Tackling Challenges in Seebeck Coefficient Measurement of Ultra-High Resistance Samples with an AC Technique

Seebeck coefficient is a widely studied semiconductor property. Conventional Seebeck coefficient measurements are based on DC voltage measurement. Normally this is performed on samples with moderate resistances (e.g., below a few MΩ level). Certain semiconductors are intrinsic and highly resistive. Many examples can be found in optical and photovoltaic materials. The hybrid halide perovskites that have gained extensive attention recently are a good example. Despite great attention from the materials and physics communities, few successful studies exist of the Seebeck coefficient of these compounds, for example CH3NH3PbI3. An AC-technique-based Seebeck coefficient measurement is reported, which makes high-quality Seebeck voltage measurements on samples with resistances up to the 100 GΩ level. This is achieved through a specifically designed setup to enhance sample isolation and increase capacitive impedance. As a demonstration, Seebeck coefficient measurement of a CH3NH3PbI3 thin film is performed at dark, with sample resistance 150 GΩ, and found S = +550 µV K−1. The strategy reported could be applied to the studies of fundamental transport parameters of all intrinsic semiconductors that have not been feasible

Surface-Plasmon-Assisted Photoelectrochemical Reduction of CO2 and NO3− on Nanostructured Silver Electrodes

Electrochemical reduction of carbon dioxide (CO2) typically suffers from low selectivity and poor reaction rates that necessitate high overpotentials, which impede its possible application for CO2 capture, sequestration, or carbon-based fuel production. New strategies to address these issues include the utilization of photoexcited charge carriers to overcome activation barriers for reactions that produce desirable products. This study demonstrates surface-plasmon-enhanced photoelectrochemical reduction of CO2 and nitrate (NO3−) on silver nanostructured electrodes. The observed photocurrent likely originates from a resonant charge transfer between the photogenerated plasmonic hot electrons and the lowest unoccupied molecular orbital (MO) acceptor energy levels of adsorbed CO2, NO3−, or their reductive intermediates. The observed differences in the resonant effects at the Ag electrode with respect to electrode potential and photon energy for CO2 versus NO3− reduction suggest that plasmonic hot-carriers interact selectively with specific MO acceptor energy levels of adsorbed surface species such as CO2, NO3−, or their reductive intermediates. This unique plasmon-assisted charge generation and transfer mechanism can be used to increase yield, efficiency, and selectivity of various photoelectrochemical processes

Directing Selectivity of Electrochemical Carbon Dioxide Reduction Using Plasmonics

Catalysts for electrochemical carbon dioxide reduction in aqueous electrolytes suffer from high energy input requirements, competition with hydrogen evolution from water reduction, and low product selectivity. Theory suggests that plasmonic catalysts can be tuned to selectively lower the energy barrier for a specific reaction in a set of competitive reactions, but there has been little experimental evidence demonstrating plasmon-driven selectivity in complicated multielectron electrochemical processes. Here, the photoactivity at a plasmonically active silver thin film electrode at small cathodic potentials selectively generates carbon monoxide while simultaneously suppressing hydrogen production. At larger cathodic potentials, the photoactivity promotes production of methanol and formate. Methanol production is observed only under illumination, not in dark conditions. The preference of the plasmonic activity for carbon dioxide reduction over hydrogen evolution and the ability to tune plasmonic activity with voltage demonstrates that plasmonics provide a promising approach to promote complex electrochemical reactions over other competing reactions

Graphene-polyelectrolyte multilayer membranes with tunable structure and internal charge

One great advantage of graphene-polyelectrolyte multilayer (GPM) membranes is their tunable structure and internal charge for improved separation performance. In this study, we synthesized GO-dominant GPM membrane with internal negatively-charged domains, polyethyleneimine (PEI)-dominant GPM membrane with internal positively-charged domains and charge-balanced dense/loose GPM membranes by simply adjusting the ionic strength and pH of the GO and PEI solutions used in layer-by-layer membrane synthesis. A combined system of quartz crystal microbalance with dissipation (QCM-D) and ellipsometry was used to analyze the mass deposition, film thickness, and layer density of the GPM membranes. The performance of the GPM membranes were compared in terms of both permeability and selectivity to determine the optimal membrane structure and synthesis strategy. One effective strategy to improve the GPM membrane permeability-selectivity tradeoff is to assemble charge-balanced dense membranes under weak electrostatic interactions. This balanced membrane exhibits the highest MgCl2 selectivity (∼86%). Another effective strategy for improved cation removal is to create PEI-dominant membranes that provide internal positively-charged barrier to enhance cation selectivity without sacrificing water permeability. These findings shine lights on the development of a systematic approach to push the boundary of permeability-selectivity tradeoff for GPM membranes

High-Performance, Wearable Thermoelectric Generator Based on a Highly Aligned Carbon Nanotube Sheet

A high-performance, wearable thermoelectric generator (TEG) was fabricated with a highly aligned carbon nanotube (CNT) sheet. The aligned CNT sheet exhibits extraordinary electrical conductivity compared to disordered CNT sheets and also can be directly fabricated as a continuous TEG without metal electrode interconnects. This provides a significant reduction in contact resistance between TE legs and electrodes compared to traditional TEGs, resulting in higher power output. In addition, the continuity of the module without any disconnected parts provides high degrees of mechanical stability and durability. This robust and scalable approach to flexible TEG fabrication paves the way for CNT applications in lightweight, flexible, and wearable electronics

Enhanced Charge Carrier Transport in 2D Perovskites by Incorporating Single-Walled Carbon Nanotubes or Graphene

Two-dimensional (2D) organic-inorganic (hybrid) perovskites are considered promising candidates to replace conventional three-dimensional (3D) perovskites for solar cell applications as they have good resistance against moisture and UV light. However, the use of 2D perovskite is associated with a significant decrease in power efficiency resulting from their low photogenerated charge carrier density and poor charge transport. To improve power efficiency in 2D perovskites, highly crystalline films (near-single-crystal quality) of 2D perovskite need to be synthesized where the alignment of the inorganic perovskite components is controlled to have vertical alignment with respect to the contacts to improve charge transport. In this work, we explored strategies to overcome this limitation by integrating 2D perovskite with single-walled carbon nanotubes or graphene to enable more efficient extraction of charge carriers toward electric contacts. Longer carrier lifetimes were achieved after the incorporation of the carbon nanostructures in the films, and at the cell level, power efficiency increased by 2-fold

Robust natural nanocomposites realizing unprecedented ultrafast precise molecular separations

Synthetic polymer membranes can potentially reduce the large energy and carbon footprints that are typically associated with traditional chemical separation technologies. Unfortunately, current production protocols negate the green benefits of membrane separation. To address this bottleneck, here we report the use of natural materials monosaccharide – glucose and polydopamine and Zr-based metal organic frameworks (MOFs) to fabricate ultrathin nanocomposite membranes via interfacial polymerization reaction. The synergistic effect of these three materials on angstrom-scale molecular transport both in organic solvent and aqueous environment was elucidated using a series of complementary techniques. We demonstrate such nature-inspired nanocomposite membranes enable structural stability even in polar aprotic solvents, and unparalleled ultra-fast, low-pressure, precise separations in both nanofiltration modes, which easily surpass state-of-the-art membranes relying on unsustainable materials. The multi-functionality of saccharide nanocomposites was elegantly harnessed to impact separation applications that contribute towards a better living environment

Design Rules for Self-Assembly of 2D Nanocrystal/Metal-Organic Framework Superstructures.

We demonstrate the guiding principles behind simple two dimensional self-assembly of MOF nanoparticles (NPs) and oleic acid capped iron oxide (Fe3 O4 ) NCs into a uniform two-dimensional bi-layered superstructure. This self-assembly process can be controlled by the energy of ligand-ligand interactions between surface ligands on Fe3 O4 NCs and Zr6 O4 (OH)4 (fumarate)6 MOF NPs. Scanning transmission electron microscopy (TEM)/energy-dispersive X-ray spectroscopy and TEM tomography confirm the hierarchical co-assembly of Fe3 O4 NCs with MOF NPs as ligand energies are manipulated to promote facile diffusion of the smaller NCs. First-principles calculations and event-driven molecular dynamics simulations indicate that the observed patterns are dictated by combination of ligand-surface and ligand-ligand interactions. This study opens a new avenue for design and self-assembly of MOFs and NCs into high surface area assemblies, mimicking the structure of supported catalyst architectures, and provides a thorough fundamental understanding of the self-assembly process, which could be a guide for designing functional materials with desired structure

Dynamic Covalent Synthesis of Crystalline Porous Graphitic Frameworks

Porous graphitic framework (PGF) is a two-dimensional (2D) material that has emerging energy applications. An archetype contains stacked 2D layers, the structure of which features a fully annulated aromatic skeleton with embedded heteroatoms and periodic pores. Due to the lack of a rational approach in establishing in-plane order under mild synthetic conditions, the structural integrity of PGF has remained elusive and ultimately limited its material performance. Here, we report the discovery of the unusual dynamic character of the C=N bonds in the aromatic pyrazine ring system under basic aqueous conditions, which enables the successful synthesis of a crystalline porous nitrogenous graphitic framework with remarkable in-plane order, as evidenced by powder X-ray diffraction studies and direct visualization using high-resolution transmission electron microscopy. The crystalline framework displays superior performance as a cathode material for lithium-ion batteries, outperforming the amorphous counterparts in terms of capacity and cycle stability. Insertion of well-defined, evenly spaced nanoscale pores into the two-dimensional (2D) layers of graphene invokes exciting properties due to the modulation of its electronic band gaps and surface functionalities. A bottom-up synthesis approach to such porous graphitic frameworks (PGFs) is appealing but also remains a great challenge. The current methods of building covalent organic frameworks rely on a small collection of thermodynamically reversible reactions. Such reactions are, however, inadequate in generating a fully annulated aromatic skeleton in PGFs. With the discovery of dynamic pyrazine formation, we succeeded in applying this linking chemistry to obtain a crystalline PGF material, which has displayed high electrical conductivity and remarkable performance as a cathode material for lithium-ion batteries. We envision that the demonstrated success will open the door to a wide array of fully annulated 2D porous frameworks, which hold immense potential for clean energy applications. We report the unusual dynamic characteristics of the C=N bonds in the pyrazine ring promoted under basic aqueous conditions, which enables the successful synthesis of two-dimensional porous graphitic frameworks (PGFs) featuring fully annulated aromatic skeletons and periodic pores. The PGF displayed high electrical conductivity and remarkable performance as a cathode material for lithium-ion batteries, far outperforming the amorphous counterparts in terms of capacity and cycle stability