Probing Oxidation Mechanisms in Plasmonic Catalysis: Unraveling the Role of Reactive Oxygen Species.

Plasmon-induced oxidation has conventionally been attributed to the transfer of plasmonic hot holes. However, this theoretical framework encounters challenges in elucidating the latest experimental findings, such as enhanced catalytic efficiency under uncoupled irradiation conditions and superior oxidizability of silver nanoparticles. Herein, we employ liquid surface-enhanced Raman spectroscopy (SERS) as a real-time and in situ tool to explore the oxidation mechanisms in plasmonic catalysis, taking the decarboxylation of p-mercaptobenzoic acid (PMBA) as a case study. Our findings suggest that the plasmon-induced oxidation is driven by reactive oxygen species (ROS) rather than hot holes, holding true for both the Au and Ag nanoparticles. Subsequent investigations suggest that plasmon-induced ROS may arise from hot carriers or energy transfer mechanisms, exhibiting selectivity under different experimental conditions. The observations were substantiated by investigating the cleavage of the carbon-boron bonds. Furthermore, the underlying mechanisms were clarified by energy level theories, advancing our understanding of plasmonic catalysis.

Binder-Free MOF-Based and MOF-Derived Nanoarrays for Flexible Electrochemical Energy Storage: Progress and Perspectives.

The fast development of Internet of Things and the rapid advent of next-generation versatile wearable electronics require cost-effective and highly-efficient electroactive materials for flexible electrochemical energy storage devices. Among various electroactive materials, binder-free nanostructured arrays have attracted widespread attention. Featured with growing on a conductive and flexible substrate without using inactive and insulating binders, binder-free 3D nanoarray electrodes facilitate fast electron/ion transportation and rapid reaction kinetics with more exposed active sites, maintain structure integrity of electrodes even under bending or twisted conditions, readily release generated joule heat during charge/discharge cycles and achieve enhanced gravimetric capacity of the whole device. Binder-free metal-organic framework (MOF) nanoarrays and/or MOF-derived nanoarrays with high surface area and unique porous structure have emerged with great potential in energy storage field and been extensively exploited in recent years. In this review, common substrates used for binder-free nanoarrays are compared and discussed. Various MOF-based and MOF-derived nanoarrays, including metal oxides, sulfides, selenides, nitrides, phosphides and nitrogen-doped carbons, are surveyed and their electrochemical performance along with their applications in flexible energy storage are analyzed and overviewed. In addition, key technical issues and outlooks on future development of MOF-based and MOF-derived nanoarrays toward flexible energy storage are also offered.

High-Sensitivity Photoelectrochemical Ultraviolet Photodetector with Stable pH-Universal Adaptability Based on Whole Single-Crystal Integrated Self-Supporting 4H-SiC Nanoarrays.

Emerging photoelectrochemical (PEC) photodetectors (PDs) have notable advantages over conventional PDs and have attracted extensive attention. However, harsh liquid environments, such as those with high corrosivity and attenuation, substantially restrict their widespread application. Moreover, most PEC PDs are constructed by assembling numerous nanostructures on current collector substrates, which inevitably contain abundant interfaces and defects, thus greatly weakening the properties of PDs. To address these challenges, a high-performance pH-universal PEC ultraviolet (UV) PD based on a whole single-crystal integrated self-supporting 4H-SiC nanopore array photoelectrode is constructed, which is fabricated using a two-step anodic oxidation approach. The PD exhibits excellent photodetection behavior, with high responsivity (218.77 mA W-1), detectivity (6.64 × 1013 Jones), external quantum efficiency (72.47%), and rapid rise/decay times (17/48 ms) under 375 nm light illumination with a low intensity of 0.15 mW cm-2 and a bias voltage of 0.6 V, which is fall in the state-of-the-art of the wide-bandgap semiconductor-based PDs reported thus far. Furthermore, the SiC PEC PD exhibits excellent photoresponse and long-term operational stability in pH-universal liquid environments. The improved photodetection performance of the SiC PEC PD is primarily attributed to the synergistic effect of the nanopore array structure, integrated self-supporting configuration, and single-crystal structure of the whole photoelectrode.

Development of sterile platform for quantification of extracellular analytes via single walled carbon nanotubes.

Progress has been made studying cell-cell signaling communication processes. However, due to limitations of current sensors on time and spatial resolution, the role of many extracellular analytes is still unknown. A single walled carbon nanotube (SWNT) platform was previously developed based on the avidin-biotin immobilization of SWNT to a glass substrate. The SWNT platform provides real time feedback about analyte concentration and has a high concentration of evenly distributed sensors, both of which are essential for the study of extracellular analytes. Unfortunately, this initial SWNT platform is synthesized through unsterile conditions and cannot be sterilized post-production due to the delicate nature of the sensors, making it unsuitable for in vitro work. Herein the multiple-step process for SWNT immobilization is modified and the platform's biocompatibility is assessed in terms of sterility, cytotoxicity, cell proliferation, and cell morphology through comparison with non-sensors controls. The results demonstrate the SWNT platform's sterility and lack of toxicity over 72 h. The proliferation rate and morphology profiles for cells growing on the SWNT platform are similar to those grown on tissue culture substrates. This novel nano-sensor platform preserves cell health and cell functionality over time, offering opportunities to study extracellular analytes gradients in cellular communication.

In Situ Coupling of Carbon Dots with Co-ZIF Nanoarrays Enabling Highly Efficient Oxygen Evolution Electrocatalysis.

Metal-organic frameworks (MOFs) are regarded as one promising class of precatalysts for electrocatalytic oxygen evolution reaction (OER), yet most of them suffer from poor conductivity and lack of coordinatively unsaturated metal sites, which hinders the fast electrochemical reconstruction and thus a poor OER activity. To address this issue, a unique heterocomposite has been constructed by in situ inserting carbon dots (CDs) into cobalt-based zeolitic imidazolate framework (Co-ZIF) nanosheet arrays (Co-ZIF/CDs/CC) in the presence of carbon cloth (CC) via one-pot coprecipitation for alkaline OER. Benefiting from the synergism between CDs and Co-ZIF subunits such as superior conductivity, strong charge interaction as well as abundant metal sites exposure, the Co-ZIF/CDs/CC exhibits an enhanced promotion effect for OER and contributes to the deep phase transformation from CDs-coupled Co-ZIF to CDs-coupled active CoOOH. As expected, the achieved Co-ZIF/CDs/CC only requires an overpotential of 226 mV to deliver 10 mA cm-2 in 1.0 M KOH, which is lower than that of Co-ZIF/CC and superior to most previously reported CC-supported MOF precatalysts. Moreover, it can also maintain a large current density of 100 mA cm-2 for 24 h with negligible activity decay.

Host-Guest Self-Assembled Interfacial Nanoarrays for Precise Metabolic Profiling.

Accurate and rapid metabolic profiling of cerebrospinal fluid (CSF) is urgently needed but remains challenging for clinical diagnosis of central nervous system diseases and biomarker discovery. Matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) holds promise for metabolic analysis. Its low signal reproducibility, however, severely restricts acquisition of quantitative MS data in clinical practice. Herein, a multifunctional self-assembled AuNPs array (MSANA)-based LDI-MS platform for direct amino acids analysis and metabolic profiling in patient CSF samples is developed. MSANA featuring a highly ordered and closely packed two-dimensional nanostructure permits capture and direct analysis of aromatic amino acids by LDI-MS with high selectivity and micromolar sensitivity. Meanwhile, the MSANA-based LDI-MS platform exhibits excellent reproducibility (RSD < 10%), largely outperforming the direct matrix spotting approach widely used now (RSD < 44%). The platform is successfully used in metabolic profiling of CSF (1 µL) within minutes for discrimination of medulloblastoma patients from non-tumor controls. Taken together, the MSANA-based LDI-MS platform shows potential clinical values toward large-scale metabolic diagnostics and pathogenic mechanism study.

Surface Engineering over Metal-Organic Framework Nanoarray to Realize Boosted and Sustained Urea Oxidation.

Facilitating C─N bond cleavage and promoting *COO desorption are essential yet challenging in urea oxidation reactions (UORs). Herein a novel interfacial coordination assembly protocol is established to modify the Co-phytate coordination complex on the Ni-based metal-organic framework (MOF) nanosheet array (CC/Ni-BDC@Co-PA) toward boosted and sustained UOR electrocatalysis. Comprehensive experimental and theoretical investigations unveil that surface Co-PA modification over Ni-BDC can manipulate the electronic state of Ni sites, and in situ evolved charge-redistributed surface can promote urea adsorption and the subsequent C─N bond cleavage. Impressively, Co-PA functionalization can impart a negatively charged catalyst surface with improved aerophobicity, not only weakening *COO adsorption and promoting CO2 departure, but also repelling CO3 2- approaching to deactivate Ni species, eventually alleviating CO2 poisoning and enhancing operational durability. Beyond that, improved hydrophilic and aerophobic characteristics would also contribute to better mass transfer kinetics. Consequently, CC/Ni-BDC@Co-PA exhibits prominent UOR performance with an ultralow potential of 1.300 V versus RHE to attain 10 mA cm-2 , a small Tafel slope of 45 mV dec-1 , and strong durability, comparable to the best Ni-based electrocatalysts documented thus far. This work affords a novel paradigm to construct MOF-based materials for promoted and sustained UOR catalysis through elegant surface engineering based on a metal-PA complex.

Metal Selenide-Based Superstructure Nanoarrays with Ultrahigh Capacity for Alkaline Zn Batteries.

Transition metal selenides (TMSs) have great potential as cathode materials for alkaline Zn batteries (AZBs) owing to their high theoretical capacity and metallic conductivity. However, achieving a high specific capacity remains a formidable challenge due to the low structural stability and sluggish reaction kinetics of single-phase TMS. Herein, a facile method for fabricating a robust CoSe2 @Ni3 Se4 @Ni(OH)2 superstructure nanoarray (CNSNA) as an AZB cathode is presented. The sophisticated design enables structural stability and abundant active surface sites for efficient charge storage. Furthermore, the redox mediator K3 [Fe(CN)6 ] is employed to expedite the reaction kinetics and introduce supplementary redox reactions, further enhancing the charge storage capability. Consequently, the CNSNA electrode delivers an exceptional specific capacitance (609.08 mAh g-1 at 1 A g-1 ), surpassing all previously reported selenide-based materials. High-rate capability (239.37 mAh g-1 at 20 A g-1 ) and long cycling stability have also been achieved. The comprehensive charge storage mechanism studies confirmed the structural integrity, kinetic improvement, and high reactivity of the CNSNA superstructure. Moreover, the corresponding AZB based on CNSNA demonstrates an extraordinarily high energy density of 516.58 Wh kg-1 . The work offers guidance in the construction of superstructure-based TMS electrode materials, paving the way for the development of high-performance AZBs.

Constructing Co@TiO2 Nanoarray Heterostructure with Schottky Contact for Selective Electrocatalytic Nitrate Reduction to Ammonia.

Electrochemical nitrate (NO3 - ) reduction reaction (NO3 - RR) is a potential sustainable route for large-scale ambient ammonia (NH3 ) synthesis and regulating the nitrogen cycle. However, as this reaction involves multi-electron transfer steps, it urgently needs efficient electrocatalysts on promoting NH3  selectivity. Herein, a rational design of Co nanoparticles anchored on TiO2  nanobelt array on titanium plate (Co@TiO2 /TP) is presented as a high-efficiency electrocatalyst for NO3 - RR. Density theory calculations demonstrate that the constructed Schottky heterostructures coupling metallic Co with semiconductor TiO2  develop a built-in electric field, which can accelerate the rate determining step and facilitate NO3 - adsorption, ensuring the selective conversion to NH3 . Expectantly, the Co@TiO2 /TP electrocatalyst attains an excellent Faradaic efficiency of 96.7% and a high NH3  yield of 800.0 µmol h-1  cm-2  under neutral solution. More importantly, Co@TiO2 /TP heterostructure catalyst also presents a remarkable stability in 50-h electrolysis test.

Synergistic Bimetallic CoCu-Codecorated Carbon Nanosheet Arrays as Integrated Bifunctional Cathodes for High-Performance Rechargeable/Flexible Zinc-Air Batteries.

The unremitting exploration of well-architectured and high-efficiency oxygen electrocatalysts is promising to speed up the surface-mediated oxygen reduction/evolution reaction (ORR/OER) kinetics of rechargeable zinc-air batteries (ZABs). Herein, bimetallic CoCu-codecorated carbon nanosheet arrays (CoCu/N-CNS) are proposed as self-supported bifunctional oxygen catalysts. The integrated catalysts are in situ constructed via a simple sacrificial-templated strategy, imparting CoCu/N-CNS with 3D interconnected conductive pathways, abundant mesopores for electrolyte penetration and ion diffusion, as well as Cu-synergized Co-Nx /O reactive sites for improved catalytic activities. By incorporating a moderate amount of Cu into CoCu/N-CNS, the bifunctional activities can be further increased due to synergistic oxygen electrocatalysis. Consequently, the optimized CoCu/N-CNS realizes a low overall overpotential of 0.64 V for OER and ORR and leads to high-performance liquid ZABs with high gravimetric energy (879.7 Wh kg-1 ), high peak power density (104.3 mW cm-2 ), and remarkable cyclic stability upon 400 h/1000 cycles at 10 mA cm-2 . More impressively, all-solid-state flexible ZABs assembled with the CoCu/N-CNS cathode exhibit superior rate performance and exceptional mechanical flexibility under arbitrary bending conditions. This CoCu/N-CNS monolith holds significant potential in advancing cation-modulated multimetallic electrocatalysts and multifunctional nanocatalysts.

Rational Construction of Heterostructured Cu3 P@TiO2 Nanoarray for High-Efficiency Electrochemical Nitrite Reduction to Ammonia.

Electroreduction of nitrite (NO2 - ) to valuable ammonia (NH3 ) offers a sustainable and green approach for NH3 synthesis. Here, a Cu3 P@TiO2 heterostructure is rationally constructed as an active catalyst for selective NO2 - -to-NH3 electroreduction, with rich nanosized Cu3 P anchored on a TiO2 nanoribbon array on Ti plate (Cu3 P@TiO2 /TP). When performed in the 0.1 m NaOH with 0.1 m NaNO2 , the Cu3 P@TiO2 /TP electrode obtains a large NH3 yield of 1583.4 µmol h-1  cm-2 and a high Faradaic efficiency of 97.1%. More importantly, Cu3 P@TiO2 /TP also delivers remarkable long-term stability for 50 h electrolysis. Theoretical calculations indicate that intermediate adsorption/conversion processes on Cu3 P@TiO2 interfaces are synergistically optimized, substantially facilitating the conversion of NO2 - -to-NH3 .

Pd-Doped Co3 O4 Nanoarray for Efficient Eight-Electron Nitrate Electrocatalytic Reduction to Ammonia Synthesis.

Ammonia (NH3 ) is an indispensable feedstock for fertilizer production and one of the most ideal green hydrogen rich fuel. Electrochemical nitrate (NO3 - ) reduction reaction (NO3 - RR) is being explored as a promising strategy for green to synthesize industrial-scale NH3 , which has nonetheless involved complex multi-reaction process. This work presents a Pd-doped Co3 O4 nanoarray on titanium mesh (Pd-Co3 O4 /TM) electrode for highly efficient and selective electrocatalytic NO3 - RR to NH3 at low onset potential. The well-designed Pd-Co3 O4 /TM delivers a large NH3 yield of 745.6 µmol h-1 cm-2 and an extremely high Faradaic efficiency (FE) of 98.7% at -0.3 V with strong stability. These calculations further indicate that the doping Co3 O4 with Pd improves the adsorption characteristic of Pd-Co3 O4 and optimizes the free energies for intermediates, thereby facilitating the kinetics of the reaction. Furthermore, assembling this catalyst in a Zn-NO3 - battery realizes a power density of 3.9 mW cm-2 and an excellent FE of 98.8% for NH3 .

Recent Advances in Self-Supported Semiconductor Heterojunction Nanoarrays as Efficient Photoanodes for Photoelectrochemical Water Splitting.

Growth of semiconductor heterojunction nanoarrays directly on conductive substrates represents a promising strategy toward high-performance photoelectrodes for photoelectrochemical (PEC) water splitting. By controlling the growth conditions, heterojunction nanoarrays with different morphologies and semiconductor components can be fabricated, resulting in greatly enhanced light-absorption properties, stabilities, and PEC activities. Herein, recent progress in the development of self-supported heterostructured semiconductor nanoarrays as efficient photoanode catalysts for water oxidation is reviewed. Synthetic methods for the fabrication of heterojunction nanoarrays with specific compositions and structures are first discussed, including templating methods, wet chemical syntheses, electrochemical approaches and chemical vapor deposition (CVD) methods. Then, various heterojunction nanoarrays that have been reported in recent years based on particular core semiconductor scaffolds (e.g., TiO2 , ZnO, WO3 , Fe2 O3 , etc.) are summarized, placing strong emphasis on the synergies generated at the interface between the semiconductor components that can favorably boost PEC water oxidation. Whilst strong progress has been made in recent years to enhance the visible-light responsiveness, photon-to-O2 conversion efficiency and stability of photoanodes based on heterojunction nanoarrays, further advancements in all these areas are needed for PEC water splitting to gain any traction alongside photovoltaic-electrochemical (PV-EC) systems as a viable and cost-effective route toward the hydrogen economy.

Biofunctional Nanodot Arrays in Living Cells Uncover Synergistic Co-Condensation of Wnt Signalodroplets.

Qualitative and quantitative analysis of transient signaling platforms in the plasma membrane has remained a key experimental challenge. Here, biofunctional nanodot arrays (bNDAs) are developed to spatially control dimerization and clustering of cell surface receptors at the nanoscale. High-contrast bNDAs with spot diameters of ≈300 nm are obtained by capillary nanostamping of bovine serum albumin bioconjugates, which are subsequently biofunctionalized by reaction with tandem anti-green fluorescence protein (GFP) clamp fusions. Spatially controlled assembly of active Wnt signalosomes is achieved at the nanoscale in the plasma membrane of live cells by capturing the co-receptor Lrp6 into bNDAs via an extracellular GFP tag. Strikingly, co-recruitment is observed of co-receptor Frizzled-8 as well as the cytosolic scaffold proteins Axin-1 and Disheveled-2 into Lrp6 nanodots in the absence of ligand. Density variation and the high dynamics of effector proteins uncover highly cooperative liquid-liquid phase separation (LLPS)-driven assembly of Wnt "signalodroplets" at the plasma membrane, pinpointing the synergistic effects of LLPS for Wnt signaling amplification. These insights highlight the potential of bNDAs for systematically interrogating nanoscale signaling platforms and condensation at the plasma membrane of live cells.

Free-Standing Nanoarrays with Energetic Electrons and Active Sites for Efficient Plasmon-Driven Ammonia Synthesis.

Direct ammonia (NH3 ) synthesis from water and atmospheric nitrogen using sunlight provides an energy-sustainable and carbon-neutral alternative to the Haber-Bosch process. However, the development of such a route with high performance is impeded by the lack of effective charge transfer and abundant active sites to initiate the nitrogen reduction reaction (NRR). Here, the authors report efficient plasmon-induced photoelectrochemical (PEC) NH3 synthesis on the hierarchical free-standing Au/Kx MoO3 /Mo/Kx MoO3 /Au nanoarrays. Endowed with energetically hot electrons and catalytically active sites, the plasmonic nanoarrays exhibit an efficient PEC NH3 synthesis rate of 9.6 µg cm-2 h-1 under visible light irradiation, which is among the highest PEC NRR systems. This work demonstrates the rationally designed plasmonic nanoarrays for highly efficient NH3 synthesis, which paves a new path for PEC catalytic reactions driven by surface plasmons and future monolithic PEC devices for direct artificial photosynthesis.

Controllable Synthesis of Ultrathin Defect-Rich LDH Nanoarrays Coupled with MOF-Derived Co-NC Microarrays for Efficient Overall Water Splitting.

Water electrolysis has attracted immense research interest, nevertheless the lack of low-cost but efficient bifunctional electrocatalysts for both hydrogen and oxygen evolution reactions greatly hinders its commercial applications. Herein, the controllable synthesis of ultrathin defect-rich layered double hydroxide (LDH) nanoarrays assembled on metal-organic framework (MOF)-derived Co-NC microarrays for boosting overall water splitting is reported. The Co-NC microarrays can not only provide abundant nucleation sites to produce a large number of LDH nuclei for favoring the growth of ultrathin LDHs, but also help to inhibit their tendency to aggregate. Impressively, five types of ultrathin bimetallic LDH nanoarrays can be electrodeposited on the Co-NC microarrays, forming desirable nanoarray-on-macroarray architectures, which show high uniformity with thicknesses from 1.5 to 1.9 nm. As expected, the electrocatalytic performance is significantly enhanced by exploiting the respective advantages of Co-NC microarrays and ultrathin LDH nanoarrays as well as the potential synergies between them. Especially, the optimal Co-NC@Ni2 Fe-LDH as both cathode and anode can afford the lowest cell voltage of 1.55 V at 10 mA cm-2 , making it one of the best earth-abundant bifunctional electrocatalysts for water electrolysis. This study provides new insights into the rational design of highly-active and low-cost electrocatalysts and facilitates their promising applications in the fields of energy storage and conversion.

Upconversion under Photon Trapping in ZnO/BN Nanoarray: An Ultrahigh Responsivity Solar-Blind Photodetecting Paper.

Solar-blind photodetectors (PDs) are widely applicable in special, military, medical, environmental, and commercial fields. However, high performance and flexible PD for deep ultraviolet (UV) range is still a challenge. Here, it is demonstrated that an upconversion of photon absorption beyond the energy bandgap is achieved in the ZnO nanoarray/h-BN heterostructure, which enables the ultrahigh responsivity of a solar-blind photodetecting paper. The direct growth of ultralong ZnO nanoarray on polycrystalline copper paper induced by h-BN 2D interlayer is obtained. Meanwhile, strong photon trapping takes place within the ZnO nanoarray forest through the cyclic state transition of surface oxygen ions, resulting in an extremely high absorption efficiency (> 99.5%). A flexible photodetecting paper is fabricated for switchable detections between near UV and deep UV signals by critical external bias. The device shows robust reliability, ultrahigh responsivity up to 700 A W-1 @ 265-276 nm, and high photoconductive gain of ≈2 × 103 . A negative differential resistance effect is revealed for driving the rapid transfer of up-converted electrons between adjacent energy valleys (Γ to A) above the critical bias (3.9 V). The discovered rationale and device structure are expected to bring high-efficiency deep UV detecting and future wearable applications.

Boosting Electrocatalytic Oxygen Evolution over Ce-Co9 S8 Core-Shell Nanoneedle Arrays by Electronic and Architectural Dual Engineering.

An dual electronic and architectural engineering strategy is a good way to rationally design earth-abundant and highly efficient electrocatalysts of the oxygen evolution reaction (OER) for sustainable hydrogen-based energy devices. Here, a Ce-doped Co9 S8 core-shell nanoneedle array (Ce-Co9 S8 @CC) supported on a carbon cloth has been designed and developed to accelerate the sluggish kinetics of the OER. Profiting from valance alternative Ce doping, a fine core-shell structure and vertically aligned nanoneedle arrayed architecture, Ce-Co9 S8 @CC integrates modulated electronic structure, highly exposed active sites, and multidimensional mass diffusion channels; together, these afford a favorable catalyzed OER. Ce-Co9 S8 @CC exhibits remarkable performance in the OER in an alkaline medium, where the overpotential requires only 242 mV to deliver a current density of 10 mA cm-2 for the OER; this is 70 mV superior to that of Ce-free Co9 S8 catalyst and other counterparts. Good stability and impressive selectivity (nearly 100 % Faradic efficiency) are also demonstrated. When integrated into a two-electrode OER//HER electrolyzer, the as-prepared Ce-Co9 S8 @CC displays a low operation potential of 1.54 V at 10 mA cm-2 and long-term stability, thus demonstrating great potential for economical water electrolysis.

Self-Supported Transition Metal-Based Nanoarrays for Efficient Energy Storage.

Rechargeable batteries and supercapacitors are currently considered as promising electrochemical energy storage (EES) systems to address the energy and environment issues. Self-supported transition metal (Ni, Co, Mn, Mo, Cu, V)-based materials are promising electrodes for EES devices, which offer highly efficient charge transfer kinetics. This review summarizes the latest development of transition metal-based materials with self-supported structures for EES systems. Special focus has been taken on the synthetic methods, the selection of substrates, architectures and chemical compositions of different self-supported nanoarrays in energy storage systems. Finally, the challenges and opportunities of these materials for future development in this field are briefly discussed. We believe that the advancement in self-supported electrode materials would pave the way towards next-generation EES.

Block copolymer self-assembly assisted fabrication of laterally organized- and stacked- nanoarrays.

Block copolymer (BCP) self-assembly processes are often seen as reliable techniques for advanced nanopatterning to achieve functional surfaces and create templates for nanofabrication. By taking advantage of the tunability in pitch, diameter and feature-to-feature separation of the self-assembled BCP features, complex, laterally organized- and stacked- multicomponent nanoarrays comprising of gold and polymer have been fabricated. The approaches not only demonstrate nanopatterning of up to two levels of hierarchy but also investigate how a variation in the feature-to-feature gap at the first hierarchy affects the self-assembly of polymer features at the second. Such BCP self-assembly enabled multicomponent nanoarray configurations are rarely achieved by other nanofabrication approaches and are particularly promising for pushing the boundaries of block copolymer lithography and in creating unique surface architectures and complex morphologies at the nanoscale.