Phosphonic Acid Groups Research Articles

Breathing effect in a Tetrapodal Lanthanide‐Phosphonate Organic Framework

The highly flexible organic linker hexamethylenediamine‐N,N,N’,N’‐tetrakis(methylphosphonic acid) (H8htp) was used in the preparation of a new 3D MOF formulated as [La2(SO4)2(H6htp)(H2O)4]∙2H2O (UAV‐15) by using hydrothermal synthesis. The flexibility of the organic linker posed a serious challenge in the preparation of crystalline materials: for this, the judicious selection of sulfuric acid to act as a mineralizing agent proved to be instrumental, acting in the retardation of the coordination of the phosphonic acid groups, as well as being an integral part the UAV‐15 by coordinating to the metal center. The material is a 3D network having channels filled with crystallization water molecules that can be easily removed by increasing of temperature (120ºC for 24h), leading to a single‐crystal‐to‐single‐crystal transformation originating [La2(SO4)2(H6htp)(H2O)3] (UAV‐15d). This transformation maintains the overall topology of UAV‐15 with only a small distortion of the framework. The reversibility of this transformation was studied, with the material reverting naturally to its original structure at ambient conditions for a period of 3 months or, in a faster way, when immersed in water at 120 ºC for 24h.

Ultra-High Adsorption Capacity of Calcium-Iron Layered Double Hydroxides for HEDP Removal through Phase Transition Processes.

Antiscalant disposal in reverse osmosis concentrate (ROC) treatment is a significant obstacle in desalination. This study investigated the adsorption performance of LDHs for removing 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP). CaFe-LDH presented a specific adsorption behavior and ultrahigh adsorption capacity for HEDP, with a maximum adsorption capacity of 335.7 mg P/g (1116.5 mg HEDP/g) at pH 7.0. X-ray diffraction (XRD) demonstrated that HEDP adsorption induced a structural transformation of CaFe-LDH from a layered configuration to a highly ordered structure, leading to a noticeable phase transition. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and Raman spectroscopy further confirmed that two distinct binding modes of HEDP, relating to chelation with Ca2+ and adsorption on Fe3+ simultaneously, are connected by phosphonic acid groups (-C-PO(OH)2), forming the CaFe-HEDP complex. X-ray fluorescence (XRF) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the CaFe-HEDP ternary complex exhibits a highly ordered arrangement in an oxygen-bridged framework. The construction of an oxygen-coordinated framework contributes to the incorporation of more HEDP into CaFe-LDH, leading to a well-aligned lattice in the new phase. These findings provide valuable insights into developing novel LDH-based adsorbents for removing phosphorus-containing antiscalants, establishing a sustainable approach to ROC management, and potential environmental risk reduction.

High-Efficiency Perovskite Solar Cells with Improved Interfacial Charge Extraction by Bridging Molecules.

The interface between the perovskite layer and electron transporting layer is a critical determinate for the performance and stability of perovskite solar cells (PSCs). The heterogeneity of the interface critically affects the carrier dynamics at the buried interface. To address this, a bridging molecule, (2-aminoethyl)phosphonic acid (AEP), is introduced for the modification of SnO2/perovskite buried interface in n-i-p structure PSCs. The phosphonic acid group strongly bonds to the SnO2 surface, effectively suppressing the surface carrier traps and leakage current, and uniforming the surface potential. Meanwhile, the amino group influences the growth of perovskite film, resulting in higher crystallinity, phase purity, and fewer defects. Furthermore, the bridging molecules facilitate the charge extraction at the interface, as indicated by the femtosecond transient reflection (fs-TR) spectroscopy, leading to champion power conversion efficiency (PCE) of 26.40% (certified 25.98%) for PSCs. Additionally, the strengthened interface enables improved operational durability of ≈1400 h for the unencapsulated PSCs under ISOS-L-1I protocol.

Role of self-assembled molecules’ anchoring groups for surface defect passivation and dipole modulation in inverted perovskite solar cells

Abstract Inverted perovskite solar cells have gained prominence in industrial advancement due to their easy fabrication, low hysteresis effects, and high stability. Despite these advantages, their efficiency is currently limited by excessive defects and poor carrier transport at the perovskite–electrode interface, particularly at the buried interface between the perovskite and transparent conductive oxide (TCO). Recent efforts in the perovskite community have focused on designing novel self-assembled molecules (SAMs) to improve the quality of the buried interface. However, a notable gap remains in understanding the regulation of atomic-scale interfacial properties of SAMs between the perovskite and TCO interfaces. This understanding is crucial, particularly in terms of identifying chemically active anchoring groups. In this study, we used the star SAM ([2-(9H-carbazol-9-yl)ethyl] phosphonic acid) as the base structure to investigate the defect passivation effects of eight common anchoring groups at the perovskite–TCO interface. Our findings indicate that the phosphonic and boric acid groups exhibit notable advantages. These groups fulfill three key criteria: they provide the greatest potential for defect passivation, exhibit stable adsorption with defects, and exert significant regulatory effects on interface dipoles. Ionized anchoring groups exhibit enhanced passivation capabilities for defect energy levels due to their superior Lewis base properties, which effectively neutralize local charges near defects. Among various defect types, iodine vacancies are the easiest to passivate, whereas iodine-substituted lead defects are the most challenging to passivate. Our study provides comprehensive theoretical insights and inspiration for the design of anchoring groups in SAMs, contributing to the ongoing development of more efficient inverted perovskite solar cells.

Multi-Substituted Phosphonated and Sulfonated Polymer Materials: Characterization and Blends with Basic Polymers

The growing demand for energy, limited resources, and climate warming call for alternative sustainable energy production. A promising candidate is the proton-exchange membrane fuel cell (PEMFC) using a proton conducting polymer as an electrolyte membrane. The most common proton-exchange membranes are based on sulfonated polymers, such as Nafion®. Since their proton conduction is driven by hydronium ions (H3O+) and hence require water, the operating temperature is limited to 100°C. Unlike in sulfonated polymer materials, the proton conduction in materials with phosphonic acid groups occurs via a hopping process and does not require water.1 This study introduces a highly substituted phosphonated and sulfonated polymer based on poly(pentafluorostyrene), which makes the material adaptable in anhydrous and hydrous operating conditions since the phosphonic acid and sulfonic acid units can conduct cooperatively. The phosphonic acid group is introduced via the nucleophilic aromatic substitution Michaelis-Arbuzov reaction. The Para-Fluoro-Thiol reaction was used to introduce sulfonic acid groups into the polymer backbone. In the past, both reaction steps were well investigated.2,3 The highly substituted polymer material was blended with a basic polymer to circumvent water solubility and investigated according to its proton conductivity, thermal stability, and mechanical properties.(1) Kumar, A. J. Mater. Chem. A 2020, 8 (43), 22632–22636. DOI: 10.1039/d0ta07732a.(2) Atanasov, V.; Oleynikov, A.; Xia, J.; Lyonnard, S.; Kerres, J. Journal of Power Sources 2017, 343, 364–372. DOI: 10.1016/j.jpowsour.2017.01.085.(3) Delaittre, G.; Barner, L. Polym. Chem. 2018, 9 (20), 2679–2684. DOI: 10.1039/c8py00287h.

Uptake and coordination behaviour of uranyl on functionalised silica

The safe decommissioning of nuclear reactors is a complex process, requiring a range of technological options for it to be done effectively. It has become more important in recent years, with the substantial number of reactors entering the decommissioning phase. This paper details the use of functionalised silica for the recovery of uranium from aqueous hydrochloric acid solutions, a potential agent for the treatment of steel reactor components during nuclear reactor decommissioning. Silica functionalised with either phosphonic acid, bistriazine, or bistriazinylbipyridine ligands was shown to extract uranium, with the commercially available phosphonic acid functionality being the most effective. Extractions of 100 % were observed at [H+] ≤ 0.24 M, further the phosphonic acid functionality also had the highest loading capacity. Increasing [H+] has a suppressive effect on uranyl recovery, which was more pronounced for the in-house synthesized silica, and was attributed to protonation of the extracting moiety. Extended x-ray absorption fine structure spectroscopy was also used to determine the uranium coordination environments on the functionalised silica, and gain insights into the extraction mechanism. The uranyl cation was bound by two phosphonic acid groups, two bis-triazine groups, and one bistriazinylbipyridine group, respectively on each respective extractant. Uranyl was found to be penta-coordinate in the equatorial plane for all systems, with oxygen and/or chloride always present in the first coordination sphere. Evaluation of the mechanism indicated that uranyl must be loading onto the phosphonic acid functionality via multiple mechanisms, to both the phosphonic acid and silica related surface groups, although preferential binding of uranyl to the phosphonic acid groups was observed.

Highly Efficient, Noble-Metal-Free, Fully Aqueous CO2 Photoreduction Sensitized by a Robust Organic Dye.

The development of efficient, selective, and durable CO2 photoreduction systems presents a long-standing challenge in full aqueous solutions owing to the presence of scarce CO2 and the fierce competition against H2 evolution, which is even more challenging when noble metals are not utilized. Herein, we present the facile decorations of four phosphonic acid groups on a donor-acceptor-type organic dye to obtain a water-soluble photosensitizer (4P-DPAIPN), which succeeds the excellent photophysical and photoredox properties of its prototype, exhibiting long-lived delayed fluorescence (>10 μs) in aqueous solutions. Combining 4P-DPAIPN with a cationic cobalt porphyrin catalyst has accomplished record-high apparent quantum yields of 9.4-17.4% at 450 nm for CO2-to-CO photoconversion among the precedented systems (maximum 13%) in fully aqueous solutions. Remarkable selectivity of 82-93% and turnover number of 2700 for CO production can also be achieved with this noble-metal-free system, outperforming a benchmarking ruthenium photosensitizer and a commercial organic dye under parallel conditions. Such high performances of 4P-DPAIPN can be well maintained under real sunlight. More impressively, no significant decomposition of 4P-DPAIPN was detected during the long-term photocatalysis. Eventually, the photoinduced electron transfer pathways were proposed.

Phosphonate Diacid Molecule Induced Crystallization Manipulation and Defect Passivation for High‐Performance Inverted MA‐Free Perovskite Solar Cells

AbstractInverted perovskite solar cells (PSCs) comprising formamidinium‐cesium (FA‐Cs) lead triiodide have garnered considerable attention due to their impressive efficiency and remarkable stability. Nevertheless, synthesizing high‐quality FA‐Cs alloyed perovskite films presents challenges, primarily attributable to the intricate interphase process involved and the absence of methylammonium (MA+) and mixed halogens. Here, the additive 3‐phosphonopropanoic acid (3‐PPA) is introduced, with bifunctional phosphonic acid groups, into the perovskite precursor to modulate the crystal growth and provide passivation at grain boundaries. In situ characterization reveals that the 3‐PPA can form a “rapid nucleation, slow growth” mechanism, resulting in perovskite films with enlarged grains and enhanced crystallinity. In addition, 3‐PPA serves to passivate grain boundary defects and release residual strain by forming molecular bridging, leading to the passivated films achieving a fluorescence lifetime of 5.79 microseconds with a favorable n‐type contact interface. As a result, the resulting devices incorporating 3‐PPA achieve a champion power conversion efficiency (PCE) of 24.05% and an ultra‐high fill factor (FF) of 84.22%. More importantly, the optimized devices exhibit satisfactory stability under various testing conditions. The findings underscore the pivotal role of multifunctional additives in crystallization control and defect passivation for high‐performance MA‐free and pure iodine PSCs.

Design and characterization of phosphonic acid-functionalized grafted sepiolite nanohybrids and their adsorption studies for removal of copper ions from aqueous solution.

In this study, we synthesized novel, economically efficient phosphonic acid-functionalized grafted sepiolite nanohybrids for selective elimination of copper ions from water. These nanohybrids were prepared by graft polymerization of glycidyl methacrylate onto sepiolite. We utilized free radical graft polymerization to graft glycidyl methacrylate (GMA) onto silanized sepiolite. The nanohybrids obtained exhibited a grafting percentage of 479% at 0.3 g of KPS initiator, 15% GMA monomer, and after 4 h of reaction. In pursuit of selectively removing metal ions from water, the nanohybrid with the highest grafting (PGE3) was chemically treated with phosphoric acid to introduce phosphonic acid groups on it. FTIR, XRD, SEM, CHO analysis, BET, and TGA analysis were utilized to characterize the developed nanohybrids. Batch adsorption studies were carried out using AAS process, examining the impact of pH, adsorbent weight, contact time, adsorbate concentration, and temperature on the adsorption process. Due to the selectivity of phosphonic acid groups towards copper ions, phosphonic acid-functionalized grafted sepiolite nanohybrid (PGE3-P) was used for copper ions removal from its aqueous solution. The maximum adsorption capacity of PGE3-P adsorbents was 134.5 mg/g for copper ions. The data from kinetic studies suggests that the adsorption process of copper ions followed a pseudosecond-order model. Furthermore, Langmuir isotherm proved to be a more fitting model in equilibrium isothermal investigations. The thermodynamic analysis of the data indicates that the adsorption of copper ions by PGE3-P is an endothermic and spontaneous process. The development of this phosphonic acid-functionalized grafted sepiolite nanohybrid adsorbent is a new contribution into the field of adsorption. The developed material can be utilized as selective adsorbent for elimination of other heavy metals from water.

Strong-bonding hole-transport layers reduce ultraviolet degradation of perovskite solar cells

The light-emitting diodes (LEDs) used in indoor testing of perovskite solar cells do not expose them to the levels of ultraviolet (UV) radiation that they would receive in actual outdoor use. We report degradation mechanisms of p-i-n–structured perovskite solar cells under unfiltered sunlight and with LEDs. Weak chemical bonding between perovskites and polymer hole-transporting materials (HTMs) and transparent conducting oxides (TCOs) dominate the accelerated A-site cation migration, rather than direct degradation of HTMs. An aromatic phosphonic acid, [2-(9-ethyl-9H-carbazol-3-yl)ethyl]phosphonic acid (EtCz3EPA), enhanced bonding at the perovskite/HTM/TCO region with a phosphonic acid group bonded to TCOs and a nitrogen group interacting with lead in perovskites. A hybrid HTM of EtCz3EPA with strong hole-extraction polymers retained high efficiency and improved the UV stability of perovskite devices, and a champion perovskite minimodule—independently measured by the Perovskite PV Accelerator for Commercializing Technologies (PACT) center—retained operational efficiency of >16% after 29 weeks of outdoor testing.

Effect of organic phosphonate types on performance of alkali-activated slag-based materials and its mechanism

The strong early hydration reaction and short setting time of alkali-activated slag composites limit its practical engineering application. Compared with traditional chemical admixture, organic phosphates show higher efficiency in delaying the hydration rate of alkali-activated slag system. However, there is limited research on the performance of alkali-activated materials modified by different organic phosphonate type, and their modification mechanism is also unclear. In this study, three typical organic phosphonates, hydroxyethylidene diphosphonic acid Tetrasodium (HEDP-4Na), aminotris (methylene phosphonic acid) tetrasodium (ATMP-4Na), and diethylenetriamine penta (methylene phosphonic acid) pentasodium (DTPMP-5Na), were selected to clarify the effect of organic phosphonate type on the properties of alkali-activated slag materials (AASM) and its mechanism under different dosage and alkali content. The results indicate that DTPMP-5Na has the most significant effect on the improvement of fresh properties of AASM, compared to other two types of organic phosphonates. Using 0.3 % DTPMP-5Na can delay the initial and final setting time of AASM by 240 % and 190 % respectively, increase the slump flow by 20 %, and reduce yield stress and plastic viscosity by 57 % and 65 % respectively. This was because DTPMP-5Na has the largest number of monomolecular phosphonic acid groups, which can chelate Ca2+ in AASM, form stable complex and cover the surface of slag particles to prevent further hydration reaction. The phosphonate reduced the hydration rate and increased the surface negative potential of slag particles. The use of phosphonates and the increase in alkali content can significantly enhance the mechanical properties of AASM. Using 0.3 % of ATMP-4Na increased the 28-day compressive and flexural strengths of AASM made with 5 % alkali content by 155 % and 53 %, respectively, compared to the reference AASM with 3 % alkali content. Additionally, the 28-day compressive and flexural strengths of reference at 7 % alkali content increased by 115 % and 12 %, respectively, compared to that at 3 % alkali content. This improvement was mainly attributed to the consumption of organic phosphonates at the early stage, which provides more activation channels for slag later, resulting in a denser structure and improved pore structure of AASM, thus enhancing its long-term mechanical properties. However, with the increase of alkali content, the effect of organic phosphonates in strengthening fresh and hardened properties of AASM decreased. The use of 0.3 % HEDP-4Na increased 28-day compressive and flexural strengths of AASM with 3 % alkali contents increased by 25 % and 27 %, respectively, compared to the reference AASM. Such improvement was limited to 4 % and 19 % for AASM made with 5 % alkali content. This can be attributed to the significant promotion of OH− concentration in the system, increasing the yield of hydration products at early age on the surface of slag, and reduced activation channels for slag over the long term. In summary, the use of ATMP-4Na is recommended in AASM, as it can significantly improve the fresh properties of AASM and provide excellent mechanical properties.

Application of organic phosphonic acid dispersant in the separation and flotation of chalcopyrite and serpentine

The floatation of target minerals is often severely deteriorated in highly muddy mineral flotation systems. In this study, it was shown that the chalcopyrite recovery was significantly decreased due to the slime-coating of the serpentine fines. To enhance the floatability of chalcopyrite in the presence of serpentines, two phosphonic acids of 1-Hydroxyethylidene-1,1-diphosphonic acid (HEDP) and ethylenediamine tetramethylene phosphonic acid (EDTMP) were applied as dispersants in the floatation process. The micro-flotation tests indicated that HEDP and EDTMP could well eliminate the adverse effect of coated serpentine on the floatability of chalcopyrite. Adsorption tests and X-ray photoelectron spectra (XPS) analysis demonstrated that HEDP and EDTMP could selectively adsorb on the serpentine surface due to the chelation of phosphonic acid groups with the magnesium atoms on the serpentine surface, which was confirmed by the flight secondary ion mass spectrometry (TOF-SIMS) characterization. The zeta potential measurements showed that the adsorption of dispersants on serpentine changed the surface charges from positive to negative, while the zeta potential of chalcopyrite became more negative due to the dissolution of copper and iron cations from the chalcopyrite surface. Therefore, the electrostatic repulsion effectively prevented the slime-coating of serpentine on the chalcopyrite surface, which was also supported by the atomic force microscope (AFM) force measurements. As a result, the use of dispersants eliminated the adverse effects of serpentinite and greatly improved the floatability of chalcopyrite. The findings in this work indicate that the phosphonic acids of HEDP and EDTMP might find their application as effective dispersants to improve the floatability of target minerals in highly muddy mineral flotation systems.

Highly selective removal of thorium from acidic solutions achieved on phosphonic acid functionalized core–shell magnetic nanocomposite: Understanding adsorption and binding mechanisms

Thorium has received widespread attention as potential nuclear fuel alternative for the next-generation thorium-based molten salt reactors. With the growth of nuclear energy, it is needful to exploit magnetic nanomaterials to remove thorium from aqueous solutions, owing to their superparamagnetism and large specific surface energy. Nevertheless, most of magnetic nanomaterials often suffered from low thorium selectivity and poor structural ability in acidic solutions. Herein, a novel core–shell magnetic nanocomposite Fe3O4@SiO2/P (AA-MMA-VPA) possessing phosphonic acid was developed by a controlled radical polymerization of vinylphosphonic acid (VPA) in the presence of Fe3O4 encapsulated by SiO2 (Fe3O4@SiO2). Due to the presence of the high content of phosphonic acid groups and the absence of any universal groups, Fe3O4@SiO2/P (AA-MMA-VPA) displayed exceptional selectivity for thorium in the presence of 11 co-existing cations. The separation factor STh/M value for Fe3O4@SiO2/P(AA-MMA-VPA) concerning all other competing cations surpassed 74.4, and the largest value for STh/M even amounted to 343.5. Further, Fe3O4@SiO2/P (AA-MMA-VPA) possessed a maximum adsorption capacity (qmax) of 485.4 mg g−1 at pH of 3.0, higher than that of other magnetic sorbents. By reason of its core–shell structure, the sorbent possessed an outstanding structure stability even after immersed into HNO3 solution at pH of 0.5 for 72 h. The sorbent could as well be magnetically recouped, and recycled at least six times without evident diminution in sorption amount. The sterling removal performance of the sorbent was assigned to the interaction of thorium with phosphonic acid, corroborated by FT-IR, XPS and DFT method. Thus, this study affords a new viewpoint for exploiting magnetic nanomaterials with sterling acidic resistance for the strongly selective entrapment of thorium from acidic media.

Proton exchange membranes with functionalized sulfonimide and phosphonic acid groups for next-generation fuel cells operating at 120 °C

Proton exchange membrane fuel cells (PEMFCs) face a significant challenge when operating in high-temperature and low-humidity environments, the hydrocarbon-based polymers that are sulfonated or phosphonated can’t meet the demand for achieving high performance. Modifying perfluorosulfonyl fluoride (PFSF) through meticulous design of side-chain chemical structures and introducing functionalized sulfonimide and phosphonic acid groups. Membranes derived from a perfluorocarbon backbone and polyacid side chain structures exhibit distinct microphase separation. The sulfonimide group exhibits hyper-acidic properties, whereas the phosphonic acid group functions as proton acceptor and donor. These two groups work synergistically to establish a distinct proton transport channel. The robust adsorption between acidic functional groups and water molecules enhances the diffusion of water molecules, resulting in an increase in proton conductivity. Moreover, Density Functional Theory (DFT) calculations reveal that the phosphonic acid group of the side chain has difficulty forming anhydrides. The prepared perfluorosulfonimide-phosphonic acid (PFSNPA) proton exchange membrane demonstrates an impressive conductivity of 263 mS·cm−1 at 120 °C. In H2/Air fuel cell tests, PFSNPA achieves an outstanding output power of 1076.1 mW·cm−2 at 120 °C and 40 % RH. This study introduces a new approach for designing and fabricating proton exchange membrane materials for high-temperature fuel cells.

Enhancing Efficiency of Large-Area Wide-Bandgap Perovskite Solar Modules with Spontaneously Formed Self-Assembled Monolayer Interfaces.

Wide-bandgap (WBG) perovskites play a crucial role in perovskite-based tandem cells. Despite recent advances using self-assembled monolayers (SAMs) to facilitate efficiency breakthroughs, achieving precise control over the deposition of such ultrathin layers remains a significant challenge for large-scale fabrication of WBG perovskite and, consequently, for the tandem modules. To address these challenges, we propose a facile method that integrates MeO-2PACz and Me-4PACz in optimal proportions (Mixed SAMs) into the perovskite precursor solution, enabling the simultaneous codeposition of WBG perovskite and SAMs. This technique promotes the spontaneous formation of charge-selective contacts while reducing defect densities by coordinating phosphonic acid groups with the unbonded Pb2+ ions at the bottom interface. The resulting WBG perovskite solar cells (PSCs) demonstrated a power conversion efficiency of 19.31% for small-area devices (0.0585 cm2) and 17.63% for large-area modules (19.34 cm2), highlighting the potential of this codeposition strategy for fabricating high-performance, large-area WBG PSCs with enhanced reproducibility. These findings offer valuable insights for advancing WBG PSCs and the scalable fabrication of modules.

Formamidinium Lead Iodide-Based Inverted Perovskite Solar Cells with Efficiency over 25 % Enabled by An Amphiphilic Molecular Hole-Transporter.

Formamidinium lead iodide (FAPbI3) represents an optimal absorber material in perovskite solar cells (PSCs), while the application of FAPbI3 in inverted-structured PSCs has yet to be successful, mainly owing to its inferior film-forming on hydrophobic or defective hole-transporting substrates. Herein, we report a substantial improvement of FAPbI3-based inverted PSCs, which is realized by a multifunctional amphiphilic molecular hole-transporter, (2-(4-(10H-phenothiazin-10-yl)phenyl)-1-cyanovinyl)phosphonic acid (PTZ-CPA). The phenothiazine (PTZ) based PTZ-CPA, carrying a cyanovinyl phosphonic acid (CPA) group, forms a superwetting hole-selective underlayer that enables facile deposition of high-quality FAPbI3 thin films. Compared to a previously established carbazole-based hole-selective material (2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl)phosphonic acid (MeO-2PACz), the crystallinity of FAPbI3 is enhanced and the electronic defects are passivated by the PTZ-CPA more effectively, resulting in remarkable increases in photoluminescence quantum yield (four-fold) and Shockley-Read-Hall lifetime (eight-fold). Moreover, the PTZ-CPA shows a larger molecular dipole moment and improved energy level alignment with FAPbI3, benefiting the interfacial hole-collection. Consequently, FAPbI3-based inverted PSCs achieve an unprecedented efficiency of 25.35 % under simulated air mass 1.5 (AM1.5) sunlight. The PTZ-CPA based device shows commendable long-term stability, maintaining over 90 % of its initial efficiency after continuous operation at 40 °C for 2000 hours.

Formamidinium Lead Iodide‐Based Inverted Perovskite Solar Cells with Efficiency over 25 % Enabled by An Amphiphilic Molecular Hole‐Transporter

AbstractFormamidinium lead iodide (FAPbI3) represents an optimal absorber material in perovskite solar cells (PSCs), while the application of FAPbI3 in inverted‐structured PSCs has yet to be successful, mainly owing to its inferior film‐forming on hydrophobic or defective hole‐transporting substrates. Herein, we report a substantial improvement of FAPbI3‐based inverted PSCs, which is realized by a multifunctional amphiphilic molecular hole‐transporter, (2‐(4‐(10H‐phenothiazin‐10‐yl)phenyl)‐1‐cyanovinyl)phosphonic acid (PTZ−CPA). The phenothiazine (PTZ) based PTZ−CPA, carrying a cyanovinyl phosphonic acid (CPA) group, forms a superwetting hole‐selective underlayer that enables facile deposition of high‐quality FAPbI3 thin films. Compared to a previously established carbazole‐based hole‐selective material (2‐(3,6‐dimethoxy‐9H‐carbazol‐9‐yl)ethyl)phosphonic acid (MeO−2PACz), the crystallinity of FAPbI3 is enhanced and the electronic defects are passivated by the PTZ−CPA more effectively, resulting in remarkable increases in photoluminescence quantum yield (four‐fold) and Shockley‐Read‐Hall lifetime (eight‐fold). Moreover, the PTZ−CPA shows a larger molecular dipole moment and improved energy level alignment with FAPbI3, benefiting the interfacial hole‐collection. Consequently, FAPbI3‐based inverted PSCs achieve an unprecedented efficiency of 25.35 % under simulated air mass 1.5 (AM1.5) sunlight. The PTZ−CPA based device shows commendable long‐term stability, maintaining over 90 % of its initial efficiency after continuous operation at 40 °C for 2000 hours.

Double-side 2D/3D heterojunctions for inverted perovskite solar cells.

Defects at the top and bottom interfaces of three-dimensional (3D) perovskite photoabsorbers diminish the performance and operational stability of perovskite solar cells owing to charge recombination, ion migration and electric-field inhomogeneities1-5. Here we demonstrate that long alkyl amine ligands can generate near-phase-pure 2D perovskites at the top and bottom 3D perovskite interfaces and effectively resolve these issues. At the rear-contact side, we find that the alkyl amine ligand strengthens the interactions with the substrate through acid-base reactions with the phosphonic acid group from the organic hole-transporting self-assembled monolayer molecule, thus regulating the 2D perovskite formation. With this, inverted perovskite solar cells with double-side 2D/3D heterojunctions achieved a power conversion efficiency of 25.6% (certified 25.0%), retaining 95% of their initial power conversion efficiency after 1,000 h of 1-sun illumination at 85 °C in air.

Effect of ionic groups on the morphology and transport properties in a novel perfluorinated ionomer containing sulfonic and phosphonic acid groups: a molecular dynamics study.

Combining the phosphonic acid group with the sulfonic acid group in PEMs has been shown to be an effective strategy for improving the fuel cell performance. However, the interplay of two different ionic groups and the resulting effect on the membrane properties have not been fully elucidated. Here, we used classical molecular dynamics simulation to investigate the morphologies, transport properties and effects of ionic groups in a novel perfluorinated PEM containing two ionic groups (PFSA-PFPA) in comparison to the corresponding homopolymers. Phase separations between hydrophilic and hydrophobic domains are confirmed in these PEMs and result from the evolution of water clusters formed around the ionic groups. The combination of both ionic groups brings a complicated morphological feature in PFSA-PFPA, with near-cylindrical aqueous domains of large length scales interconnected by tortuous domains of small sizes. And we found that the self-diffusion coefficients of water molecules are strongly related to morphologies, with the water transport in PFSA-PFPA lying between two analogous homopolymers. At the molecular level, we found that the sulfonic and phosphonic acid groups have distinct effects on the coordination behaviors and the dynamics of water molecules and hydronium ions. Strong electrostatic interactions lead to compact coordination structures and sluggish dynamics of hydronium ions around phosphonic acid groups, which determine the morphological evolution and transport properties in PFSA-PFPA. Our study affords insights into the relationship between molecular characteristics and transport properties bridged by phase-separated morphologies in a novel PEM containing both sulfonic acid and phosphonic acid groups, which deepens the understanding of the interplay between two ionic groups and may inspire the rational design of high-performance PEMs.

Adsorption mechanism of Ca2+, Mg2+, Fe3+, and Al3+ ions in phosphoric acid-nitric acid solution on 001 × 7 and S957 resins.

Selective removal of Ca2+ and Mg2+ ions using the 001 × 7 resin and Fe3+ and Al3+ ions using the S957 resin is able to achieve the deep purification of the phosphoric acid-nitric acid solution, but the adsorption behaviors of Fe3+ and Al3+ ions are seriously suppressed by phosphoric acid. In order to understand the interaction mechanism of separation processes and the influence of phosphoric acid, we first studied the bonding form of Ca2+, Mg2+, Fe3+, and Al3+ ions on 001 × 7 and S957 resins using FT-IR and XPS techniques; subsequently, quantum chemistry computation was carried out to further explore the bonding mechanism between the functional groups on resins and metal ions. FT-IR and XPS results reveal that for the adsorption process on the 001 × 7 resin, hydroxyls from sulfonic acid groups combine with Ca2+ and Mg2+ ions. Whereas Fe3+ and Al3+ ions are adsorbed on the S957 resin through an exchange reaction with hydroxyls on the phosphonic acid group but not on the sulfonic acid group. Quantum chemistry computation results reveal that the phosphonic acid group has a larger binding energy with Fe3+ and Al3+ ions. Thus, the S957 resin still presents great adsorption performance for Fe3+ and Al3+ ions despite the influence of dihydrogen phosphate ions in the phosphoric acid-nitric acid solution.