Advances of Synergistic Electrocatalysis Between Single Atoms and Nanoparticles/Clusters

Combining single atoms with clusters or nanoparticles is an emerging tactic to design efficient electrocatalysts.Both synergy effect and high atomic utilization of active sites in the composite catalysts result in enhanced electrocatalytic performance,simultaneously provide a radical analysis of the interrelationship between structure and activity.In this review,the recent advances of single-atomic site catalysts coupled with clusters or nanoparticles are emphasized.Firstly,the synthetic strategies,characterization,dynamics and types of single atoms coupled with clusters/nanoparticles are introduced,and then the key factors controlling the structure of the composite catalysts are discussed.Next,several clean energy catalytic reactions performed over the synergistic composite catalysts are illustrated.Eventually,the encountering challenges and recommendations for the future advancement of synergistic structure in energy-transformation electrocatalysis are outlined.

Optical pulling force on nanoparticle clusters with gain due to Fano-like resonance

We demonstrate that,in a simple linearly-polarized plane wave,the optical pulling forces on nanoparticle clusters with gain can be induced by the Fano-like resonance.The numerical results based on the full-wave calculation show that the optical pulling forces can be attributed to the recoil forces for the nanoparticle clusters composed of dipolar nanoparticles with three different configurations.Interestingly,the recoil forces giving rise to optical pulling forces are exactly dominated by the coupling term between the electric and magnetic dipoles excited in the nanoparticle clusters,while other higherorder terms have a negligible contribution.In addition,the optical pulling force can be tailored by modulating the Fano-like resonance via either the particle size or the gain magnitude,offering an alternative freedom degree for optical manipulations of particle clusters.

Control of the interparticle spacing in superparamagnetic iron oxide nanoparticle clusters by surface ligand engineering

Polymer-mediated self-assembly of superparamagnetic iron oxide（SPIO） nanoparticles allows modulation of the structure of SPIO nanocrystal cluster and their magnetic properties. In this study, dopamine-functionalized polyesters（DApolyester） were used to directly control the magnetic nanoparticle spacing and its effect on magnetic resonance relaxation properties of these clusters was investigated. Monodisperse SPIO nanocrystals with different surface coating materials（poly（ε-caprolactone）, poly（lactic acid）） of different molecular weights containing dopamine（DA） structure（DA-PCL2k,DA-PCL1k, DA-PLA1k）） were prepared via ligand exchange reaction, and these nanocrystals were encapsulated inside amphiphilic polymer micelles to modulate the SPIO nanocrystal interparticle spacing. Small-angle x-ray scattering（SAXS）was applied to quantify the interparticle spacing of SPIO clusters. The results demonstrated that the tailored magnetic nanoparticle clusters featured controllable interparticle spacing providing directly by the different surface coating of SPIO nanocrystals. Systematic modulation of SPIO nanocrystal interparticle spacing can regulate the saturation magnetization（Ms） and T2 relaxation of the aggregation, and lead to increased magnetic resonance（MR） relaxation properties with decreased interparticle spacing.

Photocurrent improvement of an ultra-thin silicon solar cell using the localized surface plasmonic effect of clustering nanoparticles

The cluster-shaped plasmonic nanostructures are used to manage the incident light inside an ultra-thin silicon solar cell.Here we simulate spherical,conical,pyramidal,and cylindrical nanoparticles in a form of a cluster at the rear side of a thin silicon cell,using the finite difference time domain(FDTD)method.By calculating the optical absorption and hence the photocurrent,it is shown that the clustering of nanoparticles significantly improves them.The photocurrent enhancement is the result of the plasmonic effects of clustering the nanoparticles.For comparison,first a cell with a single nanoparticle at the rear side is evaluated.Then four smaller nanoparticles are put around it to make a cluster.The photocurrents of 20.478 mA/cm2,23.186 mA/cm2,21.427 mA/cm2,and 21.243 mA/cm2 are obtained for the cells using clustering conical,spherical,pyramidal,cylindrical NPs at the backside,respectively.These values are 13.987 mA/cm2,16.901 mA/cm2,16.507 mA/cm2,17.926 mA/cm2 for the cell with one conical,spherical,pyramidal,cylindrical NPs at the backside,respectively.Therefore,clustering can significantly improve the photocurrents.Finally,the distribution of the electric field and the generation rate for the proposed structures are calculated.

Copper iodine cluster nanoparticles for tumor-targeted X-ray-induced photodynamic therapy

The weakness of visible and near-infrared light penetration depth limits the application of photodynamic therapy(PDT)in deep-seated tumors.Based on the high penetrability of X-rays,X-ray-induced PDT(X-PDT)is a promising new method for treating deep-seated tumors.However,it requires the development of suitable X-ray-induced sensitizers that could employ X-ray energy to produce reactive oxygen species(ROS)efficiently.In this study,a novel X-rayinduced sensitizer(NanoSRF)was developed through a microemulsion method,in which copper iodine cluster compound Cu_(2)I_(2)(tpp)2(2,5-dm-pz)(CIP)and rose bengal(RB)worked as scintillator and photosensitizer,respectively.CIP was synthesized by a simple mechanical grinding method,and subsequently folic acid(FA)-modified albumin was introduced to enable its alliance with RB.NanoSRF exhibited excellent dispersion stability and generated a large amount of ROS under X-ray irradiation.The results of in vitro studies demonstrated its high selectivity for FA receptor-positive cancer cells.Following systemic administration,NanoSRF accumulated in H22 tumors of xenograft-bearing mice,and Xray irradiation(5.46 Gy)induced a significant inhibition rate of 96.7%in tumor growth.This study pioneers the use of copper iodide cluster as a scintillator in X-PDT,presenting new possibilities for designing scintillators with exceptional X-ray absorption and efficient X-PDT capabilities.

Highly Ordered Lattice Orientation of ZnO Nanoparticles Formed in Confined Space

Oriented aggregation of nanoparticles has been accomplished by means of solid state reac- tion. Non-crystallized and crystallized ZnO nanoparticles/clusters could be accommodated in the lamellar spacing of inorganic-organic composite, which were prepared by thermolysis of layered solid zinc-oleate complex at 260 and 300 ℃ in air, respectively. High-resolution transmission electron microscopy and selected area electron diffraction patterns indicate that aggregates are single crystals with various defects. The photoluminescence excitation spectra of both samples show two bands at 272 and 366 nm. The former may originate from electron transfer from valence band to conduction band in ZnO clusters composed of less than 200 ZnO molecules （2R〈2 nm）.

Gas-Phase Deposited Plasmonic Nanoparticles Supported on 3D-Graphene/Nickel Foam for Highly SERS Detection

In this work, we proposed a novel three-dimensional (3D) plasmonic nanostructure based on porous graphene/nickel foam (GNF) and gas-phase deposited Ag nanoparticles (NPs). Ag NPs with high density were directly deposited on the surface of 3D GNF by performing a novel cluster beam deposition approach. In comparison with traditional Ag substrate (SiO2/Ag), such hot-spots enriched 3D nanostructure showed extremely high electromag-netic field enhancement under incident light irradiation which could be used as a sensitive chemical sensor based on surface enhanced Raman scattering (SERS). The experimental results demonstrated that the proposed nanostructure showed superior SERS performance in terms of Raman signal reproducibility and sensitivity for the probe molecules. 3D full-wave simulation showed that the enhanced SERS performance in this 3D hierarchical plasmonic nanostructure was mainly obtained from the hot-spots between Ag NPs and the near-field coupling between Ag NPs and GNF sca olds. This work can provide a novel assembled SERS substrate as a SERS-based chemical sensor in practical applications.

Preparation of gold clusters on metal oxides by deposition-precipitation with microwave drying and their catalytic performance for CO and sulfide oxidation

Gold clusters and small nanoparticles supported on metal oxides could be prepared by deposition‐precipitation followed by microwave irradiation as a drying method and then calcination.The drying method influenced the size of the Au particles.Au(III)was partly reduced during conventional oven drying,resulting in Au aggregates.In contrast,Au(III)was preserved during microwave drying owing to rapid and uniform heating,and the Au diameter was minimized to1.4nm on Al2O3.This method can be applied to several metal oxide supports having different microwave absorption efficiencies,such as MnO2,Al2O3,and TiO2.These catalysts exhibited higher catalytic activities for CO oxidation at low temperature and for selective aerobic oxidation of sulfide than those prepared by conventional methods.

Effect of size on momentum distribution of electrons around vacancies in NiO nanoparticles

Very small nickel oxide nanoparticles were prepared by a sol-gel procedure using nickel nitrate hexahydrate and ammonium hydroxide as precursors. The particles are in the range of 5 nm-11 rim. The x-ray diffraction （XRD） crystallography and high resolution transmission electron microscopy （HRTEM） were employed to characterize the samples. They were found to be polycrystalline in nature and fcc （NaCl-type） in structure, with the lattice parameter varying with annealing temperature. HRTEM pictures show that the as-prepared samples are hexagonal in shape. Positron annihilation spectroscopy was used to investigate the Doppler-broadened spectra of the samples. The S and W parameters revealed that the chemical surroundings and momentum distribution of the vacancy clusters vary with crystallite size.

Palladium-Carbon Composite Nanoparticle Films with Enhanced Electrocatalytic Activity for Hydrogen Peroxide Sensors

A nanocomposite electrocatalyst was prepared with the method of cluster beam deposition of palladium nanoparticle thin lms on carbon nanoparticle supporting layers and used as sensitive nonenzyme hydrogen peroxide sensors. An enhancement on the electrocatalytic activity of the palladium nanoparticles toward H2O2 reduction was observed, which was related to the coverage of the carbon nanoparticles. With one monolayer of carbon nanoparticles, the H2O2 detection sensitivity reached the maximum, which was more than twice of that of the pure Pd nanoparticles.

TiO2 nanoparticles in aquatic environments:impact on heavy metals distribution in sediments and overlying water

The extensive application of TiO_(2)nanoparticles(NPs)highlights the importance of investigating their influence on aquatic systems.In this work,the effect of TiO_(2)NPs on heavy metals speciation was studied on a lab scale.For this goal,a series of aquaria containing water,sediment,and TiO_(2)NPs with various concentrations were set up.The study results revealed that TiO_(2)NPs caused(copper)Cu,(mercury)Hg,(titanium)Ti,and(zinc)Zn to be adsorbed by sediments in the forms of exchangeable and Fe-Mn species.According to measurements,30μg/L of TiO_(2)NPs made Cu,Hg,Ti and Zn concentration in the water column decreased from 33,1.14,20,and 32 to 4,0.58,3,and 22.3μg/L,respectively.Manganese(Mn)was also adsorbed by sediment,and in all experiments,its concentration in the water column reduced from 44 to about 20μg/L.Due to the photocatalytic capacity of TiO_(2)NPs,arsenic(As)concentration in the water column increased from 0 to 8.7μg/L with the introduction of30μg/L of TiO_(2)NPs.The sequential extraction results showed that in all experiments,concentrations of lead(Pb),nickel(Ni),and cobalt(Co)remained constant in different chemical species of sediment,which meant conservative behavior of them in presence of TiO_(2)NPs.In addition,a remarkable change was observed in water quality parameters such as ORP,TDS,TOC,BOD,NO3’and PO_(4)after the introduction of TiO_(2)NPs to aquaria.The reason behind these changes could be related to the decomposition of sediment organic content by TiO_(2)NPs.

强吸收纳米粒子团簇的光泳力悬浮及热泳力下的迁移行为

为了探索空气中强吸收纳米粒子团簇在激光作用下的悬浮以及迁移行为,提出采用反向传输的双贝塞尔光束对纳米粒子团簇进行捕获及悬浮,而后释放团簇,观察和计算分析团簇的迁移行为.两束贝塞尔光束由锥透镜和偏振分光方式产生,进行反向水平布置,形成三维光阱,光阱刚度可通过调节两束贝塞尔光束的功率比进行控制.悬浮室内的粒子通过微弱气流进行流化,而后被光阱捕获和悬浮.采用高速摄像仪对团簇的悬浮及迁移过程进行记录,然后通过图像分析来获取粒子运动参数.以强吸收性超细煤粉粒子团簇为对象,首先对其进行悬浮和释放迁移的实验研究,而后对团簇所受的光泳力、重力、浮力、曳力以及热泳力进行计算和分析.实验和计算的结果表明:强吸收性纳米粒子团簇在激光作用下产生的光泳力占主导作用;团簇能够被稳定地悬浮在反向传输的双贝塞尔光束形成的三维势阱中,通过调整悬浮的位置而达到与重力、浮力、曳力等的动态平衡;利用悬浮的相对不稳定度分析评价强吸收性粒子团簇的稳定性,超细煤粉粒子团簇的最小相对不稳定度可达0.075;通过对团簇释放后的高速图像进行分析,可获得团簇的迁移运动参数,从而测量出团簇所受的热泳力;对于等效粒径为13—21μm的超细煤粉粒子团簇,其热泳力量级为10-11—10-10N,随着团簇粒径的增大,热泳力线性增大,与理论计算结果趋势一致.通过利用激光对粒子进行悬浮和释放的方式为热泳力的测量和研究提供了一种新的研究思路,也为气体介质中粒子的控制和输运展现了一种新的操控手段.

纳米颗粒调剖剂的制备、表征及其聚集封堵特性

研究提出了分散注入-原位聚集封堵的思路,以苯乙烯和丙烯酰胺为聚合单体,研制出一种表面含有酰胺基团且具有核壳非均质结构的纳米颗粒调剖剂,通过向油藏中注入粒径远小于油藏孔喉尺寸的纳米颗粒,将分散于地层水中的纳米颗粒移至油藏深部后,与预先注入到地层中的调控剂相接触,聚集成与水窜通道尺寸相匹配的颗粒簇,实现对水窜通道的封堵。制备的纳米颗粒热分解温度可达300℃以上,能够适用于高温油藏,并且纳米颗粒膨胀倍数小于2.0,可有效避免膨胀倍数过大导致的运移过程中剪切破碎的问题。封堵实验表明,纳米颗粒注入性良好,注入压力与注水时几乎无差别,纳米颗粒与预先注入的聚集调控剂混合后聚集成颗粒簇调剖剂,能够对岩芯孔喉进行有效封堵,在0.1μm 2岩芯中,纳米颗粒聚集堵率大于80%。

Nurturing the marriages of single atoms with atomic clusters and nanoparticles for better heterogeneous electrocatalysis

Single-atom catalysts,featuring some of the most unique activities,selectivity,and high metal utilization,have been extensively studied over the past decade.Given their high activity,selectivity,especially towards small molecules or key intermediate conversions,they can be synergized together with other active species(typically other single atoms,atomic clusters,or nanoparticles)in either tandem or parallel or both,leading to much better performance in complex catalytic processes.Although there have been reports on effectively combining the multiple components into one single catalytic entity,the combination and synergy between single atoms and other active species have not been reviewed and examined in a systematic manner.Herein,in this overview,the key synergistic interactions,binary complementary effects,and the bifunctional functions of single atoms with other active species are defined and discussed in detail.The integration functions of their marriages are in-vestigated with particular emphasis on the homogeneous and heterogeneous combinations,spatial distribution,synthetic strategies,and the thus-derived outstanding catalytic performance,together with new light shined on the catalytic mechanisms by zooming in several case studies.The dynamic nature of each of the active species and in particular their interactions in such new catalytic entities in the heterogeneous electrocatalytic processes are visited,on the basis of the in situ/operando evidence.Last,we feature the current chal-lenges and future perspectives of these integrated catalytic entities that can offer guidance for advanced catalyst design by the rational combination and synergy of binary or multiple active species.

Cell surface engineering with polyelectrolyte-stabilized magnetic nanoparticles： A facile approach for fabrication of artificial multicellular tissue-mimicking clusters

Regenerative medicine requires new ways to assemble and manipulate cells for fabrication of tissue-like constructs. Here we report a novel approach for cell surface engineering of human cells using polymer-stabilized magnetic nanoparticles （MNPs）. Cationic polyelectrolyte-coated MNPs are directly deposited onto cellular membranes, producing a mesoporous semi-permeable layer and rendering cells magnetically responsive. Deposition of MNPs can be completed within minutes, under cell-friendly conditions （room temperature and physiologic media）. Microscopy （TEM, SEM, AFM, and enhanced dark-field imaging） revealed the intercalation of nanoparticles into the cellular microvilli network. A detailed viability investigation was performed and suggested that MNPs do not inhibit membrane integrity, enzymatic activity, adhesion, proliferation, or cytoskeleton formation, and do not induce apoptosis in either cancer or primary cells. Finally, magnetically functionalized cells were employed to fabricate viable layered planar （two-cell layers） cell sheets and 3D multicellular spheroids.

The effect of neighbor distance of magnetic nanoparticle clusters on magnetic resonance relaxation properties

Superparamagnetic iron oxide （SPIO） nanoparticle clusters are one unique form which can enhance magnetic relaxivity and improve the magnetic resonance imaging contrast at the same iron concentration, comparing to single SPIO nanoparticles. Controlling of cluster size and other structural parameters have drawn great interests in this field to further improve their magnetic properties. In this study, we investigated how the interparticle distance （also known as neighbor distance） of SP10 nanocrystals within clusters affect their magnetic relaxation behaviors. To adjust the neighbor distance, different amount of cholesterol （CHO） was chosen as model spacers embedded into SPIO nanocluster systems with the help of amphiphilic diblock copolymer poly（ethylene glyco）-polyester. Small- angle X-ray scattering was applied to quantify the neighbor distance of SPIO clusters. The results demonstrated that the averaged SPIO nanocrystal neighbor distance of nan- oclusters increased with higher amount of added CHO. Moreover, these SPIO nanocrystal clusters had the promi- nent magnetic relaxation properties. Simultaneously, con- trolling of SPIO nanocrystal neighbor distance can regulate the saturation magnetization （Ms） and magnetic resonance （MR） T2 relaxation of the aggregation, and ultimately obtain better MR contrast effects with decreased neighbor distance.

Highly dispersed Pd clusters/nanoparticles encapsulated in MOFs via in situ auto-reduction method for aqueous phenol hydrogenation

In this work,a novel in situ auto-reduction strategy was developed to encapsulate uniformly dispersed Pd clusters/nanoparticles in MIL-125-NH_(2).It is demonstrated that the amino groups in MIL-125-NH_(2)can react with formaldehyde to form novel reducing groups(-NH-CH_(2)OH),which can in situ auto-reduce the encapsulated Pd^(2+)ions to metallic Pd clusters/nanoparticles.As no additional reductants are required,the strategy limits the aggregation and migration of Pd clusters and the formation of large Pd nanoparticles via controlling the amount of Pd^(2+)precursor.When applied as catalysts in the hydrogenation of phenol in the aqueous phase,the obtained Pd(1.5)/MIL-125-NH-CH_(2)OH catalyst with highly dispersed Pd clusters/nanoparticles with the size of around 2 nm exhibited 100%of phenol conversion and 100%of cyclohexanone selectivity at 70℃ after 5 h,as well as remarkable reusability for at least five cycles due to the large MOF surface area,the highly dispersed Pd clusters/nanoparticles and their excellent stability within the MIL-125-NH-CH_(2)OH framework.

Two-dimensional Sb cluster superlattice on Si substrate fabricated by a two-step method

Nanoclusters consisting of a few atoms have attracted a lot of research interests due to their exotic size-dependent properties. Here, well-ordered two-dimensional Sb cluster superlattice was fabricated on Si substrate by a two-step method and characterized by scanning tunneling microscopy. High resolution scanning tunneling microscope measurements revealed the fine structures of the Sb clusters, which consist of several Sb atoms ranging from 2 to 7. Furthermore, the electronic structure of the nanocluster displays the quantized energy-level which is due to the single-electron tunneling effects. We believe that the fabrication of Sb cluster superlattice broadens the species of the cluster superlattice and provides a promising candidate to further explore the novel physical and chemical properties of the semimetal nanocluster.

纳米铝颗粒在不同炸药环境中氧化燃烧的分子动力学模拟

为探索炸药环境对纳米铝颗粒(ANP)氧化燃烧的影响,采用分子动力学模拟方法,研究了程序升温加热、恒温加热及绝热加热下ANP在硝化甘油(NG)、黑索今(RDX)和三氨基三硝基苯(TATB)环境中的氧化燃烧机理。结果表明,NG、RDX和TATB对ANP的氧化性依次减弱,对燃烧的微观机制产生了不同的影响。在氧化形貌上,随着炸药环境氧化性的减弱,ANP在急速升温下发生崩裂的程度减弱,氧化速度变慢,最终形成的Al团簇中Al原子的主要配位数从NG环境中的7配位下降为TATB环境中的6配位。并且在TATB环境中,ANP上解离的Al原子在环境中形成了原子数约为100的大团簇结构,这也抑制了ANP的氧化进程。在团簇数量上,程序升温加热下不同炸药环境间的差异较小。而在恒温加热和绝热加热下,随着炸药环境氧化性的减弱,ANP崩裂后形成的Al团簇数量减少,并且由于小Al团簇在氧化性弱的环境中不易团聚,此后Al团簇数量会在短时间内持续增加。在化学反应特性上,NG环境中的ANP主要与炸药分解的含氧产物反应,导致形成的Al团簇氧化更加完全。而在RDX和TATB环境中,ANP还能与N2、CN等不含氧产物发生大量反应,导致形成的Al团簇中包含较多的C、H、N原子,Al团簇的氧化并不完全。

基于频率筛选的磁粒子成像量化分析研究

为实现磁粒子成像(magnetic particle imaging,MPI)中示踪剂铁量化,本研究基于仿真程序,采集二维扫描图像,筛选信号频率并重建图像,以聚类结果作为先验信息,约束水平集函数的演化,对示踪剂图像进行分割,并借助Dice系数、IoU等参数定量评估分割效果。通过计算分割区域的信号强度总和,建立MPI信号与已知示踪剂铁含量的校正曲线。结果显示,频率筛选后显著缩短了信号重建时间;基于先验的水平集方法Dice系数和IoU均大于0.90,实现了肿瘤区域较精准的分割;通过本研究建立的MPI信号强度与铁含量的校正曲线,实现了示踪剂铁量化,平均误差为3.11%,最小误差0.03%。结果表明,基于先验的水平集方法可实现较精确的图像分割和铁量化,为MPI临床前定量研究提供参考。