Phosphonic Acid Research Articles

A new type of geopolymer with good thickening and strength properties using Na2C2O4+Ca(OH)2 as the activator

Geopolymer materials exhibit excellent resistance to CO2 corrosion and low carbon emission characteristics, which are very suitable for cementing in CCUS/CCS wells. However, it is difficult to control its thickening time, which limits its popularization and application. The substitution of NaOH with Na2C2O4 and Ca(OH)2 to activate geopolymers was tried to investigate their influence on thickening time and strength of the geopolymer. The precursors used were fly ash sinker beads and slag (the mass ratio is 8:2). Results indicate that at 75°C, the thickening time of geopolymers activated by NaOH is difficult to extend with retarders, whereas those activated by Na2C2O4+Ca(OH)2 can be effectively extended using D-Gluconic acid sodium (D-GA) or ethylene diamine tetra methylene phosphonic acid sodium (EDTMPS). Additionally, geopolymers activated by Na2C2O4+Ca(OH)2 exhibit good strength properties, with compressive strengths of 25.3MPa for 24h and 25.6MPa for 48h at 75°C. Furthermore, geopolymer curing next to water-bearing rocks showed that geopolymer can also achieve excellent solidification when surrounded by water-bearing rocks, which is favorable for its application under the well cementing construction.

The Effect of Ethylene Diamine Tetra(Methylene Phosphonic Acid) Sodium on the Hydration of Tricalcium Silicate at 80 °C

The Effect of Ethylene Diamine Tetra(Methylene Phosphonic Acid) Sodium on the Hydration of Tricalcium Silicate at 80 °C

Multidentate Chelating Ligands Enable High-Performance Zinc-Bromine Flow Batteries.

Zinc bromine flow battery (ZBFB) is a promising battery technology for stationary energy storage. However, challenges specific to zinc anodes must be resolved, including zinc dendritic growth, hydrogen evolution reaction, and the occurrence of "dead zinc". Traditional additives suppress side reactions and zinc dendrite formation by altering the solvation structure of Zn2+ and adsorbing onto the zinc surface through only a limited number of zincophilic sites, resulting in weak adsorption on zinc metal and potential inability to simultaneously optimize the solvation structure of zinc ions. Obviously, increasing the number of potential zincophilic sites in the additive can significantly enhance the interaction with zinc. Herein, we propose a strong chelate, ethylenediamine tetramethylene phosphonic acid (EDTMPA) as the additive, which boasts six potent zincophilic sites, not only promotes the formation of the water-deficient inner Helmholtz plane but also plays a crucial role in restructuring the solvation environment of Zn2+. As a result, the zinc symmetric flow battery with EDTMPA exhibited exceptional coulombic efficiency of 99.4% over 800 cycles, surpassing the previous studies by a significant margin. Furthermore, the assembled ZBFB has showcased a dendrite-free and enduring cycling over 400 cycles at 80 mA cm-2.

Multidentate Chelating Ligands Enable High‐Performance Zinc‐Bromine Flow Batteries

Zinc bromine flow battery (ZBFB) is a promising battery technology for stationary energy storage. However, challenges specific to zinc anodes must be resolved, including zinc dendritic growth, hydrogen evolution reaction, and the occurrence of "dead zinc". Traditional additives suppress side reactions and zinc dendrite formation by altering the solvation structure of Zn2+ and adsorbing onto the zinc surface through only a limited number of zincophilic sites, resulting in weak adsorption on zinc metal and potential inability to simultaneously optimize the solvation structure of zinc ions. Obviously, increasing the number of potential zincophilic sites in the additive can significantly enhance the interaction with zinc. Herein, we propose a strong chelate, ethylenediamine tetramethylene phosphonic acid (EDTMPA) as the additive, which boasts six potent zincophilic sites, not only promotes the formation of the water‐deficient inner Helmholtz plane but also plays a crucial role in restructuring the solvation environment of Zn2+. As a result, the zinc symmetric flow battery with EDTMPA exhibited exceptional coulombic efficiency of 99.4% over 800 cycles, surpassing the previous studies by a significant margin. Furthermore, the assembled ZBFB has showcased a dendrite‐free and enduring cycling over 400 cycles at 80 mA cm−2.

Perovskite/Silicon Tandem Solar Cells Above 30% Conversion Efficiency on Submicron-Sized Textured Czochralski-Silicon Bottom Cells with Improved Hole-Transport Layers.

In perovskite/silicon tandem solar cells, the utilization of silicon heterojunction (SHJ) solar cells as bottom cells is one of the most promising concepts. Here, we present optimization strategies for the top cell processing and their integration into SHJ bottom cells based on industrial Czochralski (Cz)-Si wafers of 140 μm thickness. We show that combining the self-assembled monolayer [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (Me-4PACz) with an additional phosphonic acid (PA) with different functional groups, can improve film formation when used as a hole transport layer improving wettability, minimizing shunt fraction and reducing nonradiative losses at the buried interface. Transient surface photovoltage and transient photoluminescence measurements confirm that the combined Me-4PACz/PA layer has similar charge transport properties to Me-4PACz alone. Moreover, this work demonstrates the potential for thin, double-side submicron-sized textured industry-relevant silicon bottom cells yielding a high accumulated short-circuit current density of 40.2 mA/cm2 and reaching a stabilized power conversion efficiency of >30%. This work paves the way toward industry-compatible, highly efficient tandem cells based on a production-compatible SHJ bottom cell.

Configurational Isomerization‐Induced Orientation Switching: Non‐Fused Ring Dipodal Phosphonic Acids as Hole‐Extraction Layers for Efficient Organic Solar Cells

AbstractPhosphonic acid (PA) self‐assembled molecules have recently emerged as efficient hole‐extraction layers (HELs) for organic solar cells (OSCs). However, the structural effects of PAs on their self‐assembly behaviors on indium tin oxide (ITO) and thus photovoltaic performance remain obscure. Herein, we present a novel class of PAs, namely “non‐fused ring dipodal phosphonic acids” (NFR‐DPAs), featuring simple and malleable non‐fused ring backbones and dipodal phosphonic acid anchoring groups. The efficacy of configurational isomerism in modulating the photoelectronic properties and switching molecular orientation of PAs atop electrodes results in distinct substrate surface energy and electronic characteristics. The NFR‐DPA with linear (C2h symmetry) and brominated backbone exhibits favorable face‐on orientation and enhanced work function modification capability compared to its angular (C2v symmetry) and non‐brominated counterparts. This makes it versatile HELs in mitigating interfacial resistance for energy barrier‐free hole collection, and affording optimal active layer morphology, which results in an impressive efficiency of 19.11 % with a low voltage loss of 0.52 V for binary OSC devices and an excellent efficiency of 19.66 % for ternary OSC devices. This study presents a new dimension to design PA‐based HELs for high‐performance OSCs.

Multiscale insights into polyamide membrane fouling during reverse osmosis of rare earth wastewater

The rare earth elements (REEs) industrial wastewater is characterized by high ammonium nitrogen and low-strength organic compounds. Reverse osmosis (RO) process is effective for the REEs wastewater treatment. However, membrane fouling deteriorated the RO process. In this work, the fouling mechanism during RO process of REEs wastewater was elucidated via multiscale methods. A series of bench-scale fouling tests with simulated REEs wastewater containing high NH4+–N and different concentrations of 2-ethylhexyl phosphonic acid mono-(2-ethylhexyl) ester (P507) were performed with a commercial RO membrane to evaluate the fouling extent of the RO process. A critical P507 concentration (0.25 mg L−1) was observed where the fouling pattern changed qualitatively. When the P507 concentration was lower than 0.25 mg L−1, the relative flux increased and the membrane surface became more hydrophilic. When P507 reached this critical point, severe fouling occurred accompanied with a more hydrophobic membrane surface. Multiscale simulations [i.e., molecular dynamics (MD) and dissipative particle dynamics (DPD)] revealed that the fouling layer network varied with P507 concentration. This work provides in-depth insights into membrane fouling mechanism in the REEs wastewater, and has enlightening significance for fouling control strategies and the innovation of anti-fouling membrane materials.

Ultrathin Self-Assembled Monolayer for Effective Silicon Solar Cell Passivation.

Passivation technology is crucial for reducing interface defects and impacting the performance of crystalline silicon (c-Si) solar cells. Concurrently, maintaining a thin passivation layer is essential for ensuring efficient carrier transport. With an ultrathin passivated contact structure, both Silicon Heterojunction (SHJ) cells and Tunnel Oxide Passivated Contact (TOPCon) solar cells achieve an efficiency surpassing 26%. To reduce production costs and simplify solar cell manufacturing processes, the rapid development of organic material passivation technology has emerged. However, its widespread industrial production is hindered by environmental safety concerns, such as strong acid corrosion and biological and ecological safety issues. Here, we discovered a low-cost self-assembled monolayer (SAM) hole-selective transport material known as 2PACz ([2-(9H-carbazol-9-yl) ethyl] phosphonic acid) with phosphate groups to form c-Si solar cells for the first time. The ultrathin film of 2PACz with phosphate groups can establish strong and stable P-O-Si bonds on the silicon surface. Meanwhile, like 2PACz, a uniform ultrathin film with a carbazole function group can offer electron-localizing and thus hole-selective properties, which provides ideas for studying dopant-free silicon solar cells. As a result of such interfacial passivation engineering, it plays an important role in repairing porous structures, such as pyramid-textured silicon surfaces, and cutting losses during the commercialization of c-Si solar cells. Crucially, this advancement offers insights for the development of new high-efficiency ultrathin film passivation methods in the postsilicon era.

A Diphosphonic Acid-Based Interlayer for Highly Efficient and Stable Inverted Perovskite Solar Cells.

We investigate an interlayer of 6,6'-bis(4-(bis(4-methoxyphenyl)amino)phenyl)-[1,1'-binaphthalene]-(2,2'-diyl)bis(oxy)bis(propane-3,1-diyl)bis(phosphonic acid) (BINOL-PA) with undoped poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) coverage. The incorporation of the 1,10-bi-2-naphthol central core enhances π-π stacking and reduces charge recombination at the interface. Compared to PTAA alone (0.95 eV), BINOL-PA/PTAA exhibits a shorter distance from the Fermi energy (EF) to the valence-band maximum (VBM) (0.36 eV). Two phosphoric acid units in BINOL-PA fine-tune the molecular dipoles. Theoretical calculations reveal electrostatic surface potential differences between BINOL-PA and PTAA in their backbone structure. Open-circuit voltage decay (OCVD) and electrochemical impedance spectroscopy (EIS) results suggest suppressed interface recombination. The photovoltaic conversion efficiency (PCE), short-circuit current density (JSC), open-circuit voltage (VOC), and fill factor (FF) for the BINOL-PA/PTAA device are measured as 21.02%, 22.67 mA cm-2, 1.12 V, and 82.8%, respectively, all higher than those achieved by the PTAA device with a PCE of 18%. BINOL-PA/PTAA significantly elevates VOC and FF values compared with dopant-free PTAA alone. The champion device retains over 89% of its initial PCE after being exposed to an ambient environment without encapsulation for more than 30 days. The thermal aging test conducted under a nitrogen atmosphere demonstrates that the efficiency retention rate for BINOL-PA/PTAA displays 60% of its initial efficiency after 1500 h.

Evaluation of the excellent adsorption performance for lead ions of (sodium alginate/ waste para-aramid)-based polymer composite functionalized by ethylene diamine tetra (methylene phosphonic acid)

Evaluation of the excellent adsorption performance for lead ions of (sodium alginate/ waste para-aramid)-based polymer composite functionalized by ethylene diamine tetra (methylene phosphonic acid)

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.

Efficient wide-bandgap perovskite photovoltaics with homogeneous halogen-phase distribution

Wide-bandgap (WBG) perovskite solar cells (PSCs) are employed as top cells of tandem cells to break through the theoretical limits of single-junction photovoltaic devices. However, WBG PSCs exhibit severe open-circuit voltage (Voc) loss with increasing bromine content. Herein, inhomogeneous halogen-phase distribution is pointed out to be the reason, which hinders efficient extraction of carriers. We thus propose to form homogeneous halogen-phase distribution to address the issue. With the help of density functional theory, we construct a double-layer structure (D-2P) based on 2-(9H-Carbazol-9-yl)ethyl]phosphonic acid molecules to provide nucleation sites for perovskite crystallization. Homogeneous perovskite phase is achieved through bottom-up templated crystallization of halogen component. The efficient carrier extraction reduces the Shockley-Read-Hall recombination, resulting in a high Voc of 1.32 V. As a result, D-2P-treated device (1.75 eV) achieves a record power conversion efficiency of 20.80% (certified 20.70%), which is the highest value reported for WBG (more than 1.74 eV) PSCs.

Two-dimensional Ruddlesden-Popper perovskite solar cells with an efficiency exceeding 19 % by inserting a self-assembled monolayer

Two-dimensional Ruddlesden-Popper (2DRP) phase perovskites have excellent long-term environmental and structure stability. However, the efficiency of 2DRP perovskite solar cells (PSCs) still lags seriously behind 3D counterparts due to the large exciton binding energy between the large-volume organic spacer and the inorganic plate compared to their 3D analogs. Here, a thin layer of self-assembled monolayer material (2-(3,6-dibromo-9H-carbazol-9-yl)ethyl)phosphonic acid (2PACz-Br) is employed between poly (3,4-ethylene dioxythiophene): poly(styrene sulfonate) (PEDOT: PSS) and β-guanidinopropanoic acid (β-GUA)-based perovskite film (β-GUA)2(FA)4Pb5I16 for efficient and stable 2DRP-based PSCs. The 2PACz-Br-based 2DRP perovskite films show superior crystallinity and quality compared with the control perovskite films. The defect density in 2PACz-Br-based perovskite films is reduced, and the non-radiative recombination is further suppressed. The experimental results show that introducing 2PACz-Br can effectively promote the matched energy levels between the perovskite thin film and the charge-carrier transport layer. Benefiting from the conducive collection and transmission of charge carriers, (β-GUA)2(FA)4Pb5I16 (n = 5)-based PSCs can realize an outstanding power conversion efficiency of 19.13 %, much higher than that of devices without 2PACz-Br modification (17.70 %). Moreover, 2PACz-Br-based 2DRP PSCs show better stability than the control devices. Our work paves the way to efficient and stable 2DRP-based PSCs by inserting a multifunctional self-assembled monolayer.

Organic Salt Buffer Layer Enables High‐Performance NiOx‐Based Inverted Perovskite Solar Cells

The merits of a low‐cost fabrication process, suitable band structure, excellent wettability to perovskite precursor, and outstanding stability ensure NiOx as a hole transport material with beneficial characteristics to construct high‐performance perovskite solar cells (PSCs). However, direct contact between perovskite and NiOx causes delamination and chemical instability and thus results in poor carrier transport and short device lifespan. Here, we propose a solution for this issue by introducing an organic salt additive 4‐(trifluoromethyl) benzylammonium formate (TFMBAFa) in the perovskite precursor to passivate perovskite film and NiOx@(2‐(3,6‐dimethyl‐9H‐carbazol‐9‐yl) ethyl) phosphonic acid (Me‐2PACz) composited hole transport layer (HTL), and thus construct a buffer layer between perovskite‐HTL interface. The effective diminishing of NiOx/perovskite interfacial reactions and defects results in enhanced carrier transport. Consequently, the target device achieves simultaneous improvements in power conversion efficiency (24.2%), storage stability (T100 > 1400 h), thermal stability (T80 > 1000 h), and operational stability (T70 > 850 h), where T100, T80, and T70 refer to the retention of 100%, 80%, and 70% of initial PCE, respectively. This work provides an effective strategy to advance the performance of NiOx‐based inverted PSCs.

Ethanol processable inorganic-organic hybrid hole transporting layers enabled 20.12% efficiency organic solar cells.

In this study, a high-performance inorganic-organic hybrid hole transporting layer (HTL) was developed using ethanol-soluble alkoxide precursors and a self-assembled monolayer (SAM). Three metal oxides-vanadium oxide (VOx), niobium oxide (Nb2O5), and tantalum oxide (Ta2O5)-were synthesized through successive low-temperature (100 °C) thermal annealing (TA) and UV-ozone (UVO) treatments of their respective precursors: vanadium oxytriethoxide (EtO-V), niobium ethoxide (EtO-Nb), and tantalum ethoxide (EtO-Ta). Among these, the Nb2O5 film exhibited excellent transmittance, a high work function, and good conductivity, along with a more compact and uniform structure featuring fewer interfacial defects, which facilitated efficient charge extraction and transport. Furthermore, the deposition of a SAM of (2-(9H-carbazol-9-yl)ethyl)phosphonic acid (2PACz) on top of Nb2O5 further passivated defects, enhancing interfacial contact with the photoactive layer. The resulting inorganic-organic hybrid HTL of Nb2O5/2PACz demonstrated excellent compatibility with various photoactive blends, achieving impressive power conversion efficiencies of 19.44%, 19.18%, and 20.12% for the PM6:L8-BO, PM6:BTP-eC9, and D18:BTP-eC9 based organic solar cells, respectively. 20.12% is the best performance for bulk heterojunction organic solar cells with binary components as the photoactive layer.

Recognition of carboxylic acids and phosphonic acids using a 1,8-diphenylanthracene-based diguanidine in solution and solid states

A 1,8-diphenylanthracene-based diguanidine 1 has been designed and synthesized for the recognition of carboxylic acids and phosphonic acid derivatives. The diguanidine 1a forms 1:1 complexes with the dicarboxylic acids and the diphosphonic acid derivatives in a DMSO solution, and the formation of these complexes was confirmed by a DOSY NMR analysis. The binding mode towards the guanidyl group (Type I, Type II, two existing types of binding modes toward three nitrogen atoms) with a diphosphonic acid derivative was successfully demonstrated by the 2D NOESY analysis. The diguanidine 1a does not show any fluorescence in a DMSO solution, but after the addition of carboxylic acids, the formation of a stable complex or the formation of the protonated guanidinium (1a+2H+) were distinguishable by the observation of a light-blue fluorescence around 430 nm. These fluorescence observations can be determined the stability of the complexes of the diguanidine 1a with carboxylic acids. On the other hand, the DMSO solution of diguanidine 1a showed a light-blue fluorescence after the addition of phosphonic acids. Interestingly, diguanidine 1a recognized methylphosphonic acid 9a in the solid state by grinding and showed a green fluorescence, while the other phosphonic acids 9 and dicarboxylic acids (4d: pimelic acid, 4f: azelaic acid) showed a light-blue fluorescence in the solid state, and a selectivity was observed. These fluorescence characteristics of the diguanidine 1 are applicable for the detection of carboxylic acids and phosphonic acids, especially for methylphosphonic acid 9a in the solid state.

Regulation of nucleation and crystallization for blade-coating large-area CsPbBr3 perovskite light-emitting diodes

Metal halide perovskite light-emitting diodes (PeLEDs) and large-area perovskite color conversion layers for liquid crystal display exhibit great potential in the field of illumination and display. Blade-coating method stands out as a highly suitable technique for fabricating large-scale films, albeit with challenges such as uneven nucleation coverage and non-uniformity crystallization process. In this work, we developed an in-situ characterization measurement system to monitor the perovskite nucleation, and crystallization process. By incorporating formamidine acetate (FAAc) into perovskite precursor solutions, the nucleation rate and nuclei density of perovskite were increased, leading to more uniform nucleation. In addition, we inserted a layer of [2-(9H-carbazol-9-yl)ethyl] phosphonic acid above the poly(9-vinylcarbazole) hole transport layer. This layer acts as an anchor for the perovskite nano-crystal nuclei formed in the precursor, enhancing the steric hindrance of the solute and subsequently slowing down the crystal growth rate, thereby improving crystal quality. Based on these improvements, large-area perovskite nano-polycrystalline films with significantly improved uniformity and enhanced photoluminescence quantum yield were obtained. A small-area PeLED (2 mm × 2 mm) with a maximum external quantum efficiency of 25.91% was realized, marking the highest record of PeLED prepared by blade-coating method to date. An ultra-large-area PeLED (5 cm × 7 cm) was also prepared, which is the largest PeLED prepared by the solution method reported so far.

Growth and stabilization of cubic FAPbI3: On the interaction between phosphonic acids and co-evaporated perovskites

Growth and stabilization of cubic FAPbI3: On the interaction between phosphonic acids and co-evaporated perovskites

A convenient bottom up route to covalently anchor Pd(II)-PEPPSI on layered zirconium(IV) phosphonate: Efficient catalyst for Suzuki-Miyaura cross coupling of aryl chlorides

A rational and bottom-up route for assembling layered Zr(IV) phosphonate framework decorated with covalently anchored N-heterocyclic carbene NHC-Pd(II) fragment has been developed. Reaction of phosphonic acid functionalized Pd(II)-NHC precursor complex with ZrOCl2·8H2O provides easy access to a layered material with covalently anchored catalytically active Pd(II)-NHC sites. The Pd(II)-NHC functionalized Zr(IV) phosphonate showed enhanced catalytic activity in Suzuki-Miyaura cross coupling reaction of both aryl bromides and chlorides with aryl boronic acid, as compared to their homogeneous counterparts. The Zr(IV) phosphonate framework imparts remarkable robustness to the Pd(II)-NHC catalyst and allowed recycling of the catalyst up to nine catalytic cycles without any major loss of catalytic activity.

Dodecylphosphonic acid for the separation of spodumene and albite: flotation behavior and adsorption mechanism

Spodumene is an important lithium-bearing mineral, that is associated with albite and difficult to separate because of their similar surface chemical properties. Traditional fatty acid collectors often have issues, such as poor selectivity or weak collector ability, and thus developing efficient spodumene collectors is essential. In this study, the phosphonic acid surfactant dodecylphosphonic acid (DDPA) was first used as a single collector for the flotation separation of spodumene and albite, showing good selectivity and collection performance. Then, separation and adsorption mechanisms were studied using various characterization methods, including diffuse reflectance infrared Fourier transform spectroscopy, total organic carbon adsorption measurements, X-ray photoelectron spectroscopy, and zeta potential tests. Flotation tests showed that the recovery for spodumene can reach approximately 80% through single-mineral flotation under the following conditions: activation without metal ion, neutral pulp pH of 6.5–7.0, and DDPA dosage of 4 × 10−4 mol/L. By contrast, the recovery of albite was only approximately 10%. The recovery for Li2O in the artificial mixed ore test was 75.03%, and the grade was 6.30%. The separation of spodumene and albite was due to the selective adsorption of DDPA on the surface of spodumene, and more DDPA were adsorbed on the surface of spodumene than on albite under the same conditions. Adsorption mechanism analysis indicated that Al and O on the mineral surface were the active sites for DDPA adsorption. Combined with the species distribution, DDPA existed in various forms in different aqueous environments, indicating that DDPA was mainly adsorbed onto the mineral surface through chemisorption and hydrogen bonding. In summary, DDPA can be used as an effective collector for spodumene.