A New Porphyrin-based Covalent Organic Framework with High Iodine Capture Capacity and I-doping Enhanced Conductivity.

Covalent organic frameworks (COFs) are porous organic materials with well-defined and uniform structure. The material is an excellent candidate as a solid adsorbent for iodine adsorption. In the present study, we report the synthesis of COF with porphyrin moiety, TF-TA-COF, by solvothermal reaction, which was characterized by XRD, solid-state 13 C NMR, IR, TGA, and nitrogen adsorption-desorption analysis. TF-TA-COF showed a high specific surface area of 443 m2 g-1 , and exhibited good adsorption performance for iodine vapor, with an adsorption capacity of 2.74 g g-1 . XPS and Raman spectrum indicated that a hybrid of physisorption and chemisorption took place between host COF and iodine molecules. The electric properties of iodine-loaded TF-TA-COF were also studied. After doped with iodine, the conductivity of the material increased by more than 5 orders of magnitude. The photoconductivity of I2 -doped COF was also studied and TF-TA-COF showed doping-enhanced photocurrent generation.

The Fabrication of Halogen-Doped FeWO4 Heterostructure Anchored over Graphene Oxide Nanosheets for the Sunlight-Driven Photocatalytic Degradation of Methylene Blue Dye.

Rapid industrialization and urbanization are the two significant issues causing environmental pollution. The polluted water from various industries contains refractory organic materials such as dyes. Heterogeneous photocatalysis using semiconductor metal oxides is an effective remediation technique for wastewater treatment. In this research, we used a co-precipitation-assisted hydrothermal method to synthesize a novel I-FeWO4/GO sunlight-active nanocomposite. Introducing dopant reductive iodine species improved the catalytic activity of FeWO4/GO. I- ions improved the catalytic performance of H2O2 by doping into FeWO4/GO composite. Due to I- doping and the introduction of graphene as a support medium, enhanced charge separation and transfer were observed, which is crucial for efficient heterogeneous surface reactions. Various techniques, like FTIR, SEM-EDX, XRD, and UV-Vis spectroscopy, were used to characterize composites. The Tauc plot method was used to calculate pristine and iodine-doped FeWO4/GO bandgap. Iodine doping reduced the bandgap from 2.8 eV to 2.6 eV. The degradation of methylene blue (MB) was evaluated by optimizing various parameters like catalyst concentration, oxidant dose, pH, and time. The optimum conditions for photocatalysts where maximum degradation occurred were pH = 7 for both FeWO4/GO and I-FeWO4/GO; oxidant dose = 9 mM and 7 mM for FeWO4/GO and I-FeWO4/GO; and catalyst concentration = 30 mg and 35 mg/100 mL for FeWO4/GO and I-FeWO4/GO; the optimum time was 120 min. Under these optimum conditions, FeWO4/GO and I-FeWO4/GO showed 92.0% and 97.0% degradation of MB dye.

Charge Transfer Doping of Carbon Nitride Films through Noncovalent Iodination for Enhanced Photoelectrochemical Performance: Combined Experimental and Computational Insights.

To improve the photoelectrochemical (PEC) performance of photocatalysts, the doping strategy through covalent functionalization is often adopted to adjust material electronic structures. By contrast, this work demonstrates that the noncovalent interaction in the case of iodinated graphitic carbon nitride (g-CN) film can also enhance the PEC performance. Through a facile synthesis method of rapid thermal vapor condensation (RTVC), the prepared iodinated g-CN film shows a significantly improved photocurrent density (38.9 µA cm-2 ), three times that of pure g-CN film (13.0 µA cm-2 ) at 1.23 V versus reversible hydrogen electrode. Computations reveal that the noncovalent attachment of iodine anion (I- ) on g-CN plays a crucial role in modulating the bandgap states and broadening of the visible-light absorption range as well as the charge carrier separation with the photo-induced hole confined to I- and electron to g-CN film. The fully filled valence orbitals (4d10 5s2 5p6 ) of I- determine its noncovalent attachment on the g-CN film and so do the iodine species of I3 - , I5 - , etc. This work offers a favorable synthesis method to achieve efficient doping through noncovalent charge transfer between thin film and certain dopants and provides a useful modification strategy for the establishment of multi-channel transportation of charge carriers in general photocatalysts.

Facile one-pot iodine gas phase doping on 2D MoS2/CuS FET at room temperature.

Electronic devices composed of semiconducting two-dimensional (2D) materials and ultrathin 2D metallic electrode materials, accompanying synergistic interactions and extraordinary properties, are becoming highly promising for future flexible and transparent electronic and optoelectronic device applications. Unlike devices with bulk metal electrode and 2D channel materials, devices with ultrathin 2D electrode and 2D channel are susceptible to chemical reactions in both channel and electrode surface due to the high surface to volume ratio of the 2D structures. However, so far, the effect of doping was primary concerned on the channel component, and there is lack of understanding in terms of how to modulate electrical properties of devices by engineering electrical properties of both the metallic electrode and the semiconducting channel. Here, we propose the novel, one-pot doping of the field-effect transistor (FET) based on 2D molybdenum disulfide (MoS2) channel and ultrathin copper sulfide (CuS) electrodes under mild iodine gas environment at room temperature, which simultaneously modulates electrical properties of the 2D MoS2channel and 2D CuS electrode in a facile and cost-effective way. After one-pot iodine doping, effective p-type doping of the channel and electrode was observed, which was shown through decreased off current level, improvedIon/Ioffratio and subthreshold swing value. Our results open up possibility for effectively and conveniently modulating electrical properties of FETs made of various 2D semiconductors and ultrathin contact materials without causing any detrimental damage.

Adsorption and visible-light photocatalytic degradation of organic pollutants by functionalized biochar: Role of iodine doping and reactive species.

Here we developed the functionalized biochar as low-cost and heavy metal-free photocatalysts via a facile iodine doping method, which exhibit efficient adsorption and visible-light-driven photocatalytic degradation of representative organic pollutants, phenol and tetracycline. On one hand, iodine doping elevates the adsorption via creating extra pores, e.g., the adsorbed amounts of phenol by iodine-doped WSP and OSR biochar are increased by 161.8% and 146.3%, respectively, which in turn facilitates the photocatalytic oxidation of the adsorbed pollutants. On the other hand, iodine doping leads to the strong photo-induced excitation and remarkably reduced charge carrier transfer resistance, boosting the photocatalytic activity of iodine-doped biochar by more than 20 orders towards organic pollutants (e.g., phenol) degradation. The systematic analysis of reactive species reveals the active roles of O2-, H2O2, 1O2, OH, electrons, and holes in photocatalytic process and identifies O2- to be the major contributor. This work affords a facile approach to generating porous and visible-light-driven photocatalyst from biomass for efficient adsorbing and degrading organic pollutants, opening up an avenue to turn biowaste into biomaterials for sustainable environmental remediation.

Iodine-Doped Hollow Carbon Nanocages without Templates Strategy for Boosting Zinc-Ion Storage by Nucleophilicity.

Zn-ion hybrid supercapacitors (ZHCs) combining merits of battery-type and capacitive electrodes are considered to be a prospective candidate in energy storage systems. Tailor-made carbon cathodes with high zincophilicity and abundant physi/chemisorption sites are critical but it remains a great challenge to achieve both features by a sustainable means. Herein, a hydrogen-bonding interaction-guided self-assembly strategy is presented to prepare iodine-doped carbon nanocages without templates for boosting zinc-ion storage by nucleophilicity. The biomass ellagic acid contains extensional hydroxy and acyloxy groups with electron-donating ability, which interact with melamine and ammonium iodide to form organic supermolecules. The organic supermolecules further self-assemble into a nanocage-like structure with cavities under hydrothermal processes via hydrogen-bonding and π-π stacking. The carbon nanocages as ZHCs cathodes enable the high approachability of zincophilic sites and low ion migration resistance resulting from the interconnected conductive network and nanoscale architecture. The experimental analyses and theoretical simulations reveal the pivotal role of iodine dopants. The I5-/I3- doping anions in carbon cathodes have a nucleophilicity to preferentially adsorb the Zn2+ cation by the formation of C+-I5--Zn2+ and C+-I3--Zn2+. Of these, the C+-I3- shows stronger bonding with Zn2+ than C+-I5-. As a result, the iodine-doped carbon nanocages produced via this template-free strategy deliver a high capacity of 134.2 mAh/g at 1 A/g and a maximum energy and power density of 114.1 Wh/kg and 42.5 kW/kg.

Improvement of Electrical Conductivity of In Situ Iodine-Doped Polypyrrole Film Using Atmospheric Pressure Plasma Reactor with Capillary Electrodes.

To improve the electrical conductivity of polypyrrole (PPy) nanostructure film through in situ iodine (I2) doping, this study proposes an atmospheric pressure plasma reactor (APPR) where heated I2 dopant vapor is fed through capillary electrodes that serve as electrodes for discharge ignition. A large amount of the heated I2 vapor introduced into the reactor separately from a monomer gas can be effectively activated by an intense plasma via capillary electrodes. In particular, intensive plasma is obtained by properly adjusting the bluff body position in the APPR. Based on the ICCD and OES results, the I2 vapor injected through the capillary nozzle electrode is observed to form I2 charge species. The formed I2 species could directly participate in growing in situ I2-doped PPy films. Thus, in situ I2-doped PPy nanostructure films grown using the proposed APPR exhibit higher thicknesses of 15.3 µm and good electrical conductivities, compared to the corresponding non-doped films.

Iodine-doped g-C3N4 modified zinc titanate electron transporting layer for highly efficient perovskite solar cells.

The development of excellent ternary metal oxides as electron transporting layers (ETLs) is highly challenging for perovskite solar cells (PSCs). In this study, ZnTiO3 (ZTO) nanoparticles are synthesized via a facile sol-gel method, and used as an ETL in PSCs. Furthermore, for the first time, iodine-doped g-C3N4 (ICN) is introduced into ZnTiO3-based ETL as additive via a glass-assisted annealing route. Characterizations demonstrate that the ZnTiO3-based ETL with the addition of ICN will enhance the PCE, which is attributed to the improved crystalline quality and more favorable energy level alignment. Moreover, the existence of ICN will strengthen the interfacial cohesion between perovskite layer and ETL as well as retard the perovskite crystals from decomposing, leading to the high quality capping light-harvesting layer upon ICN-modified ZnTiO3 (ZTO-ICN) film. Consequently, a champion device fabricated with ZTO-ICN ETL achieves a maximum PCE of 19.17 % with an open circuit voltage (Voc) of 1.012 V, a short-circuit current density (Jsc) of 26.32 mA cm-2 and a fill factor (FF) of 0.720 under AM 1.5 G sunlight (100 mW cm-2).

Thermo-Optical and Structural Studies of Iodine-Doped Polymer: Fullerene Blend Films, Used in Photovoltaic Structures.

Optical and structural properties of a blend thin film of (1:1 wt.) of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) doped with iodine (I2) and then exposed to a stepwise heating were reported and compared with the properties of doped P3HT films. The UV-Vis(T) absorption measurements were performed in situ during annealing runs, at the precisely defined temperatures, in a range of 20-210 °C. It was demonstrated that this new method allows one to observe the changes of absorption spectra, connected with the iodine release and other structural processes upon annealing. In addition, the thermally-induced changes of the exciton bandwidth (W) and the absorption edge parameters, i.e., the energy gap (EG) and the Urbach energy (EU) were discussed in the context of different length of conjugation and the structural disorder in polymers and blends films. During annealing, several stages were distinguished and related to the following processes as: the iodine escape and an increase in P3HT crystallinity, the orderly stacking of polymer chains, the thermally inducted structural defects and the phase separation caused by an aggregation of PCBM in the polymer matrix. Moreover, the detailed X-ray diffraction studies, performed for P3HT and P3HT:PCBM films, before and after doping and then after their thermal treatment, allowed us to consider the structural changes of polymer and blend films. The effect of iodine content and the annealing process on the bulk heterojunction (BHJ) solar cells parameters was checked, by the impedance spectroscopy (IS) measurements and the J-V characteristics registration. All of the investigated P3HT:PCBM blend films showed the photovoltaic effect; the increase in power conversion efficiency (PCE) upon iodine doping was demonstrated.

Effects of Iodine Doping on Electrical Characteristics of Solution-Processed Copper Oxide Thin-Film Transistors.

In order to implement oxide semiconductor-based complementary circuits, the improvement of the electrical properties of p-type oxide semiconductors and the performance of p-type oxide TFTs is certainly required. In this study, we report the effects of iodine doping on the structural and electrical characteristics of copper oxide (CuO) semiconductor films and the TFT performance. The CuO semiconductor films were fabricated using copper(II) acetate hydrate as a precursor to solution processing, and iodine doping was performed using vapor sublimated from solid iodine. Doped iodine penetrated the CuO film through grain boundaries, thereby inducing tensile stress in the film and increasing the film's thickness. Iodine doping contributed to the improvement of the electrical properties of the solution-processed CuO semiconductor including increases in Hall mobility and hole-carrier concentration and a decrease in electrical resistivity. The CuO TFTs exhibited a conduction channel formation by holes, that is, p-type operation characteristics, and the TFT performance improved after iodine doping. Iodine doping was also found to be effective in reducing the counterclockwise hysteresis in the transfer characteristics of CuO TFTs. These results are explained by physicochemical reactions in which iodine replaces oxygen vacancies and oxygen atoms through the formation of iodide anions in CuO.

Scattering Mechanisms and Suppression of Bipolar Diffusion Effect in Bi2Te2.85Se0.15Ix Compounds.

We investigated the anisotropic thermoelectric properties of the Bi2Te2.85Se0.15Ix (x = 0.0, 0.1, 0.3, 0.5 mol.%) compounds, synthesized by ball-milling and hot-press sintering. The electrical conductivities of the Bi2Te2.85Se0.15Ix were significantly improved by the increase of carrier concentration. The dominant electronic scattering mechanism was changed from the mixed (T ≤ 400 K) and ionization scattering (T ≥ 420 K) for pristine compound (x = 0.0) to the acoustic phonon scattering by the iodine doping. The Hall mobility was also enhanced with the increasing carrier concentration. The enhancement of Hall mobility was caused by the increase of the mean free path of the carrier from 10.8 to 17.7 nm by iodine doping, which was attributed to the reduction of point defects without the meaningful change of bandgap energy. From the electron diffraction patterns, a lattice distortion was observed in the iodine doped compounds. The modulation vector due to lattice distortion increased with increasing iodine concentration, indicating the shorter range lattice distortion in real space for the higher iodine concentration. The bipolar thermal conductivity was suppressed, and the effective masses were increased by iodine doping. It suggests that the iodine doping minimizes the ionization scattering giving rise to the suppression of the bipolar diffusion effect, due to the prohibition of the BiTe1 antisite defect, and induces the lattice distortion which decreases lattice thermal conductivity, resulting in the enhancement of thermoelectric performance.

Significantly Enhanced Thermoelectric Properties of Copper Phthalocyanine/Single-Walled Carbon Nanotube Hybrids by Iodine Doping.

The copper phthalocyanine/single-walled carbon nanotube (CuPcI/SWCNT) hybrids were fabricated through doping the CuPc/SWCNT mixture using iodine vapor. It was found that both CuPc and SWCNTs were oxidized by iodine vapor resulting in great increase in carrier concentration. Moreover, the strong π-π conjugation interactions between CuPcI- and I-doped SWCNTs make the CuPcI molecules to assemble on the surface of SWCNTs in an ordered face-on packing, which benefits decreasing the carrier transport barrier across the CuPcI/SWCNT interfaces. The combination of iodine bidoping and the ordered face-on packing of CuPcI on the SWCNT surface realizes the synergetic enhancement of carrier concentration and carrier mobility and therefore the great improvement of electrical conductivity. The maximum electrical conductivity (6281 S cm-1) and thermoelectric power factor (∼304 µW m-1 K-2) at room temperature were obtained at a composition of 60 wt % SWCNTs. The power factor value is 3 orders of magnitude higher than the pure CuPcI and 1 order of magnitude higher than SWCNTs. Consequently, the highest ZT value of CuPc/SWCNT hybrids is up to 0.03, which is among the highest value of organic small-molecule complexes.

Iodine-Doping-Induced Electronic Structure Tuning of Atomic Cobalt for Enhanced Hydrogen Evolution Electrocatalysis.

The development of strategies for tuning the electronic structure of the metal sites in single-atom catalysts (SACs) is the key to optimizing their activity. Herein, we report that iodine doping within the carbon matrix of a cobalt-nitrogen-carbon (Co-N-C) catalyst can effectively modulate its electronic structure and catalytic activity toward the hydrogen evolution reaction (HER). The iodine-doped Co-N-C catalyst shows exceptional HER activity in acid with an overpotential of merely 52 mV at 10 mA cm-2, a small Tafel slope of 56.1 mV dec-1, making it among the best SACs based on both precious and nonprecious metals. Moreover, this catalyst possesses a high turnover frequency (TOF) value of 1.88 s-1 (η = 100 mV), which is about 1 order of magnitude larger than that (0.2 s-1) of the iodine-free counterpart. Experimental and theoretical studies demonstrate that the introduction of iodine dopants lowers the chemical oxidation state of the Co sites, resulting in the optimized hydrogen adsorption and facilitated HER kinetics. This work provides an alternative strategy to regulate the electronic structure of SACs for improved performance.

Fabrication and characterization of novel iodine doped hollow and mesoporous hematite (Fe2O3) particles derived from sol-gel method and their photocatalytic performances.

In this work, iodine (I) doped hollow and mesoporous Fe2O3 photocatalyst particles were fabricated for the first time through sol-gel method. Phase structure, surface morphology, particle size, specific surface area and optical band gap of the synthesized Fe2O3 photocatalysts were analyzed by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), X-ray photoelectron spectroscopy (XPS), BET surface analysis, particle size analyzer and UV-vis diffuse reflectance spectrum (UV-vis DRS), respectively. Also, electrochemical properties and photoluminescence spectra of Fe2O3 particles were measured. The results illustrated that high crystalline, hollow and mesoporous Fe2O3 particles were formed. The optical band gap values of the Fe2O3 photocatalysts changed between 2.104 and 1.93eV. Photocatalytic efficiency of Fe2O3 photocatalysts were assessed via MB solution. The photocatalytic activity results exhibited that I doping enhanced the photocatalytic efficiency. 1% mole iodine doped (I-2) Fe2O3 photocatalyst had 97.723% photodegradation rate and 8.638×10-2min-1 kinetic constant which showed the highest photocatalytic activity within 45min. Moreover, stability and reusability experiments of Fe2O3 photocatalysts were carried out. The Fe2O3 photocatalysts showed outstanding stability after four sequence tests. As a result, I doped Fe2O3 is a good candidate for photocatalysts.

Fluorene-Based Two-Dimensional Covalent Organic Framework with Thermoelectric Properties through Doping.

Organic semiconductors have great potential as flexible thermoelectric materials. A fluorene-based covalent organic framework (FL-COF-1) was designed with the aim of creating an enhanced π-π interaction among the crystalline backbones. By the introduction of fluorene units into the frameworks, the FL-COF-1 had high thermal stability with a BET surface area over 1300 m2 g-1. The open frameworks were favorable for doping with iodine and followed with the improved charge carrier mobility. The compressed pellet of I2@FL-COF-1 exhibited a high Seebeck coefficient of 2450 µV K-1 and power factor of 0.063 µW m-1 K-2 at room temperature, giving the first example of COFs' potential application as thermoelectric materials.

Effects of Iodine Doping on Optoelectronic and Chemical Properties of Polyterpenol Thin Films.

Owing to their amorphous, highly cross-liked nature, most plasma polymers display dielectric properties. This study investigates iodine doping as the means to tune optoelectronic properties of plasma polymer derived from a low-cost, renewable resource, i.e., Melaleuca alternifolia oil. In situ exposure of polyterpenol to vapors of electron-accepting dopant reduced the optical band gap to 1.5 eV and increased the conductivity from 5.05 × 10-8 S/cm to 1.20 × 10-6 S/cm. The increased conductivity may, in part, be attributed to the formation of charge-transfer complexes between the polymer chain and halogen, which act as a cation and anion, respectively. Higher levels of doping notably increased the refractive index, from 1.54 to 1.70 (at 500 nm), and significantly reduced the transparency of films.

Atmospheric Pressure Plasma Polymerization Synthesis and Characterization of Polyaniline Films Doped with and without Iodine.

Although polymerized aniline (polyaniline, PANI) with and without iodine (I2) doping has already been extensively studied, little work has been done on the synthesis of PANI films using atmospheric pressure plasma (APP) deposition. Therefore, this study characterized pure and I2-doped PANI films synthesized using an advanced APP polymerization system. The I2 doping was conducted ex-situ and using an I2 chamber method following the APP deposition. The pure and I2-doped PANI films were structurally analyzed using field emission scanning electron microscope (FE-SEM), atomic force microscope (AFM), X-ray Diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and time of flight secondary ion mass spectrometry (ToF-SIMS) studies. When increasing the I2 doping time, the plane and cross-sectional SEM images showed a decrease in the width and thickness of the PANI nanofibers, while the AFM results showed an increase in the roughness and grain size of the PANI films. Moreover, the FT-IR, XPS, and ToF-SIMS results showed an increase in the content of oxygen-containing functional groups and C=C double bonds, yet decrease in the C-N and C-H bonds when increasing the I2 doping time due to the reduction of hydrogen in the PANI films via the I2. To check the suitability of the conductive layer for polymer display applications, the resistance variations of the PANI films grown on the interdigitated electrode substrates were also examined according to the I2 doping time.

Conductive Polymer Synthesis with Single-Crystallinity via a Novel Plasma Polymerization Technique for Gas Sensor Applications.

This study proposes a new nanostructured conductive polymer synthesis method that can grow the single-crystalline high-density plasma-polymerized nanoparticle structures by enhancing the sufficient nucleation and fragmentation of the pyrrole monomer using a novel atmospheric pressure plasma jet (APPJ) technique. Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy (FE-SEM) results show that the plasma-polymerized pyrrole (pPPy) nanoparticles have a fast deposition rate of 0.93 µm·min-1 under a room-temperature process and have single-crystalline characteristics with porous properties. In addition, the single-crystalline high-density pPPy nanoparticle structures were successfully synthesized on the glass, plastic, and interdigitated gas sensor electrode substrates using a novel plasma polymerization technique at room temperature. To check the suitability of the active layer for the fabrication of electrochemical toxic gas sensors, the resistance variations of the pPPy nanoparticles grown on the interdigitated gas sensor electrodes were examined by doping with iodine. As a result, the proposed APPJ device could obtain the high-density and ultra-fast single-crystalline pPPy thin films for various gas sensor applications. This work will contribute to the design of highly sensitive gas sensors adopting the novel plasma-polymerized conductive polymer as new active layer.