching.
文摘An important area of research in nanotechnology deals with the synthesis of nanoparticles of different chemical compositions,sizes and controlled monodispersity.Currently,there is a growing need to develop environmentally benign nanoparticle synthesis in which no toxic chemicals are used in the synthesis protocol.Palladium nanoparticles(Pd Np) are of interest because of their catalytic properties and affinity for hydrogen.Our protocol for the phyto-synthesis of Pd Np under moderate p H and room temperature offers a new means to develop environmentally benign nanoparticles.Solanum trilobatum is enlightened in our present study as it is enriched with phytochemicals to reduce palladium chloride ions.Poly MVA a dietary supplement based on the nontoxic chemotherapeutic lipoic acid-palladium complex(LA-Pd) is been hypothesized as the new paradigm of cancer therapy.Hence forth we successfully conjugated lipoic acid(S-Pd Np-LA) and vitamins(S-Pd Np-Vitamin-LA) to palladium nanoparticles synthesised from Solanum trilobatum leaf extract.These nanoparticles(S-Pd Np,S-Pd Np-LA,S-Pd Np-Vitamin-LA) were characterized with UV-Vis Spectroscopy,SEM and FTIR analysis,which revealed that S-Pd Np are polydisperse and of different morphologies ranging from 60?70 nm(S-Pd Np),65?80 nm(S-Pd Np-LA) and 75?100 nm(S-Pd Np-Vitamin-LA) in size.
文摘Dislocation structures in polycrystalline Ni 3Al alloy doped with palladium deformed at room temperature have been investigated by transmission electron microscopy. The structure consists mainly of dislocations dissociated into a /2〈011〉 super partials bounding an anti phase boundary (APB). Dislocations dissociated into a /3〈112〉 super Shockley partials bounding a superlattice intrinsic stacking fault (SISF) are also common debris. The majority of the SISFs are truncated loops, i.e. the partials bounding the SISF are of similar Burgers vector. These faulted loops are generated from APB coupled dislocations, according to a mechanism for formation of SISFs proposed by Suzuki et al , and recently modified by Chiba et al . The APB energies for {111} and {010} slip planes are measured to be 144±20 mJ/m 2 and 102±11 mJ/m 2 respectively, and the SISF energy has been estimated to be 12 mJ/m 2 in this alloy. It is concluded that the dislocation structure in Ni 74.5 Pd 2Al 23.5 alloy deformed at room temperature is similar to that in binary Ni 3Al, and the difference in fault energies between these two alloys is small. Thus, it seems unlikely that the enhancement of ductility of Ni 74.5 Pd 2Al 23.5 results from only such a small decrease of the ordering energy of the alloy. SISF bounding dislocations also have no apparent influence on the ductilization of Ni 74.5 Pd 2Al 23.5 alloy.
基金supported by the Key Program of National Natural Science Foundation of China (20333030)the National High Technology Research and Development Program of China (863 Program, No. 2006AA06Z347)the National Natural Science Foundation of China (No. 20773090)
文摘Pd/YZ-Al2O3 (Y and Zr modified Al2O3, and hereafter, labelled as A1) catalysts with 4 wt% additive CeO2 and/or La2O3 were prepared and characterized by X-ray photoelectron spectroscopy (XPS), NO-temperature programmed desorption (NO-TPD), Nz-adsorption/desorption (Branauer-Emmet-Teller BET method), X-ray diffraction (XRD) and CO-chemisorption. Catalytic activities for CH4, CO and NO conversion were tested in a gas mixture simulated the emissions from natural gas vehicles (NGVs) operated under stoichiometric conditions. The results indicated that all catalysts exhibited excellent catalytic performances for CH4 and CO oxidation and the promoting effect of CeO2 or La2O3 was significant for NO conversion. XPS results showed that the electron density around Pd was increased by CeO2 and/or La2O3, the binding energy of Pd 3d decreased as the order: Pd/Al 〉 Pd/Ce/Al 〉 Pd/La/Al 〉 Pd/CeLa/Al. The electron-rich Pd showed Rh-like catalytic properties which exhibited good activity for the reduction of NO. NO-TPD results showed that the addition of CeO2 and/or La2O3 increased NO adsorption on surface, and promoted the conversion of NO.
基金The project is partially supported by the Natural Sci-ence Foundation of Hubei Province under contract No.2003ABA072.
文摘A series of solvent-stabilized palladium colloidal nanoparticles were prepared via thermal decomposition of palladium acetate methylisobutylketone (MIBK) solution in the presence of alkali and alcohol with microwave irradiation. The colloidal nanoparticles were characterized with TEM, XPS and XRD. The average diameters of nanoparticles increase from 30 to 40 nm with the increase in concentration of palladium acetate. TEM and XRD observation demonstrated that the palladium colloidal nanoparticles were clusters agglomerated from hundreds of smaller palladium crystallines with size of 3-4 nm. The influence of the concentrations of alkali and alcohol to the particle size was also discussed.
基金Project supported by Science and Technology Committee of Jiangxi Province
文摘The rare earths of ytterbium, lanthanum, praseodymium, neodymium and their binary mixtures were respectively added into the traditional electroless plating solution to prepare thin palladium film on the inner surface of porous ceramic tube. The experimental results shows that the addition of rare earths increases palladium deposition rates and the binary mixtures are superior to the single rare earths and the mixture of ytterbium-lanthanum is the most efficient. Adding the mixture of ytterbium-lanthanum can also reduce the plating temperature by 10 ~ 20℃, shrink the metal crystal size and improve the film densification compared to those by traditional electroless plating. A thin palladium film with 5μm was prepared and the film made a highly pure hydrogen with a molar fraction of more than 99.97% from a H2-N2 gas mixture. More attentions were paid to analyze the physical and chemical behaviors of the rare earths in palladium film preparation.
基金supported by the National Natural Science Foundation of China(No. 40902026)Research Foundation for Outstanding Young Teachers,China University of Geosciences (Wuhan)(No.CUGQNL0735)
文摘The Fengshan porphyry-skarn copper-molybdenum (Cu-Mo) deposit is located in the south-eastern Hubei Province in east China. Cu-Mo mineralization is hosted in the Fengshan granodiorite porphyry stock that intruded the Triassic Daye Formation carbonate rocks in the early Cretaceous (-140 Ma), as well as the contact zone between granodiorite porphyry stock and carbonate rocks, forming the porphyry-type and skaru-type association. The Fengshan granodiorite stock and the immediate country rocks are strongly fractured and intensely altered by hydrothermal fluids. In addition to intense skarn alteration, the prominent alteration types are potassic, phyllic, and propylitic, whereas argiilation is less common. Mineralization occurs as veins, stock works, and disseminations, and the main ore minerals are chalcopyrite, pyrite, molybdenite, bornite, and magnetite. The contents of palladium, platinum and gold (Pd, Pt and Au) are determined in nine samples from fresh and mineralized granodiorite and different types of altered rocks. The results show that the Pd content is systematically higher than Pt, which is typical for porphyry ore deposits worldwide. The Pt content ranges from 0.037 tol.765 ppb, and the Pd content ranges between 0.165 and 17.979 ppb. Pd and Pt are more concentrated in porphyry mineralization than skarn mineralization, and have negative correlations with Au. The reconnaissance study presented here confirms the existence of Pd and Pt in the Fengshan porphyry-skarn Cu-Mo deposit. When compared with intracontinent and island arc geotectonic settings, the Pd, Pt, and Au contents in the Fengshan porphyry Cu-Mo deposit in the intracontinent is lower than the continental margin types and island are types. A combination of available data indicates that Pd and Pt were derived from oxidized alkaline magmas generated by the partial melting of an enriched mantle source.