Chemical reactions of graphitic carbon nitride films with glass surfaces and their impact on photocatalytic activity.

Thin films of graphitic carbon nitride (g-CN), a visible-light-driven photocatalyst, have recently attracted interest for application in photoelectrochemical cells for water splitting and high-throughput photocatalysis. In typical syntheses, g-CN films are formed by heating the nitrogen-rich precursor and substrate to 500-600 °C. The heated substrate should affect the polycondensation of the precursor and thereby alter the properties of the g-CN film. In this paper, we demonstrate that soda-lime glass, such as commercial glass slides, modifies the chemical structure of g-CN. The terminal amino groups of g-CN are partially substituted with cyanamide and hydroxyl groups. The electron-withdrawing groups provide the energy offsets of the frontier orbitals between the modified and unmodified molecules, facilitating exciton dissociation. After alkali metals are removed, the modified g-CN film exhibits a faster photodegradation of methyl orange compared with a melon film. The simple protocol to activate a g-CN film without co-catalysts paves a new way to enhance photocatalytic activity via selections of substrates, including waste glass.

Insight into the effect of the configuration entropy of additives on the Seebeck coefficient.

Thermogalvanic cells have attracted considerable attention because of their potential to directly convert waste heat into electricity by using redox reactions under continuous operation with a simple, cost-effective design. An increase in the Seebeck coefficient owing to the interactions between the redox ions and the additives has been reported in recent studies. The configuration entropy of the small additives coordinated to a large ion is calculated to analyze the Seebeck coefficient obtained from the entropy difference between the redox pairs. The recently reported increase in the Seebeck coefficient owing to the introduction of guanidinium (Gdm) or urea into the Fe(CN)64-/Fe(CN)63- electrolyte is analyzed using the theoretical results. Furthermore, qualitative and quantitative analyses were also performed to determine the influence of the affinity for the additives on the entropy difference of the redox couples and on the Seebeck coefficient. This study also demonstrates the enhancement in the Seebeck coefficient caused by a membrane isolating the binding species into an appropriate hot/cold zone.

Transparent Patternable Large-Area Graphene p-n Junctions by Photoinduced Electron Doping.

We present a novel approach to achieve n-type doping in graphene and create graphene p-n junctions through a photoinduced electron doping method using photobase generators (PBGs). The unique properties of PBGs allow us to spatially and temporally control the doping process via light activation. The selective irradiation of specific regions on the graphene film enables switching their doping from p- to n-type, as confirmed by changes in the electromotive force and Seebeck and Hall coefficients. We demonstrate a stable (over 2 months) high electron mobility exceeding 1000 cm2 V-1s-1 using Hall effect measurements. The precise control of doping and the creation of p-n junctions in graphene offer exciting possibilities for various electronic, optoelectronic, and thermoelectric applications. Furthermore, we fabricate transparent graphene thermocouples with a high electromotive force of approximately ca. 80 µV/K, which validates the reliability and effectiveness of our approach for temperature sensing applications. This work paves the way for high-performance graphene-based electronic devices via controlled doping and patterning techniques. These findings provide valuable insights for the practical implementation of graphene in various fields.

Interface Engineering for High-Performance Thermoelectric Carbon Nanotube Films.

Carbon nanotubes (CNTs) stand out for their exceptional electrical, thermal, and mechanical attributes, making them highly promising materials for cutting-edge, lightweight, and flexible thermoelectric applications. However, realizing the full potential of advanced thermoelectric CNTs requires precise management of their electrical and thermal characteristics. This study, through interface optimization, demonstrates the feasibility of reducing the thermal conductivity while preserving robust electrical conductivity in single-walled CNT films. Our findings reveal that blending two functionalized CNTs offers a versatile method of tailoring the structural and electronic properties of CNT films. Moreover, the modified interface exerts a substantial influence over thermal and electrical transfer, effectively suppressing heat dissipation and facilitating thermoelectric power generation within CNT films. As a result, we have successfully produced both p- and n-type thermoelectric CNTs, attaining impressive power factors of 507 and 171 µW/mK2 at room temperature, respectively. These results provide valuable insights into the fabrication of high-performance thermoelectric CNT films.

High-Performance Isotropic Thermo-Electrochemical Cells Using Agar-Gelled Ferricyanide/Ferrocyanide/Guanidinium.

An isotropic thermo-electrochemical cell is introduced with a high Seebeck coefficient (S e) of 3.3 mV K-1 that uses a ferricyanide/ferrocyanide/guanidinium-based agar-gelated electrolyte. A power density of about 20 µW cm-2 is achieved at a temperature difference of about 10 K, regardless of whether the heat source is on the top or bottom section of the cell. This behavior is very different from that of cells with liquid electrolytes, which exhibit high anisotropy, and for which high S e values are achieved only by heating the bottom electrode. The guanidinium-containing gelatinized cell does not exhibit steady-state operation, but its performance recovers when disconnected from the external load, suggesting that the observed power drop under load conditions is not due to device degeneration. The large S e value and isotropic properties can mean that the novel system represents a major advancement from the standpoint of harvesting of low-temperature heat, such as body heat and solar thermal heat.

Tailoring organic heterojunction interfaces in bilayer polymer photovoltaic devices.

In an ideal model, a p-n junction is formed by two stacked slabs of semiconductors. Although the construction of actual devices is generally more complex, we show that such a simple method can in fact be applied to the formation of organic heterojunctions. Two films of the organic semiconductors poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) can be connected by a simple film-transfer method without disturbing their flat surfaces. Each film can further be modified with a surface-segregated monolayer to tune the strength and direction of the surface dipole moment. Using this method, we fabricated bilayer organic photovoltaic devices with interfacial dipole moments that were selected to align the energy levels at the heterojunction. The open-circuit voltages of the P3HT/PCBM devices could be tuned over a wide range between 0.3 and 0.95 V, indicating that, even if the same combination of bulk materials is used, the interfacial properties drastically alter the performance of organic photovoltaic devices.

Effects of block length in copolymers based on regioregular oligothiophenes linked with electron-accepting units.

Copolymers with an alternating structure of regioregular oligo(3-hexylthiophene) (O3HT) with different lengths and 2,5-dibutyl-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP) were synthesized through Stille coupling reaction. The light absorption of the copolymers can be rationally tuned to have a broad spectrum across the visible region by adjusting the length of O3HT. Organic solar cells fabricated with the copolymers and PCBM showed a broad photoresponse and a comparable efficiency to that of poly(3-hexylthiophene) (P3HT):PCBM cells. The external quantum efficiency and fluorescence spectra suggested that the intrachain energy transfer from the O3HT block to the vicinity of the DPP unit could limit the photovoltaic performance of the copolymers.

Interfacial modification of organic photovoltaic devices by molecular self-organization.

This feature article focuses on the relationship between the interfacial structures constructed by molecular self-organization and the properties of organic photovoltaic devices. The use of self-assembled monolayers (SAMs) is reviewed for metal and metal oxide/organic interfaces, while surface-segregated monolayers (SSMs) are introduced as a new method for the modification of organic/organic interfaces. Research up to now has clearly demonstrated the effectiveness of the control of energy levels and other properties at the interfaces to enhance photovoltaic performance. The possibility of more precise control of the interfacial structures is also discussed.

Bicyclic-ring base doping induces n-type conduction in carbon nanotubes with outstanding thermal stability in air.

The preparation of air and thermally stable n-type carbon nanotubes is desirable for their further implementation in electronic and energy devices that rely on both p- and n-type material. Here, a series of guanidine and amidine bases with bicyclic-ring structures are used as n-doping reagents. Aided by their rigid alkyl functionality and stable conjugate acid structure, these organic superbases can easily reduce carbon nanotubes. n-Type nanotubes doped with guanidine bases show excellent thermal stability in air, lasting for more than 6 months at 100 °C. As an example of energy device, a thermoelectric p/n junction module is constructed with a power output of ca. 4.7 µW from a temperature difference of 40 °C.

Design and synthesis of proton-dopable organic semiconductors.

This paper shows how protonated 3,4-ethylene dioxythiophene moieties can be used as an end group to make organic conductors. An organic semiconductor 2,5-bis(5-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene is designed and synthesized. This molecule could be doped by protonic acid in both solution and solid-state, resulting in a broad absorption in the near-infrared range corresponding to polaron and bipolaron absorption. Electrical conductivity of ca. 0.1 S cm-1 was obtained at 100 °C (to avoid the water uptake by the acid). The adducts with protons bound at the end-thiophene α-position were confirmed by 1H Nuclear Magnetic Resonance spectra.

Thermoelectrochemical Cells Based on Ferricyanide/Ferrocyanide/Guanidinium: Application and Challenges.

Ferricyanide/ferrocyanide/guanidinium-based thermoelectrochemical cells have been investigated under different loading conditions in this work. Compared with ferricyanide/ferrocyanide-based devices, the device with guanidinium-added electrolytes shows higher power and energy densities. We observed that the enhanced performance is not due to the ionic Seebeck effect of guanidinium but because of the configuration entropy change resulting from the selective binding of Gdm+ to Fe(CN)64-. However, the device with guanidinium-added electrolyte does not show steady-state operation. The two possible reasons include (1) the difficult diffusion of Fe(CN)63- into the crystal layer of (Gdm+)n[Fe(CN)64-] at the hot electrode and (2) the difficult precipitation of (Gdm+)n[Fe(CN)64-] formed at the cold side upon the binding of the reduced Fe(CN)64- with Gdm+. Nevertheless, the performance recovers once the device is disconnected from the external loading. Due to the high thermopower after adding guanidinium, we successfully fabricate self-powered sensors by connecting four flexible cells in series. The sensors can transfer humidity, temperature, and air pressure data wirelessly using body heat. Therefore, ferricyanide/ferrocyanide/guanidinium is a promising electrolyte material for applications of low-grade energy harvesting.

Outstanding Electrode-Dependent Seebeck Coefficients in Ionic Hydrogels for Thermally Chargeable Supercapacitor near Room Temperature.

Thermoelectric power generation from waste heat is an important component of future sustainable development. Ion-conducting materials are promising candidates because of their high Seebeck coefficients. This study demonstrates that ionic hydrogels based on imidazolium chloride salts exhibit outstanding Seebeck coefficients of up to 10 mV K-1. Along with their relatively high ionic conductivities (1.6 mS cm-1) and extremely low thermal conductivities (∼0.2 W m-1 K-1), these hydrogels have good potential for use in heat recovery systems. The voltage behavior in response to temperature difference (stable or transient) differs significantly depending on the metal electrode material. We evaluated the electrode-dependent temperature sensitivity of the double layer capacitance of these hydrogels, which revealed that the thermally induced polarization of ions at the interface is one of the main contributors to the thermovoltage. Our results demonstrate the potential capability for ion and metal interactions to be used as an effective baseline for exploring ionic thermoelectric materials and devices. The developed thermoelectric supercapacitor exhibits reversible charging-discharging behavior under repeated disconnecting-connecting of an external load with a constant temperature difference, which offers a novel strategy for heat-to-electricity energy conversion from steady-temperature heat sources.

Surface-segregated monolayers: a new type of ordered monolayer for surface modification of organic semiconductors.

We report a new type of ordered monolayer for the surface modification of organic semiconductors. Fullerene derivatives with fluorocarbon chains ([6,6]-phenyl-C(61)-buryric acid 1H,1H-perfluoro-1-alkyl ester or FC(n)) spontaneously segregated as a monolayer on the surface of a [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) film during a spin-coating process from the mixture solutions, as confirmed by X-ray photoelectron spectroscopy (XPS). Ultraviolet photoelectron spectroscopy (UPS) showed the shift of ionization potentials (IPs) depending on the fluorocarbon chain length, indicating the formation of surface dipole moments. Surface-sensitive vibrational spectroscopy, sum frequency generation (SFG) revealed the ordered molecular orientations of the C(60) moiety in the surface FC(n) layers. The intensity of the SFG signals from FC(n) on the surface showed a clear odd-even effect when the length of the fluorocarbon chain was changed. This new concept of the surface-segregated monolayer provides a facile and versatile approach to modifying the surface of organic semiconductors and is applicable to various organic optoelectronic devices.

Humidity control in a closed system utilizing conducting polymers.

In this study, we demonstrate that conducting polymers could be ideal materials for continuously managing humidity in a wide range of enclosed spaces. We demonstrate a simple battery-driven humidity control unit to manage the humidity in a closed environment and studied humidity-responsive nanocapsules using Zn-coordinated lipid nanovesicles. This study not only promises new applications for conducting polymers but also provides an easy approach for fabricating chambers with a controlled environment, which are often used by physicists, chemists, and biologists.

Moisture-responsive supramolecular nanotubes.

Living organisms have evolved functional structures for seeds dispersal in response to humidity changes. In this study, we construct moisture-responsive nanotubes by the supramolecular coordination of a peptide lipid with metal ions for potential applications in material delivery systems. These hydrophilic nanotubes can uptake atmospheric moisture and the water molecules are associated with unsaturated metal centers of the bis(lipid)-metal(ii) complex, thereby changing the molecular packing and inducing morphological transformation from nanotubes to sheets. The moisture responsivity of nanotubes depends on the hydration behavior of the metal ions. Co(ii)-coordinated nanotube shows higher moisture responsivity than that of the Zn(ii)-coordinated one since Co(ii) ion has stronger association with water molecules. These two nanotubes are self-assembled by the same molecular packings; however, they show different mechanisms in morphological changes. The Co(ii)-coordinated nanotube transforms into a sheet accompanied with the destruction of the complex and reverse molecular packing, whereas Zn(ii)-coordinated nanotube transforms into a sheet with a change in the complex geometry. Further, the Co(ii)-coordinated nanotubes exhibit reversible morphological changes between nanotubes and sheets, while Zn(ii)-coordinated nanotubes exhibit a one-way morphological change. These nanotubes also show potential applications in the release of fragrance oil under high humidity environments.

Reversible Protonic Doping in Poly(3,4-Ethylenedioxythiophene).

In this study, poly(3,4-ethylenedioxythiophene), a benchmark-conducting polymer, was doped by protons. The doping and de-doping processes, using protonic acid and a base, were fully reversible. We predicted possible doping sites along the polymer chain using density functional theory (DFT) calculations. This study sheds potential light and understanding on the molecular design of highly conductive organic materials.

Photoinduced Dedoping of Conducting Polymers: An Approach to Precise Control of the Carrier Concentration and Understanding Transport Properties.

Exploring the various applications of conjugated polymers requires systematic studies of their physical properties as a function of the doping density, which, consequently, calls for precise control of their doping density. In this study, we report a novel solid-state photoinduced charge-transfer reaction that dedopes highly conductive polyelectrolyte complexes such as poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate). Varying the UV-irradiation time of this material allows the carrier density inside the film to be precisely controlled over more than 3 orders of magnitude. We extract the carrier density, carrier mobility, and Seebeck coefficient at different doping levels to obtain a clear image of carrier-transport mechanisms. This approach not only leads to a better understanding of the physical properties of the conducting polymer but also is useful for developing applications requiring patterned, large-area conducting polymers.

Recent Progress on PEDOT-Based Thermoelectric Materials.

The thermoelectric properties of poly(3,4-ethylenedioxythiophene) (PEDOT)-based materials have attracted attention recently because of their remarkable electrical conductivity, power factor, and figure of merit. In this review, we summarize recent efforts toward improving the thermoelectric properties of PEDOT-based materials. We also discuss thermoelectric measurement techniques and several unsolved problems with the PEDOT system such as the effect of water absorption from the air and the anisotropic thermoelectric properties. In the last part, we describe our work on improving the power output of thermoelectric modules by using PEDOT, and we outline the potential applications of polymer thermoelectric generators.

Experimental Studies on the Anisotropic Thermoelectric Properties of Conducting Polymer Films.

We reported general methods for studying the thermoelectric properties of a polymer film in both the in-plane and through-plane directions. The bench-mark PEDOT/PSS films have highly anisotropic carrier transport properties and thermal conductivity. The anisotropic carrier transport properties can be explained by the lamellar structure of the PEDOT/PSS films where the PEDOT nanocrystals could be isolated by the insulating PSS in the through-plane direction. The anisotropic thermal conductivity was mainly attributed to the lattice contribution from PSS because the polymer chain is oriented along the substrate.