Flexible and Ultra Low Weight Energy Harvesters Based on 2D Phosphorene or Black phosphorus (BP): Current and Futuristic Prospects.

Phosphorene, or two-dimensional (2D) black phosphorus, has recently emerged as a competitor of graphene as it offers several advantages, including a tunable band gap, higher on/off current ratio, piezoelectric nature, and biocompatibility. Researchers have succeeded in obtaining several forms of phosphorene, such as nanosheets, nanorods, nanoribbons, and quantum dots, with satisfactory yields. Nanostructures with various controlled properties have been fabricated in multiple devices for energy production. These phosphorene-based devices are lightweight, flexible, and efficient, demonstrating great potential for energy-harvesting applications in sensors and nanogenerators. While ongoing exploration and advancements continue for these lightweight energy harvesters, it is essential to review the current progress in order to develop a future roadmap for the potential use of these phosphorene-based energy harvesters in space programs. They could be employed in applications such as wearable devices for astronauts, where ultralow weight is a vital component of any integrated device. This review also anticipates the growing significance of phosphorene in various emerging applications such as robots, information storage devices, and artificial intelligence.

Optimized Polymeric Membranes for Water Treatment: Fabrication, Morphology, and Performance.

Conventional polymers, endowed with specific functionalities, are extensively utilized for filtering and extracting a diverse set of chemicals, notably metals, from solutions. The main structure of a polymer is an integral part for designing an efficient separating system. However, its chemical functionality further contributes to the selectivity, fabrication process, and resulting product morphology. One example would be a membrane that can be employed to selectively remove a targeted metal ion or chemical from a solution, leaving behind the useful components of the solution. Such membranes or products are highly sought after for purifying polluted water contaminated with toxic and heavy metals. An efficient water-purifying membrane must fulfill several requirements, including a specific morphology attained by the material with a specific chemical functionality and facile fabrication for integration into a purifying module Therefore, the selection of an appropriate polymer and its functionalization become crucial and determining steps. This review highlights the attempts made in functionalizing various polymers (including natural ones) or copolymers with chemical groups decisive for membranes to act as water purifiers. Among these recently developed membrane systems, some of the materials incorporating other macromolecules, e.g., MOFs, COFs, and graphene, have displayed their competence for water treatment. Furthermore, it also summarizes the self-assembly and resulting morphology of the membrane materials as critical for driving the purification mechanism. This comprehensive overview aims to provide readers with a concise and conclusive understanding of these materials for water purification, as well as elucidating further perspectives and challenges.

Manipulation and Direct Characterization of Polymer/Small-Molecule Interface Morphology in Bulk-Heterojunction Solar Cell.

To investigate the effect of miscibility between conjugated polymers (CPs) and Y6 on bulk-heterojunction (BHJ) type morphology, we propose three different CPs with similar chemical structures but different miscibility with Y6. After selectively removing Y6 from the CP/Y6 blend films, their interface morphology and interlocked dimensions are quantitatively compared using a square-wave model. As CP-Y6 miscibility increases, a higher intermixed interface is formed, providing an enlarged CP-Y6 interface area. Conversely, as the miscibility between CP and Y6 decreases, the height and width of the interlocked dimensions formed by phase separation gradually decrease and increase, respectively. Additionally, when the CP-Y6 interface morphology and electrical properties of the corresponding organic photovoltaic (OPV) device are correlated, as the highly intermixed CP-Y6 interface develops, the exciton dissociation efficiency increases owing to the reduced exciton diffusion length to be dissociated, but the bimolecular recombination tends to deteriorate simultaneously. Furthermore, if the miscibility between CP and Y6 is excessive, the formation of a charge transport pathway through phase separation is interrupted, deteriorating the charge transport capability in BHJ-type OPVs. However, it was confirmed that introducing F atoms into the conjugated backbone of CP can reduce the bimolecular recombination, providing ameliorated light-harvesting efficiency.

Soft tissue outcomes following alveolar ridge preservation with/without primary flap closure for periodontally damaged extraction socket: A randomized clinical trial.

INTRODUCTION: The changes in soft tissue profile following alveolar ridge preservation (ARP) with/without primary flap closure (PC) in periodontally damaged sockets have yet to be discovered. METHODS: For periodontally damaged non-molar extraction sockets, ARP with PC (group PC)/without PC (group SC) was performed using granule-type xenogeneic bone substitute material and a collagen barrier. Intraoral scans were performed at the time of ARP and 4 months thereafter. Superimposition of STL files was performed to examine tissue change on the soft tissue level. The level of mucogingival junction (MGJ) was also evaluated. RESULTS: A total of 28 patient (13 in group PC, 15 in group SC) completed the study. Soft tissue profile change was evaluated only when the measurement level was located on the non-mobile tissue. Group PC tended to shrink less on the long axis of the extraction socket than group SC (-4.3 ± 3.1 mm vs. -5.9 ± 4.4 mm at the 1 mm below the pre-extraction gingival margin, p > 0.05). Profilometric analysis (on the region of interest) also have a tendency of less tissue profile change in group PC than group SC (-1.0 ± 0.8 mm vs. -1.3 ± 0.5 mm, p > 0.05). The MGJ level change was not statistically significantly different between the groups (p > 0.05) even though the MGJ level was located more apically at 4 months in group SC compared with group PC. CONCLUSIONS: Alveolar ridge preservation with PC tended to yield less soft tissue shrinkage than ARP without PC.

Towards the Future of Polymeric Hybrids of Two-Dimensional Black Phosphorus or Phosphorene: From Energy to Biological Applications.

With the advent of a new 2D nanomaterial, namely, black phosphorus (BP) or phosphorene, the scientific community is now dedicated to focusing on and exploring this 2D material offering elusive properties such as a higher carrier mobility, biocompatibility, thickness-dependent band gap, and optoelectronic characteristics that can be harnessed for multiple applications, e.g., nanofillers, energy storage devices, field effect transistors, in water disinfection, and in biomedical sciences. The hexagonal ring of phosphorus atoms in phosphorene is twisted slightly, unlike how it is in graphene. Its unique characteristics, such as a high carrier mobility, anisotropic nature, and biocompatibility, have attracted much attention and generated further scientific curiosity. However, despite these interesting features, the phosphorene or BP poses challenges and causes frustrations when it comes to its stability under ambient conditions and processability, and thus in order to overcome these hurdles, it must be conjugated or linked with the suitable and functional organic counter macromolecule in such a way that its properties are not compromised while providing a protection from air/water that can otherwise degrade it to oxides and acid. The resulting composites/hybrid system of phosphorene and a macromolecule, e.g., a polymer, can outperform and be exploited for the aforementioned applications. These assemblies of a polymer and phosphorene have the potential for shifting the paradigm from exhaustively used graphene to new commercialized products offering multiple applications.

Effect of Chlorine Substituents on the Photovoltaic Properties of Monocyanated Quinoxaline-Based D-A-Type Polymers.

A string of monocyanated quinoxaline (Qx)-based D-A-type polymers systematically decorated with electron-attracting chlorine (Cl) atoms was created for use in non-fullerene polymer solar cells (PSCs). First, coupling of the benzodithiophene (BDT) donor and Qx acceptor with the strong electron-attracting cyano (CN) unit at its 5-position yielded the monocyanated reference polymer PB-CNQ. Subsequently, the additional Cl atoms were separately or simultaneously incorporated into the thiophene side groups of the BDT donor and Qx acceptor to create other objective polymers, PBCl-CNQ, PB-CNQCl, and PBCl-CNQCl. The Cl substituents on the BDT donor and Qx acceptor are represented by the names of the polymers. Owing to the favorable contributions of Cl substituents, the inverted-type non-fullerene PSCs based on partially chlorinated PBCl-CNQ (12.80%) and PB-CNQCl (13.93%) exhibited better power conversion efficiencies (PCEs) than the device based on unchlorinated reference PB-CNQ (11.19%). However, a significantly reduced PCE of 9.84% was observed for the device based on PBCl-CNQCl, in which Cl atoms were loaded on both the BDT donor and Qx acceptor at the same time. Hence, these results reveal that optimization of the number and position of Cl substituents in monocyanated Qx-based polymers is essential for enhancing their photovoltaic nature through the synergistic effects between two strong electron-attracting CN and Cl substituents.

Primary flap closure in alveolar ridge preservation for periodontally damaged extraction socket: A randomized clinical trial.

INTRODUCTION: The effect of primary wound closure (PC) on alveolar ridge preservation (ARP) in periodontally damaged sockets has yet to be fully discovered. METHODS: Periodontally damaged sockets were allocated to one of the following groups: (1) ARP with PC (group PC), and (2) ARP without PC (group secondary wound closure [SC]). Following tooth extraction and flap elevation, granule-type xenogeneic bone substitute material and a collagen barrier were applied. Ridge change was evaluated using cone-beam computed tomographic (CBCT) scans immediately after ARP and at 4 months. Core biopsy specimens were examined histomorphometrically. RESULTS: A total of 28 patients were included in the analysis (13 in group PC, 15 in group SC). Histomorphometrically, the percentage of newly formed bone was 26.2 ± 17.7% and 24.6 ± 18.4% in groups PC and SC, respectively (independent t-test, degree of freedom [df] = 25, p > 0.05). Horizontal ridge changes on CBCT were -4.9 ± 3.1 mm and - 4.2 ± 2.5 mm in groups PC and SC at the 1 mm level below the ridge crest, respectively (independent t-test, df = 26, p > 0.05). Approximately half of the sites required additional bone augmentation at implant placement. CONCLUSIONS: ARP with/without PC yielded similar new bone formation and radiographic ridge change. This clinical trial was not registered prior to participant recruitment and randomization (https://cris.nih.go.kr/cris/search/detailSearch.do/19718).

Proton Conducting Membranes with Molecular Self Assemblies and Ionic Channels for Efficient Proton Conduction.

Supramolecular assemblies are vital for biological systems. This phenomenon in artificial materials is directly related to their numerous properties and their performance. Here, a simple approach to supramolecular assemblies is employed to fabricate highly efficient proton conducting molecular wires for fuel cell applications. Small molecule-based molecular assembly leading to a discotic columnar architecture is achieved, simultaneously with proton conduction that can take place efficiently in the absence of water, which otherwise is very difficult to obtain in interconnected ionic channels. High boiling point proton facilitators are incorporated into these columns possessing central ionic channels, thereby increasing the conduction multifold. Larger and asymmetrical proton facilitators disintegrated the self-assembly, resulting in low proton conduction efficiency. The highest conductivity was found to be approaching 10-2 S/cm for the molecular wires in an anhydrous state, which is ascribed to the continuous network of hydrogen bonds in which protons can hop between with a lower energy barrier. The molecular wires with ionic channels presented here have potential as an alternative to proton conductors operating under anhydrous conditions at both low and high temperatures.

Effect of Electron-Withdrawing Chlorine Substituent on Morphological and Photovoltaic Properties of All Chlorinated D-A-Type Quinoxaline-Based Polymers.

The choice of the chlorine (Cl) atom as an electron-withdrawing substituent in conjugated polymers leads to a higher potential in the commercialization of polymer solar cells than its fluorine counterpart because of the versatility and cost-effectiveness of the chlorination process. In addition, the population and location of Cl substituents can significantly influence the photovoltaic characteristics of polymers. In this study, three chlorinated quinoxaline-based polymers were invented to examine the numerical and positioning effects of the Cl atom on their photovoltaic characteristics. The number of Cl substituents in the reference polymer, PBCl-Qx, was adjusted to three: two Cl atoms in the benzodithiophene-type D unit and one Cl atom in the quinoxaline-type A unit. Subsequently, two more Cl atoms were selectively introduced at the 4- and 5-positions of the alkylated thiophene moieties at the 2,3-positions of the quinoxaline moiety in PBCl-Qx to obtain the additional polymers PBCl-Qx4Cl and PBCl-Qx5Cl, respectively. The conventional PBCl-Qx4Cl device exhibited a better power conversion efficiency (PCE) of 12.95% as compared to those of PBCl-Qx (12.44%) and PBCl-Qx5Cl (11.82%) devices. The highest PCE of the device with PBCl-Qx4Cl was ascribed to an enhancement in the open-circuit voltage and fill factor induced by the deeper energy level of the highest occupied molecular orbital and the favorable morphological features in its blended film with Y6.

Effect of electron-withdrawing fluorine and cyano substituents on photovoltaic properties of two-dimensional quinoxaline-based polymers.

In this study, strong electron-withdrawing fluorine (F) and cyano (CN) substituents are selectively incorporated into the quinoxaline unit of two-dimensional (2D) D-A-type polymers to investigate their effects on the photovoltaic properties of the polymers. To construct the 2D polymeric structure, electron-donating benzodithiophene and methoxy-substituted triphenylamine are directly linked to the horizontal and vertical directions of the quinoxaline acceptor, respectively. After analyzing the structural, optical, and electrochemical properties of the resultant F- and CN-substituted polymers, labeled as PBCl-MTQF and PBCl-MTQCN, respectively, inverted-type polymer solar cells with a non-fullerene Y6 acceptor are fabricated to investigate the photovoltaic performances of the polymers. It is discovered that the maximum power conversion efficiency of PBCl-MTQF is 7.48%, whereas that of PBCl-MTQCN is limited to 3.52%. This significantly reduced PCE of the device based on PBCl-MTQCN is ascribed to the formation of irregular, large aggregates in the active layer, which can readily aggravate the charge recombination and charge transport kinetics of the device. Therefore, the photovoltaic performance of 2D quinoxaline-based D-A-type polymers is significantly affected by the type of electron-withdrawing substituent.

Synthesis of Cyano-Substituted Conjugated Polymers for Photovoltaic Applications.

Three conjugated polymers, in which the electron-donating (D) 5-alkylthiophene-2-yl-substitued benzodithiophene was linked to three different electron-accepting (A) moieties, i.e., benzothiadiazole (BT), diphenylquinoxaline (DPQ), and dibenzophenazine (DBP) derivative via thiophene bridge, were synthesized using the Stille coupling reaction. In particular, the strong electron-withdrawing cyano (CN) group was incorporated into the A units BT, DPQ, and DBP to afford three D-A type target polymers PB-BTCN, PB-DPQCN, and PB-DBPCN, respectively. Owing to the significant contribution of the CN-substituent, these polymers exhibit not only low-lying energy levels of both the highest occupied molecular orbital and the lowest unoccupied molecular orbital, but also reduced bandgaps. Furthermore, to investigate the photovoltaic properties of polymers, inverted-type devices with the structure of ITO/ZnO/Polymer:PC71BM/MoO3/Ag were fabricated and analyzed. All the polymer solar cells based on the three cyano-substituted conjugated polymers showed high open-circuit voltages (Voc) greater than 0.89 V, and the highest power conversion efficiency of 4.59% was obtained from the device based on PB-BtCN with a Voc of 0.93 V, short-circuit current of 7.36 mA cm-2, and fill factor of 67.1%.

Synthesis of Trifluoromethylated Quinoxaline-Based Polymers for Photovoltaic Applications.

A series of quinoxaline-based conjugated polymers, in which the electron-donating benzodithiophene (BDT) unit is linked to the electron-accepting 6,7-difluorinated quinoxaline (DFQ) derivatives by a thiophene bridge, is synthesized. To investigate their effects on the intrinsic properties of polymers, strong electron-withdrawing trifluoromethyl (CF3 ) groups were incorporated into the meta-position of the phenyl ring at the 2,3-positions of the DFQ unit of the reference polymer, labelled PEhB-FQx, to yield the target polymer PEhB-FQxCF3. In addition, the 2-ethylhexyloxy substituents on the BDT donor in PEhB-FQxCF3 are changed to the more planar 2-ethylhexyl thiophene units to produce another target polymer PThB-FQxCF3. Owing to the significant contributions of the CF3 moiety, PEhB-FQxCF3 exhibits quite discernible optical and electrochemical properties along with significant enhancement in photovoltaic performances compared to the reference polymer PEhB-FQx. Furthermore, the incorporation of the alkylthienyl side chains on the BDT moiety confers on the resultant PThB-FQxCF3 to possess the maximum power conversion efficiency of 7.26% with an open circuit voltage of 0.88 V, short-circuit current density of 12.20 mA cm-2 , and fill factor of 67.80%.

Nitrogen-Doped Graphene for Photocatalytic Hydrogen Generation.

Photocatalytic hydrogen (H2 ) generation in a water splitting process has recently attracted tremendous interest because it allows the direct conversion of clean and unlimited solar energy into the ideal energy resource of H2 . For efficient photocatalytic H2 generation, the role of the photocatalyst is critical. With increasing demand for more efficient, sustainable, and cost-effective photocatalysts, various types of semiconductor photocatalysts have been intensively developed. In particular, on the basis of its superior catalytic and tunable electronic properties, nitrogen-doped graphene is a potential candidate for a high-performance photocatalyst. Nitrogen-doped graphene also offers additional advantages originating from its unique two-dimensional sp(2) -hybridized carbon network including a large specific surface area and exceptional charge transport properties. It has been reported that nitrogen-doped graphene can play diverse but positive functions including photo-induced charge acceptor/meditator, light absorber from UV to visible light, n-type semiconductor, and giant molecular photocatalyst. Herein, we summarize the recent progress and general aspects of nitrogen-doped graphene as a photocatalyst for photocatalytic H2 generation. In addition, challenges and future perspectives in this field are also discussed.

Nitrogen-doped graphene nanoplatelets from simple solution edge-functionalization for n-type field-effect transistors.

The development of a versatile method for nitrogen-doping of graphitic structure is an important challenge for many applications, such as energy conversions and storages and electronic devices. Here, we report a simple but efficient method for preparing nitrogen-doped graphene nanoplatelets via wet-chemical reactions. The reaction between monoketone (C═O) in graphene oxide (GO) and monoamine-containing compound produces imine (Shiff base) functionalized GO (iGO). The reaction between α-diketone in GO and 1,2-diamine (ortho-diamine)-containing compound gives stable pyrazine ring functionalized GO (pGO). Subsequent heat-treatments of iGO and pGO result in high-quality, nitrogen-doped graphene nanoplatelets to be designated as hiGO and hpGO, respectively. Of particular interest, hpGO was found to display the n-type field-effect transistor behavior with a charge neutral point (Dirac point) located at around -16 V. Furthermore, hpGO showed hole and electron mobilities as high as 11.5 and 12.4 cm(2)V(-1)s(-1), respectively.

Edge-selectively functionalized graphene nanoplatelets.

Graphene, as a single layer of graphite, is currently the focal point of research into condensed matter owing to its promising properties, such as exceptional mechanical strength, high thermal conductivity, large specific surface area, and ultrahigh electron-transport properties. Therefore, various physical and chemical synthetic procedures to prepare graphene and/or graphene nanoplatelets have been rapidly developed. Specifically, the synthesis of edge-selectively functionalized graphene (EFG) has been recently reported by using simple and scalable approaches, such as "direct" Friedel-Crafts acylation reactions in a mild acidic medium and a mechanochemical ball-milling process. In these approaches, chemical functionalization predominantly take place at the edges of the graphitic layers via the covalent attachment of targeted organic "molecular wedges". In addition, the distortion of the crystalline structures in the basal plane, which is beneficial for preserving the unique properties of the graphitic framework, can be minimized. In addition, the efficient exfoliation of graphene can be achieved, owing to the strong repulsive forces from the covalently linked wedges and strong shear forces during the reaction. Furthermore, EFG shows promising potential in many useful applications, such as highly conductive large-area films, metal-free electrocatalysts for the oxygen-reduction reaction (ORR), and as additives in composite materials with enhanced properties. Herein, we summarize the recent progress and general aspects of EFG, including synthesis, reaction mechanism, properties, and applications.

Water-dispersible, sulfonated hyperbranched poly(ether-ketone) grafted multiwalled carbon nanotubes as oxygen reduction catalysts.

To endorse sufficient water affinity to multiwalled carbon nanotubes (MWCNTs), dendritic hyperbranched poly(ether-ketone) (HPEK) was first covalently grafted to the surface of a MWCNT via a Friedel-Crafts acylation reaction. The resultant HPEK-grafted MWCNT (HPEK-g-MWCNT) was subsequently sulfonated in chlorosulfonic acid to produce sulfonated HPEK-g-MWCNT (SHPEK-g-MWCNT), which is dispersible well in water showing a zeta potential value of -57.8 mV. The SHPEK-g-MWCNT paper simply formed by filtration of aqueous dispersion has a sheet resistance as low as 63 Ω/sq. Its thin film shows a high electrocatalytic activity for oxygen reduction reaction (ORR). Thus, the newly produced water-dispersible MWCNT is a new class of high performance cathode material for ORR.

Carbon nanomaterials for advanced energy conversion and storage.

It is estimated that the world will need to double its energy supply by 2050. Nanotechnology has opened up new frontiers in materials science and engineering to meet this challenge by creating new materials, particularly carbon nanomaterials, for efficient energy conversion and storage. Comparing to conventional energy materials, carbon nanomaterials possess unique size-/surface-dependent (e.g., morphological, electrical, optical, and mechanical) properties useful for enhancing the energy-conversion and storage performances. During the past 25 years or so, therefore, considerable efforts have been made to utilize the unique properties of carbon nanomaterials, including fullerenes, carbon nanotubes, and graphene, as energy materials, and tremendous progress has been achieved in developing high-performance energy conversion (e.g., solar cells and fuel cells) and storage (e.g., supercapacitors and batteries) devices. This article reviews progress in the research and development of carbon nanomaterials during the past twenty years or so for advanced energy conversion and storage, along with some discussions on challenges and perspectives in this exciting field.

Polyaniline-grafted reduced graphene oxide for efficient electrochemical supercapacitors.

An alternative and effective route to prepare conducting polyaniline-grafted reduced graphene oxide (PANi-g-rGO) composite with highly enhanced properties is reported. In order to prepare PANi-g-rGO, amine-protected 4-aminophenol was initially grafted to graphite oxide (GO) via acyl chemistry where a concomitant partial reduction of GO occurred due to the refluxing and exposure of GO to thionyl chloride vapors and heating. Following the deprotection of amine groups, an in situ chemical oxidative grafting of aniline in the presence of an oxidizing agent was carried out to yield highly conducting PANi-g-rGO. Electron microscopic studies demonstrated that the resultant composite has fibrillar morphology with a room-temperature electrical conductivity as high as 8.66 S/cm and capacitance of 250 F/g with good cycling stability.

Multifunctional conjugated polymers with main-chain donors and side-chain acceptors for dye sensitized solar cells (DSSCs) and organic photovoltaic cells (OPVs).

A novel multifunctional conjugated polymer (RCP-1) composed of an electron-donating backbone (carbazole) and an electron-accepting side chain (cyanoacetic acid) connected through conjugated vinylene and terthiophene has been synthesized and tested as a photosensitizer in two major molecule-based solar cells, namely dye sensitized solar cells (DSSCs) and organic photovoltaic cells (OPVs). Promising initial results on overall power conversion efficiencies of 4.11% and 1.04% are obtained from the basic structure of DSSCs and OPVs based on RCP-1, respectively. The well-defined donor (D)-acceptor (A) structure of RCP-1 has made it possible, for the first time, to reach over 4% of power conversion efficiency in DSSCs with an organic polymer sensitizer and good operation stability.