Reuse of Lignin to Synthesize High Surface Area Carbon Nanoparticles for Supercapacitors Using a Continuous and Single-Step Aerosol Method.

There is a growing demand for the synthesis of high surface area carbons, also known as carbon nanoparticles (CNPs). Existing synthesis methods for high surface area carbons have limited environmental benignity and economic viability due to the requirement of multistep and batch processes and harsh activating and/or templating chemicals. Herein, we demonstrate the synthesis of high surface area CNPs from lignin, a waste byproduct, through a single-step, continuous gas phase aerosol technique without the use of activating or templating chemicals. This continuous approach requires significantly less time for synthesis: on the order of seconds in comparison to hours for conventional methods. Properties of carbon materials synthesized from lignin are controlled by temperature and residence time, and the role of these parameters inside the aerosol reactor on carbon nanoparticle size, morphology, molecular structure, and surface area is systematically investigated. Furthermore, the as-obtained carbon nanoparticles are tested for specific capacitance, and the best-performing material (surface area 925 m2/g) exhibited a specific capacitance of 247 F/g at 0.5 A/g with excellent capacity retainment of over 98% after 10,000 cycles. This is a clear demonstration of their superior performance compared with supercapacitors synthesized earlier from lignin. Overall, the simple (single-step, continuous, and rapid) operation and the avoidance of the use of activating/templating chemicals make the aerosol technique a promising candidate for the scalable and sustainable synthesis of CNPs from lignin.

Pyrochlores for Advanced Oxygen Electrocatalysis.

Fuel cells (FCs), water electrolyzers (WEs), unitized regenerative fuel cells (URFCs), and metal-air batteries (MABs) are among the emerging electrochemical technologies for energy storage, fuel (H2), oxidant (O2), and clean energy production. Their commercial applications are hindered by the low oxygen reduction reaction/oxygen evolution reaction (ORR/OER) bifunctional activity (for URFCs and MABs), OER selectivity (brine electrolysis in seawater and Martian environments), and high cost of the benchmark electrocatalysts (OER: RuO2, IrO2 and ORR: Pt/C) which affects the performance and affordability of the devices. Low-cost electrocatalysts with highly symmetric ORR/OER bifunctional activity and high OER selectivity are crucial for large-scale FC, WE, URFC, and MAB application. Recent studies have revealed that tuning the structure of pyrochlore oxides provides a pathway to enhancing OER and ORR activity over a wide range of pH. Pyrochlore oxides commonly contain a cubic A2B2O7-x structure with two types of tetrahedrally coordinated O atoms containing (1) A-O-A and (2) A-O-B types with a cationic radii mismatch of rA/rB > 1.5 and propensity toward oxygen vacancy formation. The variety of pyrochlore oxides and their tunable properties make them attractive for a wide spectrum of applications. Among all the metal oxides, Ru-based pyrochlores (e.g., Pb2Ru2O7-x) exhibit the best bifunctional oxygen electrocatalytic activity, i.e., low bifunctionality index (BI), in alkaline medium. Furthermore, pyrochlores exhibit high OER selectivity in brine electrolytes due to the presence of surface oxygen vacancies, making them suitable for space applications (brine electrolysis on Mars) and coastal hydrogen generation. Their bifunctional activity and selectivity can be further amplified by (1) substituting "A" and "B" sites of pyrochlores (AA'BB'O7-x), (2) tuning metal oxidation states of A and B by varying synthesis conditions, and (3) modulating oxygen vacancy concentration, each of which yield favorable structural and electronic variations. In recent years, research on the synthesis and understanding of pyrochlores has significantly enhanced their viability, offering a new horizon in the quest for economical and active electrocatalysts. However, an account that focuses on critical developments in this field is still lacking.In this Account, we focus on the recent development of a variety of pyrochlore electrocatalysts to understand intrinsic structure-activity-selectivity-stability relationships in these materials. Recent developments and applications of pyrochlore-based electrocatalysts are discussed under the following headings: (1) modulation of crystal and electronic structure of pyrochlores, (2) structure-activity-stability relationships of different pyrochlores for OER and ORR, (3) development of OER-selective pyrochlores for brine electrolysis, and (4) the application of pyrochlores in electrochemical devices. Finally, we highlight some unaddressed issues such as the precise identification of active sites, which can be addressed in the future through advanced in situ and ex situ characterization techniques coupled with the density functional theory-based analyses. This Account provides foundational understanding to guide the comprehensive development of highly active, selective, stable and low-cost structurally engineered pyrochlores for high performance electrochemical devices.

High-performance AEM unitized regenerative fuel cell using Pt-pyrochlore as bifunctional oxygen electrocatalyst.

The performance of fixed-gas unitized regenerative fuel cells (FG-URFCs) are limited by the bifunctional activity of the oxygen electrocatalyst. It is essential to have a good bifunctional oxygen electrocatalyst which can exhibit high activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). In this regard, Pt-Pb2Ru2O7-x is synthesized by depositing Pt on Pb2Ru2O7-x wherein Pt individually exhibits high ORR while Pb2Ru2O7-x shows high OER and moderate ORR activity. Pt-Pb2Ru2O7-x exhibits higher OER (η@10mAcm-2 = 0.25 ± 0.01 V) and ORR (η@-3mAcm-2 = -0.31 ± 0.02 V) activity in comparison to benchmark OER (IrO2, η@10mAcm-2 = 0.35 ± 0.02 V) and ORR (Pt/C, η@-3mAcm-2 = -0.33 ± 0.02 V) electrocatalysts, respectively. Pt-Pb2Ru2O7-x shows a lower bifunctionality index (η@10mAcm-2, OER- η@-3mAcm-2, ORR) of 0.56 V with more symmetric OER-ORR activity profile than both Pt (>1.0 V) and Pb2Ru2O7-x (0.69 V) making it more useful for the AEM (anion exchange membrane) URFC or metal-air battery applications. FG-URFC tested with Pt-Pb2Ru2O7-x and Pt/C as bifunctional oxygen electrocatalyst and bifunctional hydrogen electrocatalyst, respectively, yields a mass-specific current density of 715 ± 11 A/gcat-1 at 1.8 V and 56 ± 2 A/gcat-1 at 0.9 V under electrolyzer mode and fuel-cell mode, respectively. The FG-URFC shows a round-trip efficiency of 75% at 0.1 A/cm-2, underlying improvement in AEM FG-URFC electrocatalyst design.

Design of iso-material heterostructures of TiO2via seed mediated growth and arrested phase transitions.

Stabilization of different morphologies of iso-material native/non-native heterostructures is important for electron-hole separation in the context of photo-electrochemical and opto-electronic devices. In this regard, we explore the stabilities of different morphologies of rutile ("native", ground state phase) and anatase ("non-native" phase) TiO2 heterostructures through (1) seed-mediated growth and (2) a thermally induced arrested phase transition synthesis protocol. Furthermore, the experimental results are analyzed through a combination of Density Functional Tight Binding (DFTB) and Finite Element Model (FEM) methods. During the seed-mediated growth, anatase is grown over a polydispersed and polycrystalline rutile core through thermal treatment yielding core-shell, Janus and yolk-shell iso-material heterostructures as observed from HRTEM. The arrested phase transition of anatase to rutile at different annealing temperatures yields rutile crystals in the subsurface region of the anatase and rutile/core-thin anatase/shell heterostructures but does not yield a Janus structure. Small particles that can be modeled via DFTB computations suggest that: (1) a heterostructure of the rutile/core-anatase/shell is energetically more stable than the anatase/core-rutile/shell or any other Janus configuration, (2) the off-centered rutile/core-anatase shell is more favorable to the mid-centered rutile/core-anatase shell and (3) Janus heterostructures can be stabilized when the mass ratio of the rutile seed to anatase overgrowth is high. FEM simulations, performed to evaluate the importance of stress relaxation in bicrystalline materials without defects, suggest that Janus structures can be stabilized in larger particles. The present studies add to the heuristics available for synthesizing iso-material heterostructures.

Kinetically stabilized aliovalent europium-doped magnesium oxide as a UV sensitized phosphor.

Doping of size mismatched aliovalent ions is challenging due to the associated elastic and electronic stress making the thermodynamics unfavorable. Despite such features, its utilization may be viable if such systems can be made metastable by suppressing the kinetics of phase segregation. In light of such a possibility, we utilize sol-gel synthesis for preparing a size mismatched trivalent europium doped MgO (Mg(1-x)Eu(x)O:(x/2)V"(Mg)) system, which can be potentially used in optical applications. It is found that such a doped system can be metastabilized and the extent of metastability can be correlated with critical temperature (Tc) required for phase segregation which decreases with the dopant concentration. For x = 0.005, 0.01, and 0.02, Tc is above 1200 °C, 500-800 °C and less than 500 °C, respectively. As the synthesis temperature is 500 °C, these trends in critical temperatures make it impossible to metastabilize europium in MgO with x > 0.01. Doping is evident from X-ray diffraction data, excitation spectra, high resolution emission spectra, and luminescence lifetimes. A characteristic strong red emission of Eu(3+) has been observed via energy transfer from the MgO matrix to Eu(3+). Density functional theory based simulations suggest stabilization of Eu(3+) in MgO at lower doping concentration through the formation of cation vacancies which is also evident from optical studies. Furthermore, thin films deposited using the e-beam evaporation technique from the Mg(1-x)Eu(x)O:(x/2)V"(Mg) (x = 0.005) system show UV sensitized emission with CIE coordinates (0.26, 0.21).