Nickel-palladium film on p-Si prepared by potential -controlled electrodeposition has much better adherence than that deposited by other methods .To reveal the reasons of this effect ,X-ray photoelectron spectroscopy ...Nickel-palladium film on p-Si prepared by potential -controlled electrodeposition has much better adherence than that deposited by other methods .To reveal the reasons of this effect ,X-ray photoelectron spectroscopy (XPS) combmed with Ar+sput tering was used to investigate the interface of NiPd /Si .The results showed that dramatic interdiffusion of Ni, Pd and Si had occurred at atmospheric temperature .On the XPS spectra of mckel and palladium ,there are two kinds of binding energy ,contributed by pure metals and metal silicide respectively. NiSi, PdSi and Pd2Si were formed at the interface. Both of the electric field on the surface and the H atoms in the metal lattice have the possibility to promote reactions between nickel or palladium and silicon .展开更多
The catalytic performance during the 1-butyne hydrogenation using two reduced Al_(2) O_(3)-supported Pdbased catalysts was carried out in a total recirculation system with an external fixed-bed reactor.The lab-prepare...The catalytic performance during the 1-butyne hydrogenation using two reduced Al_(2) O_(3)-supported Pdbased catalysts was carried out in a total recirculation system with an external fixed-bed reactor.The lab-prepared egg-shell NiPd/CeO_(2)-Al_(2) O_(3) catalyst(NiPdCe) with Pd loading=0.5 wt%,Ni/Pd atomic ratio=1 and CeO_(2) loading=3 wt% was synthesized and characterized,and it was compared with an egg-shell Al_(2) O_(3)-supported Pd based commercial catalyst(PdCC).The reduced catalysts were characterized by X-ray diffraction,X-ray photoelectron spectroscopy,and high-resolution transmission electron microscopy.The textural characteristics and ammonia temperature-programmed desorption profiles of the fresh(unreduced) catalysts were also obtained.Both catalysts show high 1-butyne conversion and selectivity to 1-butene,but the catalysts also present important differences between hydroisomerizing and hydrogenating capabilities.NiPdCe catalyst shows higher capability for hydroisomerization reactions,while the PdCC catalyst exhibits higher hydrogenating capability.The observed catalytic performances can be interesting for some industrial processes and can provide a guideline for the development of a Pd-based catalyst with specific catalytic properties.展开更多
The presence of persistent pollutants in water poses a severe environmental threat,driving an urgent need for efficient and eco-friendly remediation strategies.In response,the scientific community is increasingly focu...The presence of persistent pollutants in water poses a severe environmental threat,driving an urgent need for efficient and eco-friendly remediation strategies.In response,the scientific community is increasingly focused on developing catalytic processes that maximize efficiency while minimizing environmental impact.In this context,we introduce recyclable catalysts based on NiPd nanoparticles(NPs)that feature tunable phase distributions and compositions.By varying Pd doping levels through Reactive Laser Ablation in Liquids(RLAL),we precisely control the catalytic and magnetic properties of these NPs.Notably,a nanocatalyst featuring the NiPd alloyed phase exhibits exceptional catalytic performance,achieving a turnover frequency of 3680 h^(-1) and 98.5%selectivity in the model transformation of 4-nitrophenol into 4-aminophenol.Additionally,it demonstrates remarkable efficiency in the chemoselective hydrogenation of various nitroarenes to functionalized anilines under mild conditions(atmospheric H_(2) pressure,33℃).Furthermore,the synergistic properties arising from the internal structure of these NPs allow them to surpass the performance of nanocatalysts made from their monometallic counterparts and simple mixtures.Overall,this study represents a significant advancement in the precise control of nanocatalyst synthesis and their associated physicochemical properties,paving the way for more efficient redox catalytic protocols,including industrially demanding hydrogenation reactions.展开更多
We report herein an innovative design and synthesis of a novel multifunctional nanocatalyst for the transfer hydrogenation(TH)of nitroarenes and olefins using water as a hydrogen source and solvent.The presented nanoc...We report herein an innovative design and synthesis of a novel multifunctional nanocatalyst for the transfer hydrogenation(TH)of nitroarenes and olefins using water as a hydrogen source and solvent.The presented nanocatalyst is composed of NiPd alloy nanoparticles(NPs)supported on reduced graphene oxide(rGO)decorated with metallic Al NPs(Al-rGO/NiPd).In the catalyst,metallic Al NPs serve as the sacrificing agent for hydrogen generation via the Al-H_(2)O reaction,NiPd NPs act as the catalyst for the transfer of the generated hydrogen to the unsaturated compounds,and rGO functions as both a support material and stabilizer for the NPs.Among all tested catalysts,Al-rGO/Ni_(40)Pd_(60)nanocatalysts are found to be the most efficient and selective catalysts in the presented TH of nitroarenes(14 examples)and olefins(14 examples)with yields reaching up to 99%under the optimized reaction conditions.Additionally,Al-rGO/Ni_(40)Pd_(60)nanocatalysts are recyclable catalysts in the TH reactions by catalyzing ten consecutive runs in the TH of nitrobenzene without a significant drop in their initial catalytic activity,which is the first example in this regard.Last but not least,the current transfer hydrogenation protocol provides selectivity for the reduction of only the-NO_(2)group of nitroarenes bearing iodo or bromo substituents on the same aromatic ring.This study is the first example of a TH protocol that employs an Al-modified nanomaterial serving as both a hydrogen generator and reusable catalyst in water without using any additional hydrogen source.展开更多
Bulk nanoporous(np)metallic actuators have attracted increasing attention due to their large strain and low stimulation voltage.However,studies focusing upon the combined effect of composition and structure on the act...Bulk nanoporous(np)metallic actuators have attracted increasing attention due to their large strain and low stimulation voltage.However,studies focusing upon the combined effect of composition and structure on the actuation performance of metallic actuators are relatively scarce,and its underlying mechanism needs to be clarified Herein,a series of bulk np-NiPd samples with differen compositions and microstructures were fabricated using a dealloying-coarsening-dealloying strategy and chargecontrolled electrochemical dealloying,and the process involves only one component of precursor alloy.It has been found that the np-NiPd cubes show a composition/structure-dependent mechanical property and electrochemical actuation performance.Specially,the npNi_(70)Pd_(30)sample with a homogeneously porous structure and good network connectivity exhibits significantly larger strain amplitude and faster strain rate than other hierarchically porous NiPd samples(np-Ni_(50)Pd_(50)and npNi_(20)Pd_(80)).Moreover,the np-Ni_(70)Pd_(30)sample demonstrates good actuation stability with high strain retention after hundreds of cycles.Notably,the maximum strain amplitude(1.17%)is even comparable to that of advanced leadfree piezoceramic,and the maximum strain rate exceeds those of many reported metallic actuator materials.Our work indicates that good network connectivity plays a vita role in facilitating large/fast strain response in metallic actuators.展开更多
A couple with a proband child of GJB2 （encoding the gap junction protein connexin 26）-associated hearing impairment and a previous pregnancy miscarriage sought for a reproductive solution to bear a healthy child. Ou...A couple with a proband child of GJB2 （encoding the gap junction protein connexin 26）-associated hearing impairment and a previous pregnancy miscarriage sought for a reproductive solution to bear a healthy child. Our study aimed to develop a cus- tomized preconception-to-neonate care trajectory to fulfill this clinical demand by integrating preimplantation genetic diagno- sis （PGD）, noninvasive prenatal testing （NIPT）, and noninvasive prenatal diagnosis （N1PD） into the strategy. Auditory and ge- netic diagnosis of the proband child was carried out to identify the disease causative mutations. The couple then received in-vitro-fertilization treatment, and eight embryos were obtained for day 5 biopsy. PGD was performed by short-tandem-repeat linkage analysis and Sanger sequencing of GJB2 gene. Transfer of a GJB2c.235delC heterozygous embryo resulted in a sin- gleton pregnancy. At the 13th week of gestation, genomic DNA （gDNA） from the trio family and cell-free DNA （cfDNA） from maternal plasma were obtained for assessment of fetal chromosomal aneuploidy and GJB2 mutations. NIPT and NIPD showed the absence of chromosomal aneuploidy and GJB2-associated disease in the fetus, which was later confirmed by inva- sire procedures and postnatal genetic/auditory diagnosis. This strategy successfully prevented the transmission of hearing im- pairment in the newborn, thus providing a valuable experience in reproductive management of similar cases and potentially other monogenic disorders.展开更多
文摘Nickel-palladium film on p-Si prepared by potential -controlled electrodeposition has much better adherence than that deposited by other methods .To reveal the reasons of this effect ,X-ray photoelectron spectroscopy (XPS) combmed with Ar+sput tering was used to investigate the interface of NiPd /Si .The results showed that dramatic interdiffusion of Ni, Pd and Si had occurred at atmospheric temperature .On the XPS spectra of mckel and palladium ,there are two kinds of binding energy ,contributed by pure metals and metal silicide respectively. NiSi, PdSi and Pd2Si were formed at the interface. Both of the electric field on the surface and the H atoms in the metal lattice have the possibility to promote reactions between nickel or palladium and silicon .
基金Project supported by the Fondo Nacional de Ciencia,Tecnología e Innovación(FONACIT-G-2005000437)Universidad Nacional de La Plata(UNLP-PID1226)+1 种基金Consejo Nacional de Investigaciones Científicas y Técnicas(CONICET-PIP0018)Agenda Nacional de Promoción Cientifica y Tecnológica(ANPCyT-PICT 2015/3546)。
文摘The catalytic performance during the 1-butyne hydrogenation using two reduced Al_(2) O_(3)-supported Pdbased catalysts was carried out in a total recirculation system with an external fixed-bed reactor.The lab-prepared egg-shell NiPd/CeO_(2)-Al_(2) O_(3) catalyst(NiPdCe) with Pd loading=0.5 wt%,Ni/Pd atomic ratio=1 and CeO_(2) loading=3 wt% was synthesized and characterized,and it was compared with an egg-shell Al_(2) O_(3)-supported Pd based commercial catalyst(PdCC).The reduced catalysts were characterized by X-ray diffraction,X-ray photoelectron spectroscopy,and high-resolution transmission electron microscopy.The textural characteristics and ammonia temperature-programmed desorption profiles of the fresh(unreduced) catalysts were also obtained.Both catalysts show high 1-butyne conversion and selectivity to 1-butene,but the catalysts also present important differences between hydroisomerizing and hydrogenating capabilities.NiPdCe catalyst shows higher capability for hydroisomerization reactions,while the PdCC catalyst exhibits higher hydrogenating capability.The observed catalytic performances can be interesting for some industrial processes and can provide a guideline for the development of a Pd-based catalyst with specific catalytic properties.
基金supported by the European Union’s Horizon Europe Widera 2021 Programme under the SURRI project,Grant Agreement No.101079345support from the European Union’s Horizon Europe Research and Innovation Programme under Marie Sklodowska-Curie grant agreements LYMON number 101151748.M.C.thanks the project DKRVO(RP/CPS/2024-28/007)+4 种基金supported by the Ministry of Education,Youth and Sports of the Czech Republic.I.S.thanks the Gen-T Plan of the Generalitat Valenciana through the program“Suport a l’estabilitzacióde les persones investigadores amb talent contractades amb càrrec a les convocatòries 2023 i anteriors del Pla GenT”(ESGENT/016/2024)Furthermore,the Grant CNS_(2)022-136183 funded by MICIU/AEI/10.13039/501100011033by“European Union NextGenerationEU/PRTR”the Grant PID2022-143164OA-I00 funded by MICIU/AEI/10.13039/501100011033 and by“ERDF/EU”Universitat Jaume I(GACUJIMA/2024/13)are also gratefully acknowledged.
文摘The presence of persistent pollutants in water poses a severe environmental threat,driving an urgent need for efficient and eco-friendly remediation strategies.In response,the scientific community is increasingly focused on developing catalytic processes that maximize efficiency while minimizing environmental impact.In this context,we introduce recyclable catalysts based on NiPd nanoparticles(NPs)that feature tunable phase distributions and compositions.By varying Pd doping levels through Reactive Laser Ablation in Liquids(RLAL),we precisely control the catalytic and magnetic properties of these NPs.Notably,a nanocatalyst featuring the NiPd alloyed phase exhibits exceptional catalytic performance,achieving a turnover frequency of 3680 h^(-1) and 98.5%selectivity in the model transformation of 4-nitrophenol into 4-aminophenol.Additionally,it demonstrates remarkable efficiency in the chemoselective hydrogenation of various nitroarenes to functionalized anilines under mild conditions(atmospheric H_(2) pressure,33℃).Furthermore,the synergistic properties arising from the internal structure of these NPs allow them to surpass the performance of nanocatalysts made from their monometallic counterparts and simple mixtures.Overall,this study represents a significant advancement in the precise control of nanocatalyst synthesis and their associated physicochemical properties,paving the way for more efficient redox catalytic protocols,including industrially demanding hydrogenation reactions.
基金Scientific and Technological Research Council of Turkey(TUBITAK)(Grant No:118Z577)。
文摘We report herein an innovative design and synthesis of a novel multifunctional nanocatalyst for the transfer hydrogenation(TH)of nitroarenes and olefins using water as a hydrogen source and solvent.The presented nanocatalyst is composed of NiPd alloy nanoparticles(NPs)supported on reduced graphene oxide(rGO)decorated with metallic Al NPs(Al-rGO/NiPd).In the catalyst,metallic Al NPs serve as the sacrificing agent for hydrogen generation via the Al-H_(2)O reaction,NiPd NPs act as the catalyst for the transfer of the generated hydrogen to the unsaturated compounds,and rGO functions as both a support material and stabilizer for the NPs.Among all tested catalysts,Al-rGO/Ni_(40)Pd_(60)nanocatalysts are found to be the most efficient and selective catalysts in the presented TH of nitroarenes(14 examples)and olefins(14 examples)with yields reaching up to 99%under the optimized reaction conditions.Additionally,Al-rGO/Ni_(40)Pd_(60)nanocatalysts are recyclable catalysts in the TH reactions by catalyzing ten consecutive runs in the TH of nitrobenzene without a significant drop in their initial catalytic activity,which is the first example in this regard.Last but not least,the current transfer hydrogenation protocol provides selectivity for the reduction of only the-NO_(2)group of nitroarenes bearing iodo or bromo substituents on the same aromatic ring.This study is the first example of a TH protocol that employs an Al-modified nanomaterial serving as both a hydrogen generator and reusable catalyst in water without using any additional hydrogen source.
基金financially supported by the National Natural Science Foundation of China(Nos.U23A20554 and 52371158)the Key Research and Development Program of Shan dong Province(No.2021ZLGX01)+2 种基金Taishan Scholar Foundation of Shandong Province,the Natural Science Foundation of Shan dong Province(No.ZR2022QB169)the Excellent Youth Science Fund Project of Shan dong Province(Overseas)(No.2023HWYQ-018)the Postdoctoral Science foundation of China(No.2022M710077)。
文摘Bulk nanoporous(np)metallic actuators have attracted increasing attention due to their large strain and low stimulation voltage.However,studies focusing upon the combined effect of composition and structure on the actuation performance of metallic actuators are relatively scarce,and its underlying mechanism needs to be clarified Herein,a series of bulk np-NiPd samples with differen compositions and microstructures were fabricated using a dealloying-coarsening-dealloying strategy and chargecontrolled electrochemical dealloying,and the process involves only one component of precursor alloy.It has been found that the np-NiPd cubes show a composition/structure-dependent mechanical property and electrochemical actuation performance.Specially,the npNi_(70)Pd_(30)sample with a homogeneously porous structure and good network connectivity exhibits significantly larger strain amplitude and faster strain rate than other hierarchically porous NiPd samples(np-Ni_(50)Pd_(50)and npNi_(20)Pd_(80)).Moreover,the np-Ni_(70)Pd_(30)sample demonstrates good actuation stability with high strain retention after hundreds of cycles.Notably,the maximum strain amplitude(1.17%)is even comparable to that of advanced leadfree piezoceramic,and the maximum strain rate exceeds those of many reported metallic actuator materials.Our work indicates that good network connectivity plays a vita role in facilitating large/fast strain response in metallic actuators.
基金supported by the National Program on Key Basic Research Project(2014CB943001 and 2012CB944700)the National Natural Science Foundation of China(81120108009 and 81530032)+3 种基金the National Health and Family Planning Commission of the People's Republic of China(201402004)Science and Technology Plan of Guangdong Province(2013B022000005)Guangdong Enterprise Key Laboratory of Human Disease Genomics(2011A060906007)Shenzhen Engineering Laboratory for Birth Defects Screening([2011]861)
文摘A couple with a proband child of GJB2 （encoding the gap junction protein connexin 26）-associated hearing impairment and a previous pregnancy miscarriage sought for a reproductive solution to bear a healthy child. Our study aimed to develop a cus- tomized preconception-to-neonate care trajectory to fulfill this clinical demand by integrating preimplantation genetic diagno- sis （PGD）, noninvasive prenatal testing （NIPT）, and noninvasive prenatal diagnosis （N1PD） into the strategy. Auditory and ge- netic diagnosis of the proband child was carried out to identify the disease causative mutations. The couple then received in-vitro-fertilization treatment, and eight embryos were obtained for day 5 biopsy. PGD was performed by short-tandem-repeat linkage analysis and Sanger sequencing of GJB2 gene. Transfer of a GJB2c.235delC heterozygous embryo resulted in a sin- gleton pregnancy. At the 13th week of gestation, genomic DNA （gDNA） from the trio family and cell-free DNA （cfDNA） from maternal plasma were obtained for assessment of fetal chromosomal aneuploidy and GJB2 mutations. NIPT and NIPD showed the absence of chromosomal aneuploidy and GJB2-associated disease in the fetus, which was later confirmed by inva- sire procedures and postnatal genetic/auditory diagnosis. This strategy successfully prevented the transmission of hearing im- pairment in the newborn, thus providing a valuable experience in reproductive management of similar cases and potentially other monogenic disorders.
