Micelles Cascade Assembly to Tandem Porous Catalyst for Waste Plastics Upcycling.

Catalytic upcycling of polyolefins into high-value chemicals represents the direction in end-of-life plastics valorization, but poses great challenges. Here, we report the synthesis of a tandem porous catalyst via a micelle cascade assembly strategy for selectively catalytic cracking of polyethylene into olefins at a low temperature. A hierarchically porous silica layer from mesopore to macropore is constructed on the surface of microporous ZSM-5 nanosheets through cascade assembly of dynamic micelles. The outer macropore arrays can adsorb bulky polyolefins quickly by the capillary and hydrophobic effects, enhancing the diffusion and access to active sites. The middle mesopores present a nanoconfinement space, pre-cracking polyolefins into intermediates by weak acid sites, which then transport into zeolites micropores for further cracking by strong Brønsted acid sites. The hierarchically porous and acidic structures, mimicking biomimetic protease catalytic clefts, ideally match the tandem cracking steps of polyolefins, thus suppressing coke formation and facilitating product escape. As a result, light hydrocarbons (C1-C7) are produced with a yield of 443 mmol gZSM-5 -1, where 74.3 % of them are C3-C6 olefins, much superior to ZSM-5 and porous silica catalysts. This tandem porous catalyst exemplifies a superstructure design of catalytic cracking catalysts for industrial and economical upcycling of plastic wastes.

Asymmetric Monolayer Mesoporous Nanosheets of Regularly Arranged Semi-Opened Pores via a Dual-Emulsion-Directed Micelle Assembly.

Constructing asymmetric two-dimensional (2D) mesoporous nanomaterials with new pore structure, tunable monolayer architectures, and especially anisotropic surfaces remains a great challenge in materials science. Here, we report a dual-emulsion directed micelle assembly approach to fabricate a novel type of asymmetric monolayer mesoporous organosilica nanosheet for the first time. In this asymmetric 2D structure, numerous quasi-spherical semiopened mesopores (∼20 nm in diameter, 24 nm in opening size) were regularly arranged on a plane, endowing the porous nanosheets (several micrometers in size) with a typical surface anisotropy on two sides. Meanwhile, lots of triangular intervoids (4.0-5.0 nm in size) can also be found among each three semiopened mesopores, enabling the nanosheet to be interconnected. Vitally, such interconnected, anisotropic porous nanosheets exhibit ultrahigh accessible surface area (∼714 m2 g-1) and good lipophilicity properties owing to the abundant semiopened mesopores. Additionally, besides the nanosheet, the configuration of the asymmetric porous structure can also be transformed into a microcapsule when controlling the emulsification size via a facile ultrasonic treatment. As a demonstration, we show that the asymmetric microcapsule shows a high demulsification efficiency (>98%) and cyclic stability (>6 recycle times). Our protocol opens up a new avenue for developing next-generation asymmetric mesoporous materials for various applications.

Chiral Skeletons of Mesoporous Silica Nanospheres to Mitigate Alzheimer's ß-Amyloid Aggregation.

Chiral mesoporous silica (mSiO2) nanomaterials have gained significant attention during the past two decades. Most of them show a topologically characteristic helix; however, little attention has been paid to the molecular-scale chirality of mSiO2 frameworks. Herein, we report a chiral amide-gel-directed synthesis strategy for the fabrication of chiral mSiO2 nanospheres with molecular-scale-like chirality in the silicate skeletons. The functionalization of micelles with the chiral amide gels via electrostatic interactions realizes the growth of molecular configuration chiral silica sols. Subsequent modular self-assembly results in the formation of dendritic large mesoporous silica nanospheres with molecular chirality of the silica frameworks. As a result, the resultant chiral mSiO2 nanospheres show abundant large mesopores (∼10.1 nm), high pore volumes (∼1.8 cm3·g-1), high surface areas (∼525 m2·g-1), and evident CD activity. The successful transfer of the chirality from the chiral amide gels to composited micelles and further to asymmetric silica polymeric frameworks based on modular self-assembly leads to the presence of molecular chirality in the final products. The chiral mSiO2 frameworks display a good chiral stability after a high-temperature calcination (even up to 1000 °C). The chiral mSiO2 can impart a notable decline in ß-amyloid protein (Aß42) aggregation formation up to 79%, leading to significant mitigation of Aß42-induced cytotoxicity on the human neuroblastoma line SH-ST5Y cells in vitro. This finding opens a new avenue to construct the molecular chirality configuration in nanomaterials for optical and biomedical applications.

Surface Stretching Enables Highly Disordered Graphitic Domains for Ultrahigh Rate Sodium Storage.

Hard carbons (HCs) with high sloping capacity are considered as the leading candidate anode for sodium-ion batteries (SIBs); nevertheless, achieving basically complete slope-dominated behavior with high rate capability is still a big challenge. Herein, the synthesis of mesoporous carbon nanospheres with highly disordered graphitic domains and MoC nanodots modification via a surface stretching strategy is reported. The MoOx surface coordination layer inhibits the graphitization process at high temperature, thus creating short and wide graphite domains. Meanwhile, the in situ formed MoC nanodots can greatly promote the conductivity of highly disordered carbon. Consequently, MoC@MCNs exhibit an outstanding rate capacity (125 mAh g-1 at 50 A g-1 ). The "adsorption-filling" mechanism combined with excellent kinetics is also studied based on the short-range graphitic domains to reveal the enhanced slope-dominated capacity. The insight in this work encourages the design of HC anodes with dominated slope capacity toward high-performance SIBs.

Emulsion-oriented assembly for Janus double-spherical mesoporous nanoparticles as biological logic gates.

The ability of Janus nanoparticles to establish biological logic systems has been widely exploited, yet conventional non/uni-porous Janus nanoparticles are unable to fully mimic biological communications. Here we demonstrate an emulsion-oriented assembly approach for the fabrication of highly uniform Janus double-spherical MSN&mPDA (MSN, mesoporous silica nanoparticle; mPDA, mesoporous polydopamine) nanoparticles. The delicate Janus nanoparticle possesses a spherical MSN with a diameter of ~150 nm and an mPDA hemisphere with a diameter of ~120 nm. In addition, the mesopore size in the MSN compartment is tunable from ~3 to ~25 nm, while those in the mPDA compartments range from ~5 to ~50 nm. Due to the different chemical properties and mesopore sizes in the two compartments, we achieve selective loading of guests in different compartments, and successfully establish single-particle-level biological logic gates. The dual-mesoporous structure enables consecutive valve-opening and matter-releasing reactions within one single nanoparticle, facilitating the design of single-particle-level logic systems.

In Situ Confinement of Ultrasmall Metal Nanoparticles in Short Mesochannels for Durable Electrocatalytic Nitrate Reduction with High Efficiency and Selectivity.

Electrocatalytic reduction is a sustainable approach for NO3 - removal and high-value N-containing compounds manufacturing, which, however, is strongly obstructed by sluggish kinetics, low selectivity, and poor stability. Herein, the in situ confinement of ultrasmall CuPd alloy nanoparticles in mesochannels of conductive core-shell structured carbon nanotubes@mesoporous carbon substrates (CNTs@mesoC@CuPd) via a simple molecule-mediated interfacial assembly method is reported. As a catalyst for electrocatalytic NO3 - reduction, the CNTs@mesoC@CuPd shows a splendid conversion efficiency (100%), N2  selectivity (98%), cycling stability (>30 days), and removal capacity as high as 30 000 mg N g-1 CuPd, which are much superior to most of the prior reports. Notably, experimental (in situ testing and isotopic labeling) and theoretical results unveil that bimetallic and monometallic catalysts for electrocatalytic NO3 - reduction exhibit exclusive selectivity for N2  and NH3 , respectively. This in situ confinement strategy is universal for the synthesis of stable and highly accessible metallic catalysts, which opens an appealing way to synthesize advanced catalysts with high activity, selectivity, and stability.

Sub-10 nm Corrugated TiO2 Nanowire Arrays by Monomicelle-Directed Assembly for Efficient Hole Extraction.

Precise synthesis of well-ordered ultrathin nanowire arrays with tunable active surface, though attractive in optoelectronics, remains challenging to date. Herein, well-aligned sub-10 nm TiO2 nanowire arrays with controllable corrugated structure have been synthesized by a unique monomicelle-directed assembly method. The nanowires with an exceptionally small diameter of ∼8 nm abreast grow with an identical adjacent distance of ∼10 nm, forming vertically aligned arrays (∼800 nm thickness) with a large surface area of ∼102 m2 g-1. The corrugated structure consists of bowl-like concave structures (∼5 nm diameter) that are closely arranged along the axis of the ultrathin nanowires. And the diameter of the concave structures can be finely manipulated from ∼2 to 5 nm by simply varying the reaction time. The arrays exhibit excellent charge dynamic properties, leading to a high applied bias photon-to-current efficiency up to 1.4% even at a very low potential of 0.41 VRHE and a superior photocurrent of 1.96 mA cm-2 at 1.23 VRHE. Notably, an underlying mechanism of the hole extraction effect for concave walls is first clarified, demonstrating the exact role of concave walls as the hole collection centers for efficient water splitting.

Synthesis of Fully Exposed Single-Atom-Layer Metal Clusters on 2D Ordered Mesoporous TiO2 Nanosheets.

A sulfhydryl monomicelles interfacial assembly strategy is presented for the synthesis of fully exposed single-atom-layer Pt clusters on 2D mesoporous TiO2 (SAL-Pt@mTiO2 ) nanosheets. This synthesis features the introduction of the sulfhydryl group in monomicelles to finely realize the controllable co-assembly process of Pt precursors within ordered mesostructures. The resultant SAL-Pt@mTiO2 shows uniform SAL Pt clusters (≈1.2 nm) anchored in ultrathin 2D nanosheets (≈7 nm) with a high surface area (139 m2 g-1 ), a large pore size (≈25 nm) and a high dispersion (≈99 %). Moreover, this strategy is universal for the synthesis of other SAL metal clusters (Pd and Au) on 2D mTiO2 with high exposure and accessibility. When used as a catalyst for hydrogenation of 4-nitrostyrene, the SAL-Pt@mTiO2 shows a high catalytic activity (TOF up to 2424 h-1 ), 100 % selectivity for 4-aminostyrene, good stability, and anti-resistance to thiourea poisoning under relatively mild conditions (25 °C, 10 bar).

Modular super-assembly of hierarchical superstructures from monomicelle building blocks.

Manipulating the super-assembly of polymeric building blocks still remains a great challenge due to their thermodynamic instability. Here, we report on a type of three-dimensional hierarchical core-satellite SiO2@monomicelle spherical superstructures via a previously unexplored monomicelle interfacial super-assembly route. Notably, in this superstructure, an ultrathin single layer of monomicelle subunits (~18 nm) appears in a typically hexagon-like regular discontinuous distribution (adjacent micelle distance of ~30 nm) on solid spherical interfaces (SiO2), which is difficult to achieve by conventional super-assembled methods. Besides, the number of the monomicelles on colloidal SiO2 interfaces can be quantitatively controlled (from 76 to 180). This quantitative control can be precisely manipulated by tuning the interparticle electrostatic interactions (the intermicellar electrostatic repulsion and electrostatic attractions between the monomicelle units and the SiO2 substrate). This monomicelle interfacial super-assembly strategy will enable a controllable way for building multiscale hierarchical regular micro- and/or macroscale materials and devices.

Unusual Mesoporous Titanium Niobium Oxides Realizing Sodium-Ion Batteries Operated at -40 °C.

Sodium-ion batteries (SIBs) are a promising candidate for grid-scale energy storage, however, the sluggish ion-diffusion kinetics brought by the large radius of Na+ seriously limits the performance of SIBs, let alone at low temperatures. Herein, a confined acid-base pair self-assembly strategy to synthesize unusual Ti0.88 Nb0.88 O4- x @C for high-performance SIBs operating at room and low temperatures is proposed. The confinement self-assembly of the acid-base pair around the micelles and confined crystallization by the carbon layer realize the formation of ordered and stoichiometric mesoporous frameworks with opened ion channels. Thus, the mesoporous Ti0.88 Nb0.88 O4- x @C exhibits rapid Na+ diffusion kinetics at 25 and -40 °C, which are one order higher than that of the nonporous one. A high reversible capacity of 233 mAh g-1 , excellent rate (a specific capacity of 103 mAh g-1 at 50 C), and cycling performances (<0.03% fading per cycle) can be observed at 25 °C. More importantly, even at -40 °C, the mesoporous Ti0.88 Nb0.88 O4- x @C can still deliver the 161 mAh g-1 capacity, a high initial Coulombic efficiency of 60% and outstanding cycling stability (99 mAh g-1 at 0.5 C after 500 cycles). It is believed this strategy opens a new avenue for constructing novel mesoporous electrode materials for low-temperature energy storage.

Gradient Hierarchically Porous Structure for Rapid Capillary-Assisted Catalysis.

Synthesis of hierarchically porous structures with uniform spatial gradient and structure reinforcement effect still remains a great challenge. Herein, we report the synthesis of zeolite@mesoporous silica core-shell nanospheres (ZeoA@MesoS) with a gradient porous structure through a micellar dynamic assembly strategy. In this case, we find that the size of composite micelles can be dynamically changed with the increase of swelling agents, which in situ act as the building blocks for the modular assembly of gradient mesostructures. The ZeoA@MesoS nanospheres are highly dispersed in solvents with uniform micropores in the inner core and a gradient tubular mesopore shell. As a nanoreactor, such hierarchically gradient porous structures enable the capillary-directed fast mass transfer from the solutions to inner active sites. As a result, the ZeoA@MesoS catalysts deliver a fabulous catalytic yield of ∼75% on the esterification of long-chain carboxylic palmitic acids and high stability even toward water interference, which can be well trapped by the ZeoA core, pushing forward the chemical equilibrium. Moreover, a very remarkable catalytic conversion on the C-H arylation reaction of large N-methylindole is achieved (∼98%) by a Pd-immobilized ZeoA@MesoS catalyst. The water tolerance feature gives a notable enhancement of 26% in catalytic yield compared to the Pd-dendritic mesoporous silica without the zeolite core.

Spiral self-assembly of lamellar micelles into multi-shelled hollow nanospheres with unique chiral architecture.

Functional carbon nanospheres are exceptionally useful, yet controllable synthesis of them with well-defined porosity and complex multi-shelled nanostructure remains challenging. Here, we report a lamellar micelle spiral self-assembly strategy to synthesize multi-shelled mesoporous carbon nanospheres with unique chirality. This synthesis features the introduction of shearing flow to drive the spiral self-assembly, which is different from conventional chiral templating methods. Furthermore, a continuous adjustment in the amphipathicity of surfactants can cause the packing parameter changes, namely, micellar structure transformations, resulting in diverse pore structures from single-porous, to radial orientated, to flower-like, and to multi-shelled configurations. The self-supported spiral architecture of these multi-shelled carbon nanospheres, in combination with their high surface area (~530 m2 g−1), abundant nitrogen content (~6.2 weight %), and plentiful mesopores (~2.5 nm), affords them excellent electrochemical performance for potassium-ion storage. This simple but powerful micelle-directed self-assembly strategy offers inspiration for future nanostructure design of functional materials.

Ultrahigh Adsorption Capacity and Kinetics of Vertically Oriented Mesoporous Coatings for Removal of Organic Pollutants.

Highly efficient removal of organic pollutants currently is a main worldwide concern in water treatment, and highly challenging. Here, vertically oriented mesoporous coatings (MCs) with tunable surface properties and pore sizes have been developed via the single-micelle directing assembly strategy, which show good adsorption performances toward a wide range of organic pollutants. The micelle size and structure can be precisely regulated by oil molecules based on their n-octanol/water partition coefficients (Log P) in the oil-water diphase assembly system, which are critical to the pore size and pore surface property of the MCs. The affinity and steric effects of the MCs can be on-demand adjusted, as a result, the MCs show a ultrahigh adsorption capacity (263 mg g-1 ), surface occupancy ratio (≈41.92%), and adsorption rate (≈10.85 mg g-1  min-1 ) for microcystin-LR, which is among the best performances up to date. The MCs also show an excellent universality to remove organic pollutants with different properties. Moreover, overcoming the challenges proposed by particulate absorbents, the MCs are stable and can be easily regenerated and reused without secondary contamination. This work paves a new route to the synthesis of high-quality MCs for water purification.

Inorganic-organic competitive coating strategy derived uniform hollow gradient-structured ferroferric oxide-carbon nanospheres for ultra-fast and long-term lithium-ion battery.

The gradient-structure is ideal nanostructure for conversion-type anodes with drastic volume change. Here, we demonstrate an inorganic-organic competitive coating strategy for constructing gradient-structured ferroferric oxide-carbon nanospheres, in which the deposition of ferroferric oxide nanoparticles and polymerization of carbonaceous species are competitive and well controlled by the reaction thermodynamics. The synthesized gradient-structure with a uniform size of ~420 nm consists of the ferroferric oxide nanoparticles (4-8 nm) in carbon matrix, which are aggregated into the inner layer (~15 nm) with high-to-low component distribution from inside to out, and an amorphous carbon layer (~20 nm). As an anode material, the volume change of the gradient-structured ferroferric oxide-carbon nanospheres can be limited to ~22% with ~7% radial expansion, thus resulting in stable reversible specific capacities of ~750 mAh g-1 after ultra-long cycling of 10,000 cycles under ultra-fast rate of 10 A g-1. This unique inorganic-organic competitive coating strategy bring inspiration for nanostructure design of functional materials in energy storage.

Precisely Controlled Vertical Alignment in Mesostructured Carbon Thin Films for Efficient Electrochemical Sensing.

Two-dimensional carbon materials, incorporating a large mesoporosity, are attracting considerable research interest in various fields such as catalysis, electrochemistry, and energy-related technologies owing to their integrated functionalities. However, their potential applications, which require favorable mass transport within mesopore channels, are constrained by the undesirable and finite mesostructural configurations due to the immense synthetic difficulties. Herein, we demonstrate an oriented monomicelle assembly strategy, for the facile fabrication of highly ordered mesoporous carbon thin films with vertically aligned and permeable mesopore channels. Such a facile and reproducible approach relies on the swelling and fusion effect of hydrophobic benzene homologues for directional monomicelle assembly. The orientation assembly process shows precise controllability and great universality, affording mesoporous carbon films with a cracking-free structure over a centimeter in size, highly tunable thicknesses (13 to 85 nm, an interval of ∼12 nm), mesopore size (8.4 to 13.5 nm), and switchable growth substrates. Owing to their large permeable mesopore channels, electrochemical sensors based on vertical mesoporous carbon films exhibit an ultralow limit of detection (50 nmol L-1) and great sensitivity in dopamine detection.

Surface-Confined Winding Assembly of Mesoporous Nanorods.

Bending and folding are important stereoscopic geometry parameters of one-dimensional (1D) nanomaterials, yet the precise control of them has remained a great challenge. Herein, a surface-confined winding assembly strategy is demonstrated to regulate the stereoscopic architecture of uniform 1D mesoporous SiO2 (mSiO2) nanorods. Based on this brand-new strategy, the 1D mSiO2 nanorods can wind on the surface of 3D premade nanoparticles (sphere, cube, hexagon disk, spindle, rod, etc.) and inherit their surface topological structures. Therefore, the mSiO2 nanorods with a diameter of ∼50 nm and a variable length can be bent into arc shapes with variable radii and radians, as well as folded into 60, 90, 120, and 180° angular convex corners with controllable folding times. Additionally, in contrast to conventional core@shell structures, this winding structure induces partial exposure and accessibility of the premade nanoparticles. The functional nanoparticles can exhibit large accessible surface and efficient energy exchanges with the surroundings. As a proof of concept, winding-structured CuS&mSiO2 nanocomposites are fabricated, which are made up of a 100 nm CuS nanosphere and the 1D mSiO2 nanorods with a diameter of ∼50 nm winding the nanosphere in the perimeter. The winding structured nanocomposites are demonstrated to have fourfold photoacoustic imaging intensity compared with the conventional core@shell nanostructure with an inaccessible core because of the greatly enhanced photothermal conversion efficiency (increased by ∼30%). Overall, our work paves the way to the design and synthesis of 1D nanomaterials with controllable bending and folding, as well as the formation of high-performance complex nanocomposites.

Synthesis of sandwich-like graphene@mesoporous nitrogen-doped carbon nanosheets for application in high-performance supercapacitors.

Nanostructured mesoporous carbon materials have been an attractive material for electrochemical energy storage in the recent decades. However, the controllable synthesis of two-dimensional mesoporous carbon with tunable thickness and desired pore structure is highly challenging. Here, a series of graphene@mesoporous nitrogen-doped carbon (denoted as G@mesoNC) core-shell structured nanosheets with tunable thicknesses have been fabricated via a sample hydrothermal method by using cellulose as the green and cheap carbon precursor. The resultant G@mesoNC nanosheets exhibit a distinct sandwich-like structure with tunable thicknesses (from 10 to 30 nm), a large surface area (562 m2 g-1), a narrow pore size distribution (2.3 nm) and a high nitrogen content (7.95%). Significantly, when being used as the electrode for supercapaciors, the resultant G@mesoNC nanosheets showcase a high specific capacitance of 264 F g-1. Most importantly, there is no substantial capacitance decay after 2500 cycles, indicating the perfect cyclic stability of G@mesoNC nanosheets. Our method paves a new way for synthesizing carbon electrodes for energy storage.

Sequential Chemistry Toward Core-Shell Structured Metal Sulfides as Stable and Highly Efficient Visible-Light Photocatalysts.

A universal sequential synthesis strategy in aqueous solution is presented for highly uniform core-shell structured photocatalysts, which consist of a metal sulfide light absorber core and a metal sulfide co-catalyst shell. We show that the sequential chemistry can drive the formation of unique core-shell structures controlled by the constant of solubility product of metal sulfides. A variety of metal sulfide core-shell structures have been demonstrated, including CdS@CoSx , CdS@MnSx , CdS@NiSx , CdS@ZnSx , CuS@CdS, and more complexed CdS@ZnSx @CoSx . The obtained strawberry-like CdS@CoSx core-shell structures exhibit a high photocatalytic H2 production activity of 3.92 mmol h-1 and an impressive apparent quantum efficiency of 67.3 % at 420 nm, which is much better than that of pure CdS nanoballs (0.28 mmol h-1 ), CdS/CoSx composites (0.57 mmol h-1 ), and 5 %wt Pt-loaded CdS photocatalysts (1.84 mmol h-1 ).

Spherical Mesoporous Materials from Single to Multilevel Architectures.

Mesoporous materials with various structures have attracted considerable attention due to their distinctive properties such as large pore sizes, high surface areas, tunable pore structures, and controllable framework compositions. Among them, spherical mesoporous materials (SMMs) are of great interest owing to the unique spherical shape, which show the closed packing nature and lowest surface energy. The open mesopores and short channels of SMMs not only increase the density of high accessible active sites but also facilitate the mass diffusion with short length. These characteristics are particularly useful for applications in catalysis, adsorption, energy storage and conversion, biomedicine, and so on. In addition, the creation of a spherical shape is conformable to the law of natural selection because objects in nature tend to minimize energy, while the sphere is one of the most perfect matter structures. Therefore, the design and synthesis of SMMs are very important from both fundamental and technological viewpoints. Compared to the simple single-level, SMMs with more complex multilevel structures inevitably bring unusual mechanical, electrical, and optical properties, which are highly desired for practical applications. For example, the construction of core-shell structured SMMs has inspired great attention as they can combine multiple components into one functional unit, exhibiting ameliorated or new physicochemical properties, which cannot be obtained from the isolated one. The presence of a hollow cavity in the yolk-shell structure allows sufficient exposure of the core while maintaining the protective ability of the shell, which is conducive to retaining the distance-dependent properties of the core. Multishelled hollow structures consisting of two or more mesoporous shells are expected to show superior activities in various applications compared to their bulk counterparts because more active interfaces and unique compartmentation environments can be provided. Therefore, SMMs from single to multilevel structure represent a class of advanced nanostructured materials with unique structures and fascinating properties. In this Account, we highlight the progresses on the synthesis and applications of SMMs from single to multilevel architectures. The synthetic strategies have been summarized and categorized into (i) the modified Stöber method, (ii) the hydrothermal strategy, (iii) the biphase stratification approach, (iv) the nanoemulsion assembly method, (v) the evaporation induced aggregating assembly (EIAA) method, and (vi) the confined self-assembly strategy. Special emphasis is placed on the synthetic principles and underlying mechanisms for precise control of SMMs over the particle sizes, pore sizes, pore structures and functionalities as well as different levels of architectures. Moreover, the implementation performances in catalysis, drug delivery, and energy related fields have been highlighted. Finally, the opportunities and challenges for the future development of SMMs in terms of synthesis and applications are proposed.

Versatile Nanoemulsion Assembly Approach to Synthesize Functional Mesoporous Carbon Nanospheres with Tunable Pore Sizes and Architectures.

Functional mesoporous carbons have attracted significant scientific and technological interest owning to their fascinating and excellent properties. However, controlled synthesis of functional mesoporous carbons with large tunable pore sizes, small particle size, well-designed functionalities, and uniform morphology is still a great challenge. Herein, we report a versatile nanoemulsion assembly approach to prepare N-doped mesoporous carbon nanospheres with high uniformity and large tunable pore sizes (5-37 nm). We show that the organic molecules (e.g., 1,3,5-trimethylbenzene, TMB) not only play an important role in the evolution of pore sizes but also significantly affect the interfacial interaction between soft templates and carbon precursors. As a result, a well-defined Pluronic F127/TMB/dopamine nanoemulsion can be facilely obtained in the ethanol/water system, which directs the polymerization of dopamine into highly uniform polymer nanospheres and their derived N-doped carbon nanospheres with diversely novel structures such as smooth, golf ball, multichambered, and dendritic nanospheres. The resultant uniform dendritic mesoporous carbon nanospheres show an ultralarge pore size (∼37 nm), small particle size (∼128 nm), high surface area (∼635 m2 g-1), and abundant N content (∼6.8 wt %), which deliver high current density and excellent durability toward oxygen reduction reaction in alkaline solution.