Mesoporous Transition Metal Oxides Research Articles

Selectivity of Control of Oxygen Reduction Reaction over Mesoporous Transition Metal Oxides Catalysts for Electrified Purification Technologies

Introduction: The use of abundant feedstocks, such as water and air, in manufacturing of value-added products is important in achieving the UN’s Sustainable Development Goals.1 In this context, electrified direct synthesis of chemicals from oxygen in the air is of special interest since it avoids greenhouse gas emissions if the electricity used to drive the synthesis comes from sustainable sources such as solar- and wind-power. The controlling of oxygen reduction path over catalysts incorporation with oxygen evolution reaction as auxiliary reaction enables the electrosynthesis of value-added chemicals, oxygen and hydroxyl radical. The development of cheap materials e.g., mesoporous transition metal oxides, is urged to replace the expensive and scarce of platinum group metal (PGM)-based catalysts, with the ability to provide competitive reaction rate in alkaline media.2 Experimental: A template-free hydrothermal method is developed for the synthesis of mesoporous NiO and NiCo2O4. The materials’ physicochemical properties are characterized by X-ray diffraction, physisorption, electron microscopy, selected electron area diffraction, and X-ray photoelectron spectroscopy. The electrochemical properties and electrocatalytic oxygen activity are evaluated via cyclic voltammetry and electrochemical impedance spectra in alkaline electrolyte using a standard three electrodes electrochemical working station equipped with (ring) rotating disk electrode (RDE/RRDE) techniques.The catalysts coated on carbon fiber paper (CFP) are used as electrode assembled with anion exchange membrane in two-electrodes-electrochemical cell for device test. NiO- and NiCo2O4-modified CFP are used as cathode and anode, respectively, for constructing electrochemical generator of hydroxyl radical. 50 mL min-1 O2 flow was maintained in catholyte to enable oxygen saturation. 20 mg L-1 rhodamine B (RhB)was fed into cathode. Off-line UV-vis measurements were used for RhB quantification. In Electrochemical oxygen purifier, NiCo2O4-modified CFP are used as electrodes. 0.1 - 3 M KOH aqueous solutions were used as anolyte and air-saturated catholyte. The volume of produced oxygen on the anode after 2 h was collected and measured by a water displacement method. Results and Discussion: A facile template-free hydrothermal synthesis is developed for bifunctional oxygen electrocatalysts (OER and ORR) of NiO and NiCo2O4. Physicochemical characterization shows that both NiO and NiCo2O4 are mesoporous with the pore size within a range of 2 - 8 nm and specific surface areas of 60 and 120 m2 g-1, respectively. In addition, NiO and NiCo2O4 possess cubic crystal structures with the corresponding crystal sizes of ~6.0 and 9.3 nm.Electrochemical analysis shows that mesoporous NiCo2O4 has about two times larger capacitance and eight times smaller charge transfer resistance compared to NiO. NiCo2O4 shows higher electrocatalytic activity in OER and selectivity to water as the terminal product of ORR. On the contrary, ORR over NiO yielded hydroxyl radicals, as a product of a Fenton-like reaction of H2O2. The product selectivity in ORR is used to construct two electrolyzers of electrified purification of oxygen and generation of hydroxyl radicals. The optimization of configuration of hydroxyl radical generator enables the degradation of RhB up to 90% after 1 hour, and the electrochemical oxygen purifier shows high efficiency of about 100%. Significance: It is demonstrated that the synthesized mesoporous transition metal oxides via a simple template-free hydrothermal route, and the materials can be used as alternatives to PGM-based electrocatalysts for driving electrochemical cell towards to various products. The work also clearly shows how the composition and structure of catalysts affect the oxygen reactions, and the selectivity of ORR used for producing value-added chemicals coupling with OER. It is shown that the established electrochemical oxygen purifier and hydroxyl radical generator have a high conversion efficiency. Schematic 1. (a) Scheme of operation of the hydroxyl radical generator, (b) the degradation efficiency and rate constants as function of current densities; (c) Scheme of the oxygen purifier, and (d) the generated oxygen volume as a function of working power of the electrochemical cell with different anolyte concentrations. Acknowledgements: This work was supported by the competence center FunMat-II funded by the Swedish Agency for Innovation Systems (Vinnova, grant no 2016-05156), the Swedish Energy Agency (project no 42022-1), and Swedish Research Council (VR 2019-05577, Flexible metal-air primary batteries). Reference: 1 United Nations. Transforming our world: The 2030 agenda for sustainable developement. (UN General Assembly, New York, 2015).2 Yang, Y. et al. Electrocatalysis in Alkaline Media and Alkaline Membrane-Based Energy Technologies. Chem. Rev. 6, 6117–6321 (2022). Figure 1

Selectivity Control of Oxygen Reduction Reaction over Mesoporous Transition Metal Oxide Catalysts for Electrified Purification Technologies

Direct electrification of oxygen-associated reactions contributes to large-scale electrical storage and the launch of the green hydrogen economy. The design of the involved catalysts can mitigate the electrical energy losses and improve the control of the reaction products. We evaluate the effect of the interface composition of electrocatalysts on the efficiency and productivity of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), both mechanistically and at device levels. The ORR and OER were benchmarked on mesoporous nickel(II) oxide and nickel cobaltite (NiO and NiCo2O4, respectively) obtained by a facile template-free hydrothermal synthesis. Physicochemical characterization showed that both NiO and NiCo2O4 are mesoporous and have a cubic crystal structure with abundant surface hydroxyl species. NiCo2O4 showed higher electrocatalytic activity in OER and selectivity to water as the terminal product of ORR. On the contrary, ORR over NiO yielded hydroxyl radicals as products of a Fenton-like reaction of H2O2. The product selectivity in ORR was used to construct two electrolyzers for electrified purification of oxygen and generation of hydroxyl radicals.

Lattice‐Matching Formed Mesoporous Transition Metal Oxide Heterostructures Advance Water Splitting by Active Fe–O–Cu Bridges

AbstractDeveloping efficient bifunctional electrocatalysts toward oxygen/hydrogen evolution reactions is crucial for electrochemical water splitting toward hydrogen production. The high‐performance electrocatalysts depend on the catalytically active and highly accessible reaction sites and their structural robustness, while the rational design of such electrocatalysts with desired features avoiding tedious manufacture is still challenging. Here, a facile method is reported to synthesize mesoporous and heterostructured transition metal oxides strongly anchored on a nickel skeleton (MH‐TMO) containing identified Fe–Cu oxide interfaces with high intrinsic activity, easy accessibility for reaction intermediates, and long‐term stability for alkaline oxygen/hydrogen evolution reactions. The MH‐TMO with the electrocatalytically active Fe–O–Cu bridge has an optimal oxygen binding energy to facilitate adsorption/desorption of oxygen intermediates for oxygen molecules. Associated with the high mass transport through the nanoporous structure, MH‐TMO exhibits impressive oxygen evolution reaction catalysis, with an extremely low overpotential of around 0.22 V at 10 mA cm−2 and low Tafel slope (44.5 mV dec−1) in 1.0 M KOH, realizing a current density of 100 mA cm−2 with an overpotential as low as 0.26 V. As a result, the alkaline electrolyzer assembled by the bifunctional MH‐TMO catalysts operates with an outstanding overall water‐splitting output (1.49 V@10 mA cm−2), outperforming one assembled with noble‐metal‐based catalysts.

A facile preparation of hausmannite as a high-performance catalyst for toluene combustion

Mesoporous transition metal oxide catalysts are well-used in the elimination of volatile organic compounds. In this study, we developed an efficient method for the preparation of mesoporous-Mn 3 O 4 (m-Mn 3 O 4 ) without the use of templates or surfactants. In this method, KCl protects oxygen defects on the surface of fresh Mn 3 O 4 crystallites. m-Mn 3 O 4 shows higher ameliorative catalytic activity than bulk-Mn 3 O 4 (b-Mn 3 O 4 ) and calcined-Mn 3 O 4 (c-Mn 3 O 4 ), achieving toluene catalytic oxidation of T 10 and T 90 (the temperature at a conversion rate of about 10% and 90%) at 191 ℃ and 230 ℃, respectively (WHSV = 40,000 ml·g −1 ·h −1 ). Based on various characterizations, the prepared m-Mn 3 O 4 has large specific surface area and abundant oxygen defects, and thus can provide more surface active sites, which give it superior toluene combustion activity.

Template-free Synthesis of Mesoporous and Crystalline Transition Metal Oxide Nanoplates with Abundant Surface Defects

Summary Mesoporous transition metal oxides with crystalline walls show promising applications in catalysis and energy storage. Syntheses of those crystalline mesoporous oxides, however, currently remain as an unmet challenge because of the large volume shrinkage during crystallization in a sol-gel process. Here, we demonstrate a facile and general template-free method to prepare six mesoporous transition metal oxides, e.g., CuO, CoO, and spinel MCo2O4 (M = Co, Cu, Mn, Zn), with highly crystalline walls and continuous mesopores in the forms of two-dimensional nanoplates or nanosheets. The method is based on the thermal crystalline transformation from basic carbonates to mesoporous metal oxides. The crystal interconversion not only endows the crystallinity and mesoporosity of oxides but also generates abundant surface-step defects that show remarkable enhancement of the catalytic activity of porous oxides. Our method likely provides an alternative paradigm for cost-effective and universal synthesis of crystalline mesoporous oxides beyond the traditional templating methods.

Ordered mesoporous Pt/Fe3O4–CeO2 heterostructure gel particles with enhanced catalytic performance for the reduction of 4‐nitrophenol

The unique physicochemical properties of ordered mesoporous transition metal oxides have attracted more and more attention. The hydrolysis process of metal oxide precursors is difficult to control, and it is difficult to synthesize an ordered mesoporous transition metal oxide material using the conventional template method. Ordered mesoporous Pt/Fe3O4–CeO2 heterostructure gel materials with excellent catalytic properties were successfully prepared using aerogel technology and the chemical deposition method. The Pt/Fe3O4–CeO2 material was an n–n combined heterostructured semiconductor material which consisted of a magnetic Fe3O4 layer, a CeO2 core and Pt noble metal doped nanoparticles. A layer of Fe3O4 thin film was formed on the surface of ordered mesoporous Pt/CeO2 gel matrix material using the chemical deposition method. The intriguing heterostructural features could facilitate reactant diffusion and exposure of active sites which could enhance synergistic catalytic effects between the Pt nanoparticles and CeO2 nanoparticles. Compared with Pt/CeO2, the prepared Pt/Fe3O4–CeO2 showed enhanced catalytic activity in the reduction of 4‐nitrophenol at room temperature. The catalytic activity of the heterostructure catalysts was systematically investigated using 4‐nitrophenol reduction as a model reaction. The results showed that the Pt (0.1%)/Fe3O4–CeO2 sample exhibited the optimal catalytic performance toward catalytic reduction of 4‐nitrophenol to 4‐aminophenol. The study provided a method for the preparation of heterostructure nanocatalysts with high efficiency, which would be effective for application in various catalytic reactions.

A general method to produce mesoporous oxide spherical particles through an aerosol method from aqueous solutions

Mesoporous transition metal oxides (MTMO) with large surface area, nanocrystalline framework, and controlled porosity have brilliant prospects in fields such as energy, environment, catalysis, or nanomedicine. However, the green, reproducible, and scalable production of MTMO are still a bottleneck for their industrial applications. Although spray-drying methods permit to obtain MTMO in a potentially scalable fashion, the use of highly acidic alcoholic precursor solutions presents two main limitations: corrosion and flammability, which hinder their production in large quantities and lower cost. In this work, we present a general, reproducible, simple, and environment-friendly aerosol method for the synthesis of spherical MTMO particles from mildly acidic aqueous solutions. Acetylacetonate and acetate are used as condensation-controlling agents. Mixed oxides of high valence cations (M(IV) such as Ti, Zr, Ce, and their mixed oxides) were prepared with a yield over 95%, virtually without changing the formulation of the precursor mixture, which can be extended potentially to M(III) or M(V) oxides. The replacement of organic solvents by water allows working in air atmosphere, making this approach much safer, cheaper and environmentally friendly than the current aerosol-based routes. We also present the beneficial effect of mesoporous titania spheres as an additive to nickel electrodes used in the hydrogen evolution reaction, as a demonstrator to potential applications. A threefold increase in the electrocatalytic hydrogen production is observed in mesoporous titania-modified nickel electrodes with respect to a pure nickel catalyst. This performance can be further improved ~25% upon UVA-visible irradiation, due to the photoelectrocatalytic effect of the mesoporous TiO2.

A General and Straightforward Route to Noble Metal-Decorated Mesoporous Transition-Metal Oxides with Enhanced Gas Sensing Performance.

Controllable and efficient synthesis of noble metal/transition-metal oxide (TMO) composites with tailored nanostructures and precise components is essential for their application. Herein, a general mercaptosilane-assisted one-pot coassembly approach is developed to synthesize ordered mesoporous TMOs with agglomerated-free noble metal nanoparticles, including Au/WO3 , Au/TiO2 , Au/NbOx , and Pt/WO3 . 3-mercaptopropyl trimethoxysilane is applied as a bridge agent to cohydrolyze with metal oxide precursors by alkoxysilane moieties and interact with the noble metal source (e.g., HAuCl4 and H2 PtCl4 ) by mercapto (SH) groups, resulting in coassembly with poly(ethylene oxide)-b-polystyrene. The noble metal decorated TMO materials exhibit highly ordered mesoporous structure, large pore size (≈14-20 nm), high specific surface area (61-138 m2 g-1 ), and highly dispersed noble metal (e.g., Au and Pt) nanoparticles. In the system of Au/WO3 , in situ generated SiO2 incorporation not only enhances their thermal stability but also induces the formation of ε-phase WO3 promoting gas sensing performance. Owning to its specific compositions and structure, the gas sensor based on Au/WO3 materials possess enhanced ethanol sensing performance with a good response (Rair /Rgas = 36-50 ppm of ethanol), high selectivity, and excellent low-concentration detection capability (down to 50 ppb) at low working temperature (200 °C).

SYNTHESIS OF MESOPOROUS NANOPARTICLES VIA MICROWAVE-ASSISTED METHOD FOR PHOTOCATALYTIC DEGRADATION OF PHENOL DERIVATIVES

Mesoporous transition metal oxides have gained attention widely since they possess both optical and electronic properties of transition metal oxides especially for photocatalytic degradation application. In this research work, mesoporous titania nanoparticles (MTN) and mesoporous zinc oxide nanoparticles (MZN) were successfully synthesized using microwave (MW)-assisted method to degrade phenol derivatives under visible light irradiation. The microwave sintering effect on the surface of these modified structures was studied to relate with their photocatalytic performance. The characterization results indicated that MW-assisted method was mainly contributed in generating Ti3+ site defects (TSD) and oxygen vacancies (OV) in MTN while for MZN contained only OV as one of the strategies in light-absorption modification for TiO2 and ZnO to enhance their photoactivity. MTN also showed the degradation of 2-chlorophenol was up to 97% while degradation of phenol by MZN was up to 87%.

Templated Growth of Crystalline Mesoporous Materials: From Soft/Hard Templates to Colloidal Templates.

Mesoporous non-siliceous materials, in particular mesoporous transition metal oxides (m-TMOs), are of interest due to their fascinating electronic, redox, and magnetic properties for a wide range of applications in catalysis and energy storage. Control of the porosity (e.g., pore size, wall thickness, and surface area) and the crystalline degree (e.g., phase composition, crystallinity, and crystal grain size) of m-TMOs are critical for those applications. To crystallize TMOs, high temperature annealing is often needed to remove the amorphous defects and/or tune the compositions of different crystalline phases. This has brought many challenges to surfactant or block copolymer templates used in the process of evaporation-induced-self-assembly to prepare m-TMOs. In this review, we summarize the most recent achievements including the findings in our own laboratory on the use of organosilicate-containing colloids for the templated growth of mesoporous materials. We review a few key examples of preparing crystalline mesoporous oxides using different templating methods. The colloidal templating method by which mesoporous nanostructures can be stabilized up to 1,000°C is highlighted. The applications of m-TMOs and meso metal-oxide hybrids synthesized using organosilicate-containing colloidal templates in photocatalysis and high-temperature catalysis are also discussed.

A general ligand-assisted self-assembly approach to crystalline mesoporous metal oxides

Mesoporous transition metal oxides with high crystallinity and large pore volumes were successfully synthesized by a widely applicable ligand-assisted self-assembly approach. In this approach, a carboxyl-containing ligand is employed as a coordination agent to retard the hydrolysis and condensation rates of the precursors. The ligands interact with the PEO chains of P123 via hydrogen bonds, which cooperatively ensures the controllable co-assembly of template micelles and the metal source during solvent evaporation. The X-ray diffraction, transmission electron microscopy, and nitrogen sorption results show that the obtained mesoporous metal oxides are constructed from numerous highly crystalline nanoparticles and possess close-packed mesostructures with uniform pore size distributions. A series of mesoporous transition metal oxides (Co3O4, Mn2O3, Fe3O4, NiO, CuO, ZnO, and Cr2O3) and multi-metal oxide composite materials (Co3O4/Fe3O4, Co3O4/NiO, and Fe3O4/NiO) were successfully synthesized. By employing the crystalline Co3O4/Fe3O4 composites as electrocatalysts, high catalytic activity can be achieved during the oxygen evolution reaction. A low overpotential of 322 mV at a current density of 10 mA cm−2 is exhibited, which shows that this approach has great significance not only in synthesis but also in electrocatalysis.

Template free synthesize mesoporous manganese dioxides for water treatment

Mesoporous materials present infinite application prospect for their special pore structure and large specific surface area. However, the synthesis process of mesoporous transition metal oxides always needs a template such as mesoporous silica to create the porous structure, thus the synthesis technology became complicated and energy consumption. In this work, 3D mesoporous MnO2 microsphere have been successfully prepared by a facile and simple hydrothermal process through introducing a certain amount of Ni2+. A high specific surface area (426 m2/g) was realized due to the mesoporous and ultrathin nanosheets structure. Owing to the special pore structure and 3D morphology assembled with ultrathin nanosheets (∼4 nm). These 3D mesoporous MnO2 shows a high-efficiency catalytic activity contrast with commercial MnO2 and 1D MnO2 nanorods and displays admirable repeatability as well as structure stability in dye degradation.

Kinetic and catalytic analysis of mesoporous metal oxides on the oxidation of Rhodamine B

In this study, we demonstrate the synthesis and catalytic activity of different mesoporous transition metal oxides, silica (SiO2), copper oxide (CuO), chromium oxide (Cr2O3), iron oxide (Fe2O3) cobalt oxide (Co3O4), cerium oxide (CeO2) and nickel oxide (NiO), on the oxidation of a pollutant dye, Rhodamine B (RhB). These metal oxides were synthesized by inverse micelle formation method and characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), adsorption-desorption isotherms (BET) and H2-temperature programmed reduction (TPR). UV–vis spectrophotometry was used to monitor the time-resolved absorbance of RhB at λmax = 554 nm. Mesoporous copper oxide was calcined at different final heating temperatures of 250, 350, 450 and 550 °C, and each mesoporous copper oxide catalyst showed unique physical properties and catalytic behavior. Mesoporous CuO-550 with the smallest characteristic path length δ, proved to be the catalyst of choice for the oxidation of RhB in aqueous media. We observed that the oxidation of RhB in aqueous media is dependent on the crystallite size and characteristic path length of the mesoporous metal oxide. The Langmuir-Hinshelwood model was used to fit the experimental data and to prove that the reaction occurs on the surface of the mesoporous CuO. The thermodynamic parameters, EA, ΔH#, ΔS# and ΔG# were calculated and catalyst recycling and reusability were demonstrated.

Effect of the metal-support interaction on the activity and selectivity of methanol oxidation over Au supported on mesoporous oxides.

To elucidate the factors affecting the catalytic properties of supported Au catalysts on the metal oxide support we investigated Au NPs deposited on crystallized mesoporous transition-metal oxides (m-oxides: Co3O4, NiO, and α-Fe2O3) prepared using the nanocasting method. The metal-oxide interaction in Au/mesoporous oxides resulted in higher catalytic activity for converting methanol to CO2 as a full oxidation product than pure m-oxides. Au/m-Fe2O3 exhibited high activity and low selectivity for methyl formate as a partial oxidative coupling product. We correlate the change in activity and selectivity with the interface between the Au and m-oxides.

Discovering Synthesis Routes to Hexagonally Ordered Mesoporous Niobium Nitrides Using Poloxamer/Pluronics Block Copolymers

Ordered mesoporous transition metal nitrides are interesting as high-surface-area catalyst supports, as materials for energy conversion and storage devices, and as a platform for investigating mesostructured superconductors. The Pluronics/poloxamer family of ABA triblock copolymers has been widely used to produce crystalline ordered mesoporous transition metal oxides, but is considered to pose a major challenge in the synthesis of the corresponding nitrides and other classes of inorganic materials. We report a synthesis of hexagonally-ordered mesoporous niobium nitrides based on commercially available ABA triblock copolymers of the poloxamer/Pluronics family. Employing in situ small- and wide-angle synchrotron x-ray scattering (SAXS/WAXS), we demonstrate that successful thermal processing conditions are confined to a narrow parameter window, which explains previous challenges to access such nitrides. These studies further suggest synthesis of high quality nitrides via e.g. rapid thermal processing. We ant...

Catalytic Reduction of N2O by CO Over Mesoporous Transition Metal Oxides

Catalytic Reduction of N₂O by CO Over Mesoporous Transition Metal Oxides

Random alloy nanoparticles of Pd and Au immobilized on reducible metal oxides and their catalytic investigation

Well-dispersed, random alloy, palladium-gold nanoparticles (2.66±0.51nm) were immobilized onto several reducible mesoporous transition metal oxide materials. The composites (palladium-gold nanoparticles immobilized onto mesoporous transition metal oxide (PdAu–MTMO)) were characterized through several analytical methods such as UV–vis spectroscopy, BET, XRD, FT-IR, ICP-OES, TEM and TPR analyses. Catalytic oxidation of morin (quercetin) was performed as a model reaction in the presence of hydrogen peroxide to investigate the synergic catalytic activity of the composite. Silica was used as inert support to isolate the catalytic activity of the metal nanoparticles (32.69±9.93kJmol−2). Synergistic interaction of PdAu–MTMO was mechanically described according to Langmuir-Hinshelwood and Mars-van Krevelen approaches. The TOF of PdAu–Co3O4 (6073.23±85.01s−1mol−1) was considerably larger than that of random alloy nanoparticles (PdAu–SiO2 (25.71±2.35s−1mol−1)). The Arrhenius-type plot was constructed to determine the synergistic activity of the composite, where PdAu–Co3O4 described the best synergistic interaction.

Protocol for the Nanocasting Method: Preparation of Ordered Mesoporous Metal Oxides

Ordered mesoporous transition metal oxides have attracted considerable research attention due to their unique properties and wide applications. The preparation of these materials has been reported in the literature using soft and hard templating pathways. Compared with soft templating, hard templating, namely, nanocasting, is advantageous for synthesizing rigid mesostructures with high crystallinity and has already been applied to numerous transition metal oxides such as Co3O4, NiO, Fe2O3, and Mn3O4. However, nanocasting is often complicated by the multiple steps involved: first, the preparation of ordered mesoporous silica as the hard template, then infiltration of the metal precursor into the pores, and finally, formation of the metal oxide and removal of the hard template. In this paper, we provide a complete protocol that covers the preparation of most widely used ordered mesoporous silica templates (MCM-41, KIT-6, SBA-15) and the nanocasting process for obtaining ordered mesoporous metal oxides, with...

Mesoporous transition metal oxides quasi-nanospheres with enhanced electrochemical properties for supercapacitor applications

In this report, we obtain mesoporous transition metal oxides quasi-nanospheres (includes MnO2, NiO, and Co3O4) by utilizing mesoporous silica nanospheres as a template for high-performance supercapacitor electrodes. All samples have a large specific surface area of approximately 254–325m2g−1 and a relatively narrow pore size distribution in the region of 7nm. Utilization of a nanosized template resulted in a product with a relative uniform morphology and a small particle diameter in the region of 50–100nm. As supercapacitor electrodes, MnO2, NiO, and Co3O4 exhibit an outstanding capacity as high as 838–1185Fg−1 at 0.5Ag−1 and a superior long-term stability with minimal loss of 3–7% after 6000 cycles at 1Ag−1. Their excellent electrochemical performances are attributed to favorable morphologies with a large surface area and a uniform architecture with abundant pores. The associated enhancement of electrolyte ion circulation within the electrode facilitates a significant increase in availability of Faradic reaction electroactive sites.

Surfactant-templating strategy for ultrathin mesoporous TiO2 coating on flexible graphitized carbon supports for high-performance lithium-ion battery

The electrochemical performance of nanocomposites could greatly be improved by rationally designing flexible core-shell heterostructures. Typically, the uniform coating of a thin mesoporous crystalline transition metal oxide shell on flexible graphitized carbon supports can provide both fast ion and electron transport pathways, which is an ideal material for high-performance lithium-ion batteries. Herein, we report a surfactant-templating assembly coating method to deposit an ultrathin mesoporous crystalline TiO2 shell on flexible graphitized carbon supports by using amphiphilic triblock copolymer Pluronic F127 as a template. Taking multi-wall carbon nanotubes (CNTs) as an example support, the obtained flexible CNTs@mTiO2 hybrid mesoporous nanocables exhibit an ultra-high surface area (∼137m2/g), large internal pore volume (∼0.26cm3/g), uniform accessible mesopores (∼6.2nm) and ultrathin highly-crystalline mesoporous anatase shells (∼20nm in thickness). As an anode material for lithium battery, the flexible CNTs@mTiO2 hybrid mesoporous nanocables show high-rate capacity (∼210mAhg−1 at 20C, 1C=170mAg−1), high Coulombic efficiency (nearly 100% during 1000 cycles at 20C) and ultralong-cycling life (keeping ∼210mAhg−1 after 1000 cycles at 20C). The strong synergistic coupling effect between CNT cores and thin mesoporous TiO2 shells, high surface area, accessible large pores and highly crystalline thin mesoporous shells result in excellent performance in lithium batteries. This versatile surfactant-templating assembly coating method can be easily extended to deposit an ultrathin mesoporous TiO2 layer on flat graphene (GR) to form a uniform sandwich-like flexible GR@mTiO2 nanoflakes, which opens up a new opportunity for depositing thin mesoporous transition-metal oxides on graphitized carbon supports for advanced applications in energy conversion and storage, photocatalysis, sensors and drug delivery, etc.