ROS Balance Autoregulating Core-Shell CeO_(2)@ZIF-8/Au Nanoplatform for Wound Repair

Reactive oxygen species(ROS)plays important roles in living organisms.While ROS is a double-edged sword,which can eliminate drug-resistant bacteria,but excessive levels can cause oxidative damage to cells.A core–shell nanozyme,Ce O_(2)@ZIF-8/Au,has been crafted,spontaneously activating both ROS generating and scavenging functions,achieving the multifaceted functions of eliminating bacteria,reducing inflammation,and promoting wound healing.The Au Nanoparticles(NPs)on the shell exhibit high-efficiency peroxidase-like activity,producing ROS to kill bacteria.Meanwhile,the encapsulation of Ce O_(2) core within ZIF-8 provides a seal for temporarily limiting the superoxide dismutase and catalase-like activities of Ce O_(2) nanoparticles.Subsequently,as the ZIF-8 structure decomposes in the acidic microenvironment,the Ce O_(2) core is gradually released,exerting its ROS scavenging activity to eliminate excess ROS produced by the Au NPs.These two functions automatically and continuously regulate the balance of ROS levels,ultimately achieving the function of killing bacteria,reducing inflammation,and promoting wound healing.Such innovative ROS spontaneous regulators hold immense potential for revolutionizing the field of antibacterial agents and therapies.

高度有序ZIF-8/Au纳米复合结构阵列的构筑及其表面增强拉曼光谱的应用

采用气-液界面自组装方式制备得到有序单层聚苯乙烯(PS)微球阵列,以此为模板,采用磁控溅射沉积方法结合热处理技术获得单层六方非密排Au纳米颗粒阵列。随后采用水热法成功制得高度有序ZIF-8/Au纳米复合结构有序阵列。探究了生长机理以及反应温度、反应时间对微观形貌和光学特性的影响,进一步探究了该复合结构阵列作为表面增强拉曼散射(SERS)活性基底的灵敏度和均一性。结果表明:当水热反应温度从25℃升高至100℃时,ZIF-8纳米颗粒的数量逐步增多,同时尺寸随之增大,表面等离激元共振(SPR)峰和衍射峰均发生了红移。当水热反应时间从10 min增至60 min时,ZIF-8纳米颗粒从围绕Au纳米颗粒选择性生长到蔓延至整个材料表面。在样品表面沉积特定厚度的Ag膜后,测得4-氨基苯硫酚(4-ATP)和罗丹明6G(R6G)两种探针分子的检测极限均为10-11mol·L^(-1),4-ATP和R6G的SERS强度与分子溶液浓度呈线性关系,相关系数R2分别为0.9801和0.9844。随机选取10个不同位置测试4-ATP的SERS谱图,得到相对标准偏差(RSD)为8.86%,表明ZIF-8/Au纳米复合结构有序阵列作为SERS基底具有良好的均匀性和稳定性。

基于Au/In键合的静电扭转微镜的设计与工艺研究

采用Au/In键合技术并引入凸点层设计,制备了用于光通信领域的二维平行板式静电扭转微镜阵列。相较于其他键合技术,Au/In键合实现了低温键合并与硅通孔技术相容。此外,相对于梳齿驱动,采用平行板电容的扭转微镜有助于实现更高的占空比,便于阵列制造。凸点层的设计提升了键合强度,平均键合强度达8.97 MPa。微镜的实测结果与有限元仿真基本一致,内、外轴分别在13.7 V和18.2 V的直流电压下实现了0.7°的机械转角。

Silicalite-1封装Au纳米颗粒催化剂的制备及性能研究

金属负载型催化剂广泛应用于工业催化领域。然而,金属活性位点在反应中的聚集和流失,是该类催化材料长久以来的痛点。文章以Silicalite-1为载体,Au纳米颗粒为活性中心,通过一种简单有效的合成方法,将Au纳米颗粒完全封装于Silicalite-1内部,可有效抑制Au纳米颗粒流失,提高催化剂的稳定性。SEM、TEM、XRD、XPS、N 2物理吸附脱附等表征结果证明了催化剂的封装结构。催化剂对硝基化合物还原反应表现出优异的催化活性,以及较高的循环稳定性,极大提高了工业应用前景。

Structure–performance relationship of Au nanoclusters in electrocatalysis:Metal core and ligand structure

Remarkable progress has characterized the field of electrocatalysis in recent decades,driven in part by an enhanced comprehension of catalyst structures and mechanisms at the nanoscale.Atomically precise metal nanoclusters,serving as exemplary models,significantly expand the range of accessible structures through diverse cores and ligands,creating an exceptional platform for the investigation of catalytic reactions.Notably,ligand‐protected Au nanoclusters(NCs)with precisely defined core numbers offer a distinct advantage in elucidating the correlation between their specific structures and the reaction mechanisms in electrocatalysis.The strategic modulation of the fine microstructures of Au NCs presents crucial opportunities for tailoring their electrocatalytic performance across various reactions.This review delves into the profound structural effects of Au NC cores and ligands in electrocatalysis,elucidating their underlying mechanisms.A detailed exploration of the fundamentals of Au NCs,considering core and ligand structures,follows.Subsequently,the interaction between the core and ligand structures of Au NCs and their impact on electrocatalytic performance in diverse reactions are examined.Concluding the discourse,challenges and personal prospects are presented to guide the rational design of efficient electrocatalysts and advance electrocatalytic reactions.

Mineralogical study and significance of the basalt-hosted Carlin-type Au deposits in southwestern Guizhou Province,China

The Jiadi and Damaidi gold deposits in southwest Guizhou Province are the largest basalt-hosted Carlintype gold deposits recently discovered in China.This study uses the Tescan Integrated Mineral Analyzer,supported by detailed field investigations,regional geological data,and extensive sample collections,including mineralized ore,altered wall rock,and unaltered basalt samples,for orebearing and geochemical analyses.Comparative analysis between altered and unaltered basalt samples revealed a mineral assemblage of sericite,quartz,and pyrite.This mineral composition forms through the hydrothermal alteration of unaltered basalt,originally containing feldspar,pyroxene,and ilmenite.The wall rock primarily features sericite,quartz,and hematite.During the alteration process,major,trace,and rare earth elements notably migrate.In the Jiadi deposit,K_(2)O,Rb,Au,and REE significantly increase,while Na_(2)O,CaO,MgO,and MnO decrease.SiO_(2),Al_(2)O_(3),and Fe_(2)O_(3)levels remain relatively stable.In the Damaidi deposit,K_(2)O,Rb,and Au enrich,contrasting with the depletion of Na_(2)O,CaO,MgO,and MnO,while SiO_(2),Fe_(2)O_(3),Al_(2)O_(3),TiO_(2),and REE show no significant changes.In the wall rock,TiO_(2),Al_(2)O_(3),K_(2)O,and REE increase,while Na_(2)O,CaO,MgO,and MnO decrease;SiO_(2)and Fe_(2)O_(3)content remains unchanged.The mineralization process likely originated from mid-to low-temperature,reductive magmatic hydrothermal fluids rich in CO_(2),CH_(4),N_(2),H^(+),S^(2-),HS^(-),H_(3)AsO_(3),and[Au(HS_(2)]^(-).These fluids migrated to tectonically weak zones in the Lianhuashan area,where Emeishan basalts are present.They reacted with Fe-bearing minerals in the basalt,such as ferro-hornblende and ilmenite,forming pyrite,arsenic-bearing pyrite,and arsenopyrite,thus enriching Au in these minerals.Additionally,K^(+)and H^(+)in the fluid reacted with plagioclase in the basalt,forming sericite and quartz.As the fluid entered the wall rock from structural weak zones,its oxidation increased,leading to the complete or partial reaction of Fe-bearing minerals in the wall rock,resulting in the formation of hematite or magnetite.This mineralization process is similar to that observed in carbonate-hosted Carlin-type gold deposits in southwest Guizhou,with the primary distinction being the iron source.In carbonate deposits,iron originates from ferridolomite within the wall rock,while in basalt-hosted deposits,it derives from ferripyroxene and ilmenite.

Unravelling the role of the combined effect of metallic charge transfer channel and SiO_(x) overlayer in the Zr/Si-Fe_(2)O_(3):Au:SiO_(x) nanorod arrays to boost photoelectrochemical water splitting

Hematite(α-Fe_(2)O_(3)) based photoanodes have been extensively studied due to various intriguing features that make them viable candidates for a photoelectrochemical(PEC) water splitting photoanode.Herein,we propose a Zr-doped Fe_(2)O_(3) photoanode decorated with facilely spin-coated Au nanoparticles(NPs) and microwave-assisted attached Si co-doping in conjunction with a SiO_(x) overlayer that displayed a remarkable photocurrent density of 2.01 mA/cm^(2) at 1.23 V vs.RHE.The kinetic dynamics at the photoelectrode/-electrolyte interface was examined by employing systematic electrochemical investigations.The Au NPs played a dual role in increasing PEC water splitting.First,the Schottky interface that was formed between Au NPs and Zr-Fe_(2)O_(3) lectrode ensured the prevention of electron flow from the photoanode to the metal,increasing the number of available charges as well as suppressing surface charge recombination.Second,Au extracted photoholes from the bulk of the Zr-Fe_(2)O_(3) and transported them to the outer SiO_(x) overlayer,while the SiO_(x) overlayer efficiently collected the photoholes and promoted the hole injection into the electrolyte.Further,Si co-doping enhanced bulk conductivity by reducing bulk charge transfer resistance and improving charge carrier density.This study outlines a technique to design a metallic charge transfer path with an overlayer for solar energy conversion.

Nano-Au-decorated hierarchical porous cobalt sulfide derived from ZIF-67 toward optimized oxygen evolution catalysis:Important roles of microstructures and electronic modulation

Enhancing both the number of active sites available and the intrinsic activity of Co-based electrocatalysts simultaneously is a desirable goal.Herein,a ZIF-67-derived hierarchical porous cobalt sulfide decorated by Au nanoparticles(NPs)(denoted as HP-Au@CoxSy@ZIF-67)hybrid is synthesized by low-temperature sulfuration treatment.The well-defined macroporous-mesoporous-microporous structure is obtained based on the combination of polystyrene spheres,as-formed CoxSy nanosheets,and ZIF-67 frameworks.This novel three-dimensional hierarchical structure significantly enlarges the three-phase interfaces,accelerating the mass transfer and exposing the active centers for oxygen evolution reaction.The electronic structure of Co is modulated by Au through charge transfer,and a series of experiments,together with theoretical analysis,is performed to ascertain the electronic modulation of Co by Au.Meanwhile,HP-Au@CoxSy@ZIF-67 catalysts with different amounts of Au were synthesized,wherein Au and NaBH4 reductant result in an interesting“competition effect”to regulate the relative ratio of Co^(2+)/Co^(3+),and moderate Au assists the electrochemical performance to reach the highest value.Consequently,the optimized HP-Au@CoxSy@ZIF-67 exhibits a low overpotential of 340 mV at 10 mA cm^(-2)and a Tafel slope of 42 mV dec-1 for OER in 0.1 M aqueous KOH,enabling efficient water splitting and Zn-air battery performance.The work here highlights the pivotal roles of both microstructural and electronic modulation in enhancing electrocatalytic activity and presents a feasible strategy for designing and optimizing advanced electrocatalysts.

Green synthesis of MIL⁃101/Au composite particles and their sensitivity to Raman detection of thiram

Metal⁃organic framework(MOF)MIL⁃101 and surface plasmon polariton(SPP)supported gold nanoparti⁃cles(Au NPs)hybrid systems were developed as a highly sensitive and reproducible surface⁃enhanced Raman scat⁃tering(SERS)detection platform,in which a green electrostatic self⁃assembly technology was adopted to construct the substrate.In an aqueous solution,the electronegativity of the particles can be used to prepare the composite sub⁃strate without any surface modifier.Due to the enrichment capacity of MIL⁃101 and the electromagnetic enhance⁃ment from Au NPs,the well⁃designed MIL⁃101/Au composites possessed ultrahigh sensitivity with the detection limit of Rhodamine 6G(R6G)as low as 10^(-10) mol·L^(-1).Meanwhile,the substrate exhibits high stability,excellent reproduc⁃ibility,and recyclability.Additionally,the novel substrate can be explored for direct capture,and sensitively detect pesticide residues such as thiram.

Coupling Au with BO_(x) matrix induced by Closo-boron cluster for electrochemical synthesis of ammonia

Au is considered as one of the most promising catalysts for nitrogen reduction reaction(NRR),however maximizing the activity utilization rate of Au and understanding the synergistic effects between Au and carriers pose ongoing challenges.Herein,we systematically explore the synergistic catalytic effect of incorporating Au with boron clusters for accelerating NRR kinetics.An in-situ abinitio strategy is employed to construct B-doped Au nanoparticles(2-6 nm in diameter)loaded on BO_(x) substrates(AuBO_(x)),in which B not only modulates the surface electronic structure of Au but also forms strong coupling interactions to stabilize the nanoparticles.The electrochemical results show that Au-BO_(x) possesses excellent NRR activity(NH_(3) yield of 48.52μg h^(-1)mg_(cat)^(-1),Faraday efficiency of 56.18%),and exhibits high stability and reproducibility throughout the electrocatalytic NRR process.Theoretical calculations reveal that the introduction of B induces the formation of both Au dangling bond and Au-B coupling bond.which considerably facilitates the hydrogenation of~*N_(2)^(-)~*NH_(3).The present work provides a new avenue for the preparation of metal-boron materials achieved by one-step reduction and doping process,utilizing boron clusters as reducing and stabilizing agents.

Controllable Synthesis of Au NRs and Its Flexible SERS Optical Fiber Probe with High Sensitivity

The surface-enhanced Raman scattering(SERS) optical fiber probes were successfully prepared by self-assembling on polyelectrolyte multilayers. Gold nanorods(Au NRs) were used as SERS enhancement material to give excellent biological affinity and stability to the SERS optical fiber probes. Au NRs were synthesized by seed growth method. The synergistic effect between AgNO_(3) and surfactant was investigated, and the highest yield was found when AgNO_(3) was 500 uL. Meanwhile, different SERS optical fiber probes were obtained by selecting silane coupling agent, polyelectrolyte multilayer and graphene oxide(GO) to treat quartz fiber. It was found that the SERS optical fiber probes obtained by the self-assembled on polyelectrolyte multilayers method performed better than those by other methods. In addition, Mapping was combined with finite element simulation to analyze the electromagnetic field distribution at the fiber end face.The electromagnetic field distribution of Au NRs was investigated, the difference of electromagnetic field intensity around the Au NRs with different arrangements was compared, the strongest signal was obtained when the Au NRs were head-to-head. Finally, sensitivity of the optimized SERS optical fiber probes could reach 10^(-9)mol/L, with excellent stability and repeatability.

Geology and mineralization of the Dongping supergiant alkalic-hosted Au-Te deposit(>100 t Au)in Northern Hebei Province,China:A review

The Dongping deposit is the largest alkalic-hosted gold deposit in China containing>100 t of Au.This paper presents a new understanding for Dongping ore system,based on the previous studies.The mineralization originally occurred at 400-380 Ma,simultaneous with emplacement of the Shuiquangou alkaline complex,and was overprinted by the hydrothermal activity in the Yanshanian.Isotope compositions of ores indicate metals of the deposit are mainly provided by the Shuiquangou complex.Ore-forming fluids are characterized by increasing oxygen fugacity and decreasing sulfur fugacity,while tellurium fugacity increased in the Stage II-2 and decreased in Stage II-3.These systematic changes are closely related to the processes of mineral precipitation and fluid evolution.Sulfide precipitation from Stage Ⅰ to Stage Ⅱ was triggered by fluid boiling,which leads to the precipitation of Pb-Bi-Te,due to decrement of sulfur fugacity.Condensation of gas phase containing high concentration of H_2Te leads to precipitation of Te-Au-Ag minerals and native tellurium.Based on these hypotheses,this paper present a polyphase metallogenic model as follow.During the Devonian,fluids were released from alkaline magmas,which carried ore-forming materials form the surrounding rocks and precipitate the early ores.During the Jurassic-Cretaceous,fluorine-rich fluids exsolved from highly factionated Shangshuiquan granite,which extracted and concentrated Au from the Shuiquangou complex and the Sanggan Group metamorphic rocks,and finally formed the Dongping gold deposit.

TiO_2纳米管负载Ag、Au、Pt纳米粒子的微波合成与表征

TiO2 nanotubes were prepared under normal pressure at a temperature of 120 ℃. Ag, Au, Pt nanoparticles supported on TiO2 nanotubes were prepared by m icrowave assisted heating polyol process. TEM images showed that microwave prepa red Ag, Au, Pt nanoparticles supported on TiO2 nanotubes were small and well dis persed on the surface of the TiO2 nanotubes. UV-Vis absorption spectra showed th at the absorbance of Ag/TiO2 nanotubes and Au/TiO2 nanotubes in the visible ligh t range increased greatly compared to the single titania nanotubes.

基于同时平衡原理的Au-I^--H_2O系热力学分析

采用同时平衡原理对Au-I--H2O系的浸金热力学进行分析,分别研究溶液与固体Au以及Au I沉淀与固体Au平衡时的φ-p H关系、Au I存在条件和溶液中含金组分的变化规律。结果表明:随着溶液中含金组分的总浓度cT(Au)的降低或含碘组分的总浓度cT(I-)的增加,还原电位φsol/Au迅速降低,Au3+/Au2O3的平衡p H值增大,非常有利于金的碘化浸出;随着溶液中cT(I-)逐渐增加,出现Au I沉淀且其沉淀量呈先增大后减小的趋势;在cT(Au)为1×10-4 mol/L的条件下,当溶液中cT(I-)浓度大于0.0021 mol/L时,可避免Au I沉淀的生成,金主要以Au I2-络合离子形式存在。Au-I--H2O系的浸金热力学分析为金的高效碘化浸出提供了理论依据。

水洗处理对Au/TiO_2催化剂光催化活性的影响

以Au(S2O3)32-为金前驱体,分别采用水洗(W)和旋蒸(E)工艺制备了Au/TiO2催化剂.用UV-Vis漫反射光谱(DRS)、X射线衍射(XRD)、透射电子显微镜(TEM)和原子吸收光谱(AAS)对制备的催化剂样品进行了表征,通过光催化降解甲基橙对催化剂光催化活性进行了评价.结果表明,通过水洗处理,催化剂样品表面形成了具有较好分散性的金纳米粒子(2-5nm),而旋蒸工艺制备的样品表面形成一层金的包覆结构.Au/TiO2催化剂的光催化活性与制备工艺密切相关.在相似的金负载量下,水洗法制备的样品比旋蒸法制备的样品具有更高的光催化活性.

Au／TiO2催化剂制备条件对巴豆醛选择加氢的影响

采用沉积-沉淀法制备了纳米Au/TiO2催化剂,以X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)等手段对催化剂进行了系统的表征,并考察了该催化剂在巴豆醛液相加氢制巴豆醇反应中的催化性能.通过改变活化气氛、负载量和还原温度,能够调节Au粒子的尺寸及金属与载体间的相互作用.在673K还原条件下制备Au质量分数为9.2%的Au/TiO2催化剂上,Au粒子的平均粒径为2nm,初始加氢速率达到13.7×10-5mol·s-1·g-1,同时巴豆醇最高收率可达69.9%.结合表征结果,该催化剂良好的巴豆醛选择加氢性能归属为载体TiO2在还原条件下产生的氧缺陷位对Au纳米粒子的锚定作用及给电子作用.

Au改性纳米TiO_2材料对NPE-10光催化降解的活性

以钛酸四丁酯和氯金酸为原料,通过溶胶-凝胶法制备了Au掺杂的纳米TiO2光催化剂粉体,并用XRD、BET、XPS和固体紫外可见吸收光谱等技术对其晶相结构、比表面积、表面组成及紫外可见光响应范围进行了表征,对其光催化降解非离子表面活性剂壬基酚聚氧乙烯醚(NPE-10)的活性进行了考察.结果表明,掺杂的Au在纳米TiO2粉体材料中可能以两种形态存在,即以Au3+离子形式替代Ti4+进入TiO2晶格和以Au原子态形式暴露于粉体表面.前者使TiO2在480～650nm出现了更强的光吸收;后者中处于表面原子态的Au又会成为光生电子的受体,有效地避免了光生电子空穴对的复合.通过对掺杂量及处理温度的优化,在nAu3+/nTi4+=0.005,500℃煅烧的条件下可以制得具有较高的光催化活性的Au/TiO2粉体.对NPE-10的光催化氧化试验显示,日光照射4h后降解效率可以达到91.8%;而用未改性的纳米TiO2,在同样条件下,NPE-10的光催化降解效率仅能达到50.2%,商品DegussaP-25也只能达到66%.

Au/TiO_2的制备及其光催化氧化丙烯的研究

采用浸渍法制备了Au/TiO2光催化剂,使用X射线能谱(XPS)和透射电子显微镜(TEM)对样品进行了表征.结果表明,Au颗粒的尺度约为4—6nm;Au4f7/2的结合能为83.3eV,与Au0的标准峰位(84.0eV)相比,向低结合能方向移动了0.7eV,使其表现出俘获电子的特性.以丙烯的光催化氧化为指标反应,对制备的Au/TiO2的活性进行了评价,结果显示,Au/TiO2的光催化活性明显高于单一TiO2的,且当Au的担载量在0.1—5.0%范围内变化时,催化活性随着担载量的增加而显著增加.

Au/TiO_2催化剂的制备及低级醇类的光催化消除

采用沉积-沉淀法制备Au/TiO2催化剂,并用IR、TG-DTA、XRD、TEM、BET、FL、XPS、UV-visDRS和PL等分析方法对其进行表征;测试和计算在甲醇的光催化消除反应中Au/TiO2催化剂的动力学参数;以低级醇类消除反应为模式反应评价催化剂在紫外光照下的光催化性能。结果表明:Au质量分数为1%的Au/TiO2催化剂在200℃下活化4h的光催化活性最佳,0.15g催化剂可将初始浓度为7.0g/m3、流速为12.5mL/min的甲醇和初始浓度为2.14g/m3、流速为5mL/min的乙醇以及初始浓度为2.21g/m3、流速为4mL/min的正丙醇完全消除;得到的反应活化能Ea=14.80kJ/mol,拟合的曲线线性关系好(R=0.9811),符合一级动力学反应规律。

LED可见光下Au/TiO_2光催化氧化甲醛表观动力学

甲醛是室内空气中典型的挥发性有机化合物(VOCs)之一。等离子激元型光催化剂可吸收可见光,可在室温常压下利用太阳光驱动光催化氧化脱除室内空气中甲醛的反应,其表观反应动力学研究对设计等离子激元型光催化剂及应用于脱除VOCs等污染物具有重要意义。研究了LED可见光下等离子激元型Au/TiO2光催化脱除气相中甲醛的表观反应动力学,考察不同波长的可见光源、光强及反应气相对湿度对表观反应动力学的影响,根据对实验数据的分析求得LED可见光催化氧化甲醛表观反应速率常数k(I,H)。结果表明,在13%相对湿度、蓝光光强为38.5mW·cm-2的条件下,光反应的甲醛转化率达77%,是暗反应的近5倍。在LED红、绿、蓝、白光照射下,随着光强增加,甲醛转化率快速增加后缓慢增至基本不变。相同光强(低于42 mW·cm-2)和湿度条件下,红、绿、蓝光源的甲醛转化率相近,白光略低于其他光源。干气氛下,光反应和暗反应的甲醛转化率几乎为0。湿气氛下,光反应和暗反应均有甲醛转化率,光反应的甲醛转化率更高。不同光源条件下甲醛转化率随相对湿度变化规律相似。相对湿度为21.9%时甲醛转化率最高,而后保持不变,基本在80%左右。通过对红、绿、蓝、白光的数据拟合计算,得到表观动力学参数k(I)H、k(H)I、k(I,H)以及速率方程。