Sourav Biswas

A general approach to crystalline and monomodal pore size mesoporous materials

Mesoporous oxides attract a great deal of interest in many fields, including energy, catalysis and separation, because of their tunable structural properties such as surface area, pore volume and size, and nanocrystalline walls. Here we report thermally stable, crystalline, thermally controlled monomodal pore size mesoporous materials. Generation of such materials involves the use of inverse micelles, elimination of solvent effects, minimizing the effect of water content and controlling the condensation of inorganic frameworks by NO(x) decomposition. Nanosize particles are formed in inverse micelles and are randomly packed to a mesoporous structure. The mesopores are created by interconnected intraparticle voids and can be tuned from 1.2 to 25 nm by controlling the nanoparticle size. Such phenomena allow the preparation of multiple phases of the same metal oxide and syntheses of materials having compositions throughout much of the periodic table, with different structures and thermal stabilities as high as 800 °C.

Ni- and Mn-Promoted Mesoporous Co3O4: A Stable Bifunctional Catalyst with Surface-Structure-Dependent Activity for Oxygen Reduction Reaction and Oxygen Evolution Reaction

Efficient bifunctional catalysts for electrochemical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are highly desirable due to their wide applications in fuel cells and rechargeable metal air batteries. However, the development of nonprecious metal catalysts with comparable activities to noble metals is still challenging. Here we report a one-step wet-chemical synthesis of Ni-/Mn-promoted mesoporous cobalt oxides through an inverse micelle process. Various characterization techniques including powder X-ray diffraction (PXRD), N2 sorption, transmission electron microscopy (TEM), and scanning electron microscopy (SEM) confirm the successful incorporation of Ni and Mn leading to the formation of Co-Ni(Mn)-O solid solutions with retained mesoporosity. Among these catalysts, cobalt oxide with 5% Ni doping demonstrates promising activities for both ORR and OER, with an overpotential of 399 mV for ORR (at -3 mA/cm(2)) and 381 mV (at 10 mA/cm(2)) for OER. Furthermore, it shows better durability than precious metals featuring little activity decay throughout 24 h continuous operation. Analyses of cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), Raman, and O2-temperature-programmed desorption (O2-TPD) reveal that redox activity of Co(3+) to Co(4+) is crucial for OER performance, while the population of surface oxygen vacancies and surface area determine ORR activities. The comprehensive investigation of the intrinsic active sites for ORR and OER by correlating different physicochemical properties to the electrochemical activities is believed to provide important insight toward the rational design of high-performance electrocatalysts for ORR and OER reactions.

Absorption-Dominated Electromagnetic Wave Suppressor Derived from Ferrite-Doped Cross-Linked Graphene Framework and Conducting Carbon

To minimize electromagnetic (EM) pollution, two key parameters, namely, intrinsic wave impedance matching and intense absorption of incoming EM radiation, must satisfy the utmost requirements. To target these requirements, soft conducting composites consisting of binary blends of polycarbonate (PC) and poly(vinylidene fluoride) (PVDF) were designed with doped multiwalled carbon nanotubes (MWCNTs) and a three-dimensional cross-linked graphene oxide (GO) framework doped with ferrite nanoparticles. The doping of α-MnO2 onto the MWCNTs ensured intrinsic wave impedance matching in addition to providing conducting pathways, and the ferrite-doped cross-linked GO facilitated the enhanced attenuation of the incoming EM radiation. This unique combination of magnetodielectric coupling led to a very high electromagnetic shielding efficiency (SE) of -37 dB at 18 GHz, dominated by absorption-driven shielding. The promising results from the composites further motivated us to rationally stack individual composites into a multilayer architecture following an absorption-multiple reflection-absorption pathway. This resulted in an impressive SE of -57 dB for a thin shield of 0.9-mm thickness. Such a high SE indicates >99.999% attenuation of the incoming EM radiation, which, together with the improvement in structural properties, validates the potential of these materials in terms of applications in cost-effective and tunable solutions.

Tunable mesoporous manganese oxide for high performance oxygen reduction and evolution reactions

Understanding the origin of manganese oxide activity for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is a key step towards rationally designing of highly active catalysts capable of competing with the widely used, state-of-art noble metal catalysts. Herein, we present a bifunctional, thermally stable cesium-promoted mesoporous manganese oxide (Cs-MnOx) tuned by simple heat treatment from an amorphous to a crystalline phase with controlled surface and bulk active Mn centers. The Cs-MnOx material exhibited the highest ORR activity (0.87 V vs. RHE at −3 mA cm−2) among all noble-metal-free manganese oxide catalysts reported to date with superior activity compared to state-of-the-art Pt/C catalyst. In addition, Cs-MnOx exhibited comparable OER performance with the highly active Ir/C and RuO2 catalysts. Extensive characterization and density functional theory (DFT) computations suggested that the stabilization of the surface and bulk enriched Mn3+ species, increase of relative basicity and maintaining active crystalline phase due to Cs incorporation, are the main decisive factors for the profound ORR and OER activities. Findings from our study provide general guidance for designing of cost effective and active metal oxide based electrocatalysts.

Mesoporous Manganese Oxide Catalyzed Aerobic Oxidative Coupling of Anilines To Aromatic Azo Compounds.

Herein we introduce an environmentally friendly approach to the synthesis of symmetrical and asymmetrical aromatic azo compounds by using air as the sole oxidant under mild reaction conditions in the presence of cost-effective and reusable mesoporous manganese oxide materials.

Manganese Oxide Nanoarray-Based Monolithic Catalysts: Tunable Morphology and High Efficiency for CO Oxidation

A generic one-pot hydrothermal synthesis route has been successfully designed and utilized to in situ grow uniform manganese oxide nanorods and nanowires onto the cordierite honeycomb monolithic substrates, forming a series of nanoarray-based monolithic catalysts. During the synthesis process, three types of potassium salt oxidants have been used with different reduction potentials, i.e., K2Cr2O7, KClO3, and K2S2O8, denoted as HM-DCM, HM-PCR, and HM-PSF, respectively. The different reduction potentials of the manganese source (Mn(2+)) and oxidants induced the formation of manganese oxide nanoarrays with different morphology, surface area, and reactivity of carbon monoxide (CO) oxidation. K2Cr2O7 and KClO3 can induce sharp and long nanowires with slow growth rates due to their low reduction potentials. In comparison, the nanoarrays of HM-PSF presented shorter nanorods but displayed an efficient 90% CO oxidation conversion at 200 °C (T90) without noble-metal loading. Reducibility tests for the three monolithic catalysts by hydrogen temperature-programmed reduction revealed an activation energy order of HM-PSF > HM-DCM > HM-PCR for CO oxidation. The characterizations of oxygen temperature-programmed desorption and X-ray photoelectron spectroscopy indicated the abundant surface-adsorbed oxygen and lattice oxygen contributing to the superior reactivity of HM-PSF. The straightforward synthetic process showed a scalable, low-cost, and template-free method to fabricate manganese oxide nanoarray monolithic catalysts for exhaust treatment.

Ligand‐Assisted Co‐Assembly Approach toward Mesoporous Hybrid Catalysts of Transition‐Metal Oxides and Noble Metals: Photochemical Water Splitting

A bottom-up synthetic approach was developed for the preparation of mesoporous transition-metal-oxide/noble-metal hybrid catalysts through ligand-assisted co-assembly of amphiphilic block-copolymer micelles and polymer-tethered noble-metal nanoparticles (NPs). The synthetic approach offers a general and straightforward method to precisely tune the sizes and loadings of noble-metal NPs in metal oxides. This system thus provides a solid platform to clearly understand the role of noble-metal NPs in photochemical water splitting. The presence of trace amounts of metal NPs (≈0.1 wt %) can enhance the photocatalytic activity for water splitting up to a factor of four. The findings can conceivably be applied to other semiconductors/noble-metal catalysts, which may stand out as a new methodology to build highly efficient solar energy conversion systems.

FeCo-Anchored Reduced Graphene Oxide Framework-Based Soft Composites Containing Carbon Nanotubes as Highly Efficient Microwave Absorbers with Excellent Heat Dissipation Ability

Conducting polymer composites containing ferromagnetic grafted-graphene derivatives are already appreciated for their lightweight, flexibility, and cost effectiveness in terms of microwave absorption. To further leverage the said properties of this wonder material, we propose a highly efficient replacement by blending conducting multiwall carbon nanotube (MWCNT) and FeCo anchored covalent cross-linked reduced graphene oxide (rGO) with poly(vinylidene fluoride) (PVDF). Interconnected conducting network of MWCNTs introduces higher electrical conductivity in the blend which is essential for microwave absorption. FeCo-anchored porous interconnected rGO framework was designed via solvent-mediated in situ coreduction in the presence of Fe(II) and Co(II) precursors. Resulting cross-linked-rGO/FeCo displays fascinating coexistence of ferromagnetism and conducting-dielectric behavior, while largely preserving the robust 3D porous interconnected structure. Coupled with conducting MWCNTs, diamine cross-linked rGO/FeCo in a soft polymer matrix yields remarkably high total shielding effectiveness (SET) of -41.2 dB at 12 GHz, for a meager 10 wt % filler content. In addition, the composite materials display efficient heat dissipation abilities in conjunction with the trend in their thermal conductivities. This new-age microwave-absorbing material, powered by multifunctionality and tunable magnetodielectric properties, henceforth offers an amendable, cost-effective replacement to the existing solutions.

High-rate and long-life of Li-ion batteries using reduced graphene oxide/Co3O4 as anode materials

Metal oxides as Li-ion battery anodes have received a great deal of attention because they offer a higher specific capacity than state-of-the-art commercial graphite. However, a large volume change and severe particle aggregation during battery operation have greatly impeded their practical application. Herein, we report a facile one-step microwave-assisted route for growing Co3O4 nanoparticles on reduced graphene oxide that results in a high performance anode material for Li-ion batteries. The lithium battery performances of several systems with varied reduced graphene oxide contents were studied. The optimized composites exhibit a high surface area of 222 m2 g−1, and a wide pore size distribution of 1.4 to 300 nm. More importantly, the Li-ion battery shows a high capacity of ∼1300 mA h g−1 at a high rate of 1C (1C = 890 mA g−1), long life of over 600 cycles, good capacity retention, and excellent rate capability. The synthesis process is simple, energy efficient, and time-saving, providing a new path in designing high-performance electrodes for Li-ion batteries.

Bimodification of Mesoporous Silicon Oxide by Coupled “In Situ Oxidation at the Interface and Ion Exchange” and its Catalytic Activity in the Gas-Phase Toluene Oxidation

A bimodification synthesis method—“in situ oxidation at the interface (IOI) coupled with an ion exchange”—has been developed for the internal surface modification of mesoporous silicon oxide (MPS) templates. First, manganese oxide was formed at the internal surface of the MPS template through IOI. In the IOI method, high‐valent oxo‐anions of manganese (MnO4−) were used for the selective oxidation of poly(ethylene oxide) (PEO) groups of the Pluronic P123 (PEO20PPO70PEO20; PPO=poly(propylene oxide)) surfactant and they formed manganese oxide at the organic–inorganic (corona) interface. The oxide formation was restricted at the corona interface by a positively charged CTA+ (cetyltrimethylammonium) head group of the cationic surfactant CTABr. Then, the second modification of the MPS template was also performed by introducing promoter cations (Cs+, K+, or H+) through an ion exchange reaction between the cations and CTA+. The bimodified MPSMnX (X=Cs, K, or H) samples preserved the mesoporosity and high surface area of the MPS template. The bimodified MPSMnX samples were found to be more active, selective, and stable than the singly modified MPSMn sample for the gas‐phase oxidation of toluene.