Organic Ligands Research Articles

Adsorption studies of tetracycline hydrochloride and diclofenac sodium on NH2-MIL-53(Al/Zr) sodium alginate gel spheres

Metal-organic frameworks are emerging inorganic-organic hybrid materials that can be self-assembled from metal ions and organic ligands via coordination bonds. These materials possess large specific surface area, tunable pore structure, abundant active center, diversity of functional groups as well as high mechanical and thermal stability which promote their applications in adsorption and catalysis studies. In this study, NH2-MIL-53(Al/Zr) was prepared and embedded into sodium alginate gel spheres (NH2-MIL-53(Al/Zr)-SA) and its adsorption properties towards TC and DCF in solution were investigated. According to XRD and FTIR analysis, the structure of the raw material was not changed after making the gel spheres. The maximum adsorption towards TC (pH =3) and DCF (pH =5) reached 98.5 mg·g−1 and 192 mg·g−1, respectively. The process was consistent with Langmuir and Freundlich, suggesting that there was both monolayer and multilayer adsorption which infers the presence of physical adsorption (intra-particle diffusion) and non-homogeneous chemical adsorption. The thermodynamic parameters showed that the adsorption process was a spontaneous entropy increasing reaction. The regeneration rate of spent NH2-MIL-53(Al/Zr)-SA could still reach 99.1 % after three cycles, indicating good regeneration performance. This study can provide a basis for the application of NH2-MIL-53(Al/Zr)-SA in wastewater treatment.

Solvent-Induced Structural Rearrangement in Ultrasound-Assisted Synthesis of Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) are crystalline extended structures featuring permanent porosity, assembled from metal ions and organic ligands, often synthesized by the solvothermal method (50-260°C, 12-72h). Here, an alternative synthetic approach-solvent-induced structural rearrangement in ultrasound-assisted synthesis is presented. Six representative Zn-based MOFs, each composed of distinct secondary building units, are synthesized within 2-180min consuming less solvent (>0.03m) at room temperature. It is observed that ultrasonication induces the construction of a coordination network, and subsequent solvent exchange triggers structural rearrangement to yield MOFs of high crystallinity and porosity. Furthermore, the scalability of this method is demonstrated through the bulk synthesis of MOF-5, MOF-74, ZIF-8, and MFU-4l within 90min. The initiation of nucleation through ultrasound and the subsequent transformation induced by solvent exchange offer an alternative method for efficiently synthesizing MOFs in bulk, potentially broadening their range of applications.

2D Zn (II) Metal‐Organic Framework as a Highly Sensitive Luminescent Sensor for Detection of the Cr2O72− and Fe3+

AbstractIn this work, NH2‐containing organic ligand 5‐Aminoisophthalic acid (AIPA), and trans‐1,2‐bis(4‐pyridyl)ethene (bpe) were selected as organic ligands to construct a new two‐dimensional luminescent Zn(II) metal‐organic framework [Zn(AIPA)(bpe)1/2]⋅named MOF‐1. It is worth noting that MOF‐1 exhibited excellent thermal stability and chemical stability in common solvents and different pH aqueous solution. As we expected, the luminescence sensing investigations demonstrated that MOF‐1 could be deemed as a multifunctional fluorescence sensor toward Cr2O72− and Fe3+ via a “turn‐off” effect. Notably, MOF‐1 had high selectivity and sensitivity for Fe3+ and Cr2O72− with low detection limits of 9.72×10−5 M and 1.95×10−5 M, respectively. Furthermore, the possible quenching mechanisms were also explored in detail.

Electrostatic Self-Assembly Synthesis of Pd/In2O3 Nanocatalysts with Improved Performance Toward CO2 Hydrogenation to Methanol.

CO2 hydrogenation to methanol has emerged as a promising strategy for achieving carbon neutrality and mitigating global warming, in which the supported Pd/In2O3 catalysts are attracting great attention due to their high selectivity. Nonetheless, conventional impregnation methods induce strong metal-support interaction (SMSI) between Pd and In2O3, which leads to the excessive reduction of In2O3 and the formation of undesirable PdIn alloy in hydrogen-rich atmospheres. Herein, we innovatively synthesized Pd/In2O3 nanocatalysts by the electrostatic self-assembly process between surface-modified composite precursors with opposite charges. And the organic ligands concurrently serve as Pd nanoparticle protective agents. The resultant Pd/In2O3 nanocatalyst demonstrates the homogeneous distribution of Pd nanoparticles with controllable sizes on In2O3 supports and the limited formation of PdIn alloy. As a result, it exhibits superior selectivity and stability compared to the counterparts synthesized by the conventional impregnation procedure. Typically, it attains a maximum methanol space-time yield of 0.54 gMeOH h-1gcat -1 (300 °C, 3.5 MPa, 21,000 mL gcat -1 h-1). Notably, the correlation characterization results reveal the significant effect of small-size, highly dispersed Pd nanoparticles in mitigating MSI. These results provide an alternative strategy for synthesizing highly efficient Pd/In2O3 catalysts and offer a new insight into the strong metal-support interaction.

The "energy gap law" for mid-infrared nanocrystals.

Colloidal quantum dots are of increasing interest for mid-infrared detection and emission, but device performances will vastly benefit from reducing the non-radiative recombination. Empirically, the photoluminescence quantum yield decreases exponentially toward the mid-infrared, which appears similar to the energy gap law known for molecular fluorescence in the near-infrared. For molecules, the mechanism is electron-vibration coupling and fast internal vibrational relaxation. Here, we explore the possible mechanisms for inorganic quantum dots. The primary mechanism is assigned to an electric dipole near-field energy transfer from the quantum dot electronic transitions to the infrared absorption of surface organic ligands and then to the multiphonon absorption of the quantum dot inorganic core or the surrounding inorganic matrix. In order to obtain luminescent quantum dots in the 3-10μm range, we motivate the importance of using inorganic matrices, which have a higher infrared transparency compared to organic materials. At longer wavelengths, inter-quantum dot energy transfer is noted to be much faster than radiative relaxation, indicating that bright mid-infrared colloidal quantum dot films might then benefit from dilution.

Carboxylic acid modulated in situ growth of Zr-based MOFs on carboxylated cotton fabrics for removal of Cr(VI) from aqueous solutions

In this paper, carboxylated cotton fabric (CF-Ph-COOH) were obtained as active substrate by diazonium radical polymerization modification of cotton fibers. Then the MOF fabric composites were prepared by in situ growth of metal zirconium ions (Zr) and organic ligands on the surface of carboxylated cotton fabrics under carboxylic acid modifier. MOF fabric composites with controllable morphologies structures were achieved by regulating organic ligands, reaction time the type and dosage of regulator (formic acid and acetic acid). The prepared acetic acid regulated MOF fabric composites were designated as CF-HAc1-UiO-66, CF-HAc2-UiO-66, CF-HAc1-UiO-66-NH2, and CF-HAc2-UiO-66-NH2, respectively, and the formic acid regulated as CF-FA-UiO-66 and CF-FA-UiO-66-NH2. The fabricated carboxylic acid modulated MOF fabric composites were well characterized using SEM, TGA, XRD, FTIR, and XPS spectra. The adsorption experiment results show that carboxylic acid modulated Zr based MOF fabric composites can serve as adsorbent for effective removal of Cr(VI) from water, in which the CF-FA-UiO-66-NH2 was prepared under the ratio of ZrCl4 and BDC-NH2 is 1.006 and with 5.47 M formic acid regulator exhibits that the optimal adsorption efficiency and the removal efficiency is 79.5 %. In addition, the adsorption of Cr(VI) in water by CFA-UiO-66-NH2 showed a quasi-secondary kinetic model following the Langmuir adsorption model, showing a a typical of chemisorption. What’s more, the Cr(VI) removal efficiency and saturated adsorption capacity of CF-FA-UiO-66-NH2 was up to 80 % and 318.85 mg/g, respectively. The prepared CF-FA-UiO-66-NH2 MOF fabric composite was recyclable for removal of Cr(VI), and could be used as the potential adsorbent membrane for waste water treatment.

Degradation of Bisphenol A by manganese minerals: The impact of inorganic and organic ligands

Manganese minerals are ubiquitous in aquatic environments, where both inorganic and organic components can form complexes with them, thereby impacting the release of reactive Mn(III) and the fate of pollutants. The available information about these processes remains insufficient, however, impeding the study of the migration and transformation of pollutants in the environment. In this study, pyrophosphate and humic acid were selected as inorganic and organic ligands typical of aquatic environments, and their impacts on the degradation of Bisphenol A by the β- and δ- variants of MnO2 were investigated. The results indicate that 1.0–5.0 mM pyrophosphate promotes the generation of reactive Mn(III) from β-MnO2, resulting in enhanced degradation of Bisphenol A. Pyrophosphate inhibits δ-MnO2-mediated degradation of Bisphenol A due to competition for reactive sites. Humic acids increase the degradation of Bisphenol A mediated by δ-MnO2 by forming complexes with reactive Mn(III) released from the δ-MnO2. The degradation of Bisphenol A mediated by minerals in the presence of ligands occurs primarily through hydroxylation, one-electron transfer, and free radical coupling. These findings provide new insights into the role of ligands in the reductive dissolution of manganese minerals and their synergistic effect on the fate of Bisphenol A in aqueous environments.

Synergistic promotion of microalgal growth and copper removal from synthetic wastewater by nanoscale zero-valent iron particles.

The increasing concentrations of heavy metals in livestock wastewater pose a serious threat to the environmental safety and human health, limiting its resource utilisation. In the present study, microalgae and nanoscale zero-valent iron were selected to construct a coupled system for copper-containing wastewater treatment. The addition of 50 mg·L-1 nanoscale zero-valent iron (50 nm) was the optimal value for the experiment, which could significantly increase the biomass of microalgae. In addition, nanoscale zero-valent iron stimulated microalgal secretion of extracellular polymeric substances, increasing the contents of binding sites, organic ligands, and functional groups on the microalgal surfaces and ultimately promoting the settling of microalgae and binding of heavy metals. The coupled system could quickly adapt to copper-containing wastewater of 10 mg·L-1, and the copper removal rate reached 94.99%. Adsorption and uptake by organisms, together with the contribution of zero-valent iron nanoparticles, are the major copper removal pathways. Overall, this work offers a novel technical solution for enhanced treatment of copper-containing livestock wastewater, which will help improve the efficiency and quality of wastewater treatment.

A Spectroscopic Method for Distinguishing Two Novel Sandwich-Type Tungsten Oxide Cluster Compounds.

This study introduces two novel sandwich-type tungsten-oxygen cluster compounds synthesized by hydrothermal methods, H4(C6H12N2H2)3{Na(H2O)2[Mn2(H2O)(GeW9O34)]}2 (Compound 1) and H2(C6H12N2H2)3.5{Na3(H2O)4[Co2(H2O)(GeW9O34)]2}·17H2O (Compound 2). The two compounds comprise cluster anions [GeW9O34]10- coordinated with transition metal atoms, either Mn or Co, and are stabilized by organic ligands. These compounds are crystallized in the hexagonal crystal system and P63/m space group. The two compounds were characterized through various techniques. Fourier transform infrared (IR) spectroscopy showed absorption peaks of anionic backbone vibrations of the Keggin cluster at 500-1000 cm-1, IR spectral peaks of δ(N-H) and νas(C-N) of the ligand triethylenediamine at 1000-2000 cm-1, and IR spectral peaks of the ligand νas(N-H) and νas(O-H) of water at 3000-3500 cm-1. Despite similar one-dimensional (1D) IR spectra due to the same cluster anions and similar molecular structures, the two compounds exhibited distinct responses in two-dimensional correlation spectroscopy with IR under magnetic and thermal perturbations. Under magnetic perturbation, Compound 1 showed a strong response peak for νas(W-Ob-W), while Compound 2 exhibited a strong response peak for νas(W=Od), possibly linked to differing magnetic particles. Similarly, Compound 1 displayed a strong response peak under thermal perturbation for νas(W-Oc-W). In contrast, Compound 2 showed a strong response peak for νas(W=Od); these results may be attributed to the different hydrogen bonding connections between the two compounds, which affect the groups in distinct ways through vibration and transmit these vibrations to the W-O bonds. The research presented in this paper expands the theoretical and experimental data of 2D correlation IR spectroscopy.

Prominent Intrinsic Proton Conduction in Two Robust Zr/Hf Metal-Organic Frameworks Assembled by Bithiophene Dicarboxylate.

To date, developing crystalline proton-conductive metal-organic frameworks (MOFs) with an inherent excellent proton-conducting ability and structural stability has been a critical priority in addressing the technologies required for sustainable development and energy storage. Bearing this in mind, a multifunctional organic ligand, 3,4-dimethylthiophene[2,3-b]thiophene-2,5-dicarboxylic acid (H2DTD), was employed to generate two exceptionally stable three-dimensional porous Zr/Hf MOFs, [Zr6O4(OH)4(DTD)6]·5DMF·H2O (Zr-DTD) and [Hf6O4(OH)4(DTD)6]·4DMF·H2O (Hf-DTD), using solvothermal means. The presence of Zr6 or Hf6 nodes, strong Zr/Hf-O bonds, the electrical influence of the methyl group, and the steric effect of the thiophene unit all contribute to their structural stability throughout a wide pH range as well as in water. Their proton conductivity was fully examined at various relative humidities (RHs) and temperatures. Creating intricate and rich H-bonded networks between the guest water molecules, coordination solvent molecules, thiophene-S, -COOH, and -OH units within the framework assisted proton transfer. As a result, both MOFs manifest the maximum proton conductivity of 0.67 × 10-2 and 4.85 × 10-3 S·cm-1 under 98% RH/100 °C, making them the top-performing proton-conductive Zr/Hf-MOFs. Finally, by combining structural characteristics and activation energies, potential proton conduction pathways for the two MOFs were identified.

Boosting potassium and sodium-ion storage performance by in-situ self-assembly of a Co-based π-d conjugated coordination polymer on graphene nanosheets

To obtain anode materials with good electrochemical performances in both potassium ion batteries (PIBs) and sodium-ion batteries (SIBs), a Co-based π-d conjugated coordination polymer (Co-HHTP) is in-situ assembled on graphene (G) nanosheets using a facile one-step solvothermal method. The resulting Co-HHTP/G composite shows improved electrochemical performances over pure Co-HHTP. After 300 cycles of using as an anode of PIBs/SIBs for the first time, the reversible specific capacity of the Co-HHTP/G composite is found to be 381/277 mAh g−1 at 100 mA g−1. After undergoing 500 cycles at 1000 mA g−1, the material's reversible specific capacities remain at 234/164 mAh g−1 for PIBs/SIBs. The improved performances of the Co-HHTP/G composite electrode are due to the incorporation of graphene. This incorporation not only reduces structural stacking and promotes active site utilization, but also increases electrical conductivity and structural stability. According to the ex-situ X-ray photoelectron spectrometer (XPS) spectra, the Co-HHTP/G's energy storage mechanism throughout the process of potassisation/depotassisation is found to be linked to the aromatic rings presented in the organic ligands.

Silver and Copper Nanoparticle-Loaded Self-Assembled Pseudo-Peptide Thiourea-Based Organic-Inorganic Hybrid Gel with Antibacterial and Superhydrophobic Properties for Antifouling Surfaces.

The escalating threat of antimicrobial resistance has become a global health crisis. Therefore, there is a rising momentum in developing biomaterials with self-sanitizing capabilities and inherent antibacterial properties. Despite their promising antimicrobial properties, metal nanoparticles (MNPs) have several disadvantages, including increased toxicity as the particle size decreases, leading to oxidative stress and DNA damage that need consideration. One solution is surface functionalization with biocompatible organic ligands, which can improve nanoparticle dispersibility, reduce aggregation, and enable targeted delivery to microbial cells. The existing research predominantly concentrates on the advancement of peptide-based hydrogels for coating materials to prevent bacterial infection, with limited exploration of developing surface coatings using organogels. Herein, we have synthesized organogel-based coatings doped with MNPs that can offer superior hydrophobicity, oleophobicity, and high stability that are not easily achievable with hydrogels. The self-assembled gels displayed distinct morphologies, as revealed by scanning electron microscopy and atomic force microscopy. The cross-linked matrix helps in the controlled and sustained release of MNPs at the site of bacterial infection. The synthesized self-assembled gel@MNPs exhibited excellent antibacterial properties against harmful bacteria such as Escherichia coli and Staphylococcus aureus and reduced bacterial viability up to 95% within 4 h. Cytotoxicity testing against metazoan cells demonstrated that the gels doped with MNPs were nontoxic (IC50 > 100 μM) to mammalian cells. Furthermore, in this study, we coated the organogel@MNPs on cotton fabric and tested it against Gram +ve and Gram -ve bacteria. Additionally, the developed cotton fabric exhibited superhydrophobic properties and developed a barrier that limits the interaction between bacteria and the surface, making it difficult for bacteria to adhere and colonize, which holds potential as a valuable resource for self-cleaning coatings.

Morphology-controlled nickel-organic framework nanosheet arrays for efficient urea electrolysis in alkaline media

Urea electrolysis is considered as a promising energy-saving hydrogen production technique to substitute the water electrolysis, but it is restricted by the lack of efficient and cost-effective catalysts. Herein, nickel foam supported three-dimensional (3D) nickel-organic framework nanosheet arrays (Ni-BDC-t/NF, where t is the reaction time) comprising Ni2+ and an organic ligand of 4,4-biphenyl dicarboxylic acid (BDC) are synthesized as catalyst for urea electrolysis in alkaline media. Benefiting from the highly exposed Ni active sites and fast electron transfer rate endowed by 3D nanosheet array architecture, the structurally optimized Ni-BDC-10/NF exhibits preeminent electrocatalytic activity and durability toward urea oxidation reaction (UOR). To deliver a high current density of 100 mA cm−2, the required UOR potential of Ni-BDC-10/NF is only 1.50 V vs. RHE. Significantly, by further coupling with the cathodic hydrogen evolution reaction, the urea electrolysis system based on Ni-BDC-10/NF self-supporting anode exhibits a dramatic voltage decrease by 340 mV at a current density of 50 mA cm−2 as compared with that of water electrolysis under the same conditions. This study provides some new ideas for developing high-efficiency nickel-based organic framework catalysts and their application in urea-related energy storage devices.

Cd(II)-based complex loaded with drug doxorubicin hydrogels against leukemia and reinforcement learning

A new 3D metal–organic frameworks [Cd6(L)4(bipy)3(H2O)2·H2O] (1) was gained by employing Cd(II) and organic ligand [H3L = 4,4′,4′′-(benzene-1,3,5-triyltris(oxy))tribenzoic acid)benzene acid; bipy = 4,4′-bipyridine] in the solvothermal condition, which has been fully examined via single-X ray diffraction, FTIR and elemental analysis and so on. Using natural polysaccharides hyaluronic acid (HA) and carboxymethyl chitosan (CMCS) as raw materials, we successfully prepared HA/CMCS hydrogels and observed their internal micromorphology by scanning electron microscopy. Using doxorubicin (Dox) as a drug model, we synthesized a novel metal gel particle loaded with doxorubicin, and their encapsulation and release effects were studied using fluorescence spectroscopy, followed by further investigation of their components through thermogravimetric analysis. Based on this, the therapeutic effect on leukemia was evaluated. Finally, an enhanced learning method for automatically designing new ligand structures from host ligands was proposed. Through generative modeling and molecular docking simulations, the biological behavior of the host and predicted cadmium complexes was extensively studied.

Organic A‐Site Cations Improve the Resilience of Inorganic Lead‐Halide Perovskite Nanocrystals to Surface Defect Formation

AbstractLead halide perovskite nanocrystals (LHP NCs) are generally prone to surface defect formation during the purification process, resulting in a reduced photoluminescence (PL) quantum yield. The purification of LHP NCs using antisolvents leads to the detachment of surface atoms and ligandsin the form of alkylammonium‐halides or A‐carboxylates (A: Cs, methylammonium, MA, or formamidinium, FA. Currently, intense research is being carried out to improve the surface stability of LHP NCs using various long‐chain organic ligands that strongly bind to the surface of NCs. Herein, the findings on the higher surface stability of hybrid (MAPbBr3 and FAPbBr3) LHP NCs compared to that of inorganic CsPbBr3 NCs against purification with polar antisolvents are reported. It is discovered that the CsPbBr3 NC surface stability can be enhanced (reaching that of hybrid perovskite NCs) by the incorporation of a small amount of MA or FA A‐site organic cations into their lattice, corroborated by the evidence that the PL quantum yield of mixed A‐cation CsxFA1‐xPbBr3 and CsxMA1‐xPbBr3 NCs remains unaffected after several purification cycles. It is hypothesized that this is attributed to hydrogen bonding between the organic A‐site cations and the neighboring halides on the surface. These findings are not only fundamentally important but are also expected to have wide implications in the field of metal‐halide perovskite optoelectronics.

Bis(acyl)phosphide Complexes of U(III)/U(IV): A Case of a Hidden Redox-Active Ligand.

The recently reported tris(bis(2,4,6-triisopropylbenzoyl)-phosphide)uranium (UIII(trippBAP)3, 2) complex (Inorg. Chem. 2022, 61 (32), 12508-12517) demonstrated a silent 31P NMR spectrum. This complex was described as a U(III) complex with an organic radical ligand fragment. Moreover, the EPR spectrum of 2 was indicative of an organic radical in the ligand framework complexed to uranium, in contrast to that of UIV(mesBAP)4, 1. Herein, with the help of relativistic density functional theory (DFT) calculations, the electronic structures of 1, 2, and U(mesBAP)3 (4) are examined in an effort to understand the unusual 31P NMR spectrum of 2. Results indicate the reduction of the carbonyl bonds and delocalization of the electrons over the ligands, indicative of U → L backbonding. Additionally, the reduced acyl carbons are found to exist as ketyl radicals [O═C• -] that are responsible for the silent 31P NMR spectra of 2. These findings demonstrate the redox noninnocent nature of BAP- in 2 and 4, causing uranium to exist in a formal oxidation state of +4.

Toward coupling across inorganic/organic hybrid interfaces: polyaniline-coated gold nanoparticles with 4-aminothiophenol as gold-anchoring moieties

AbstractThe chemical binding between metal nanoparticles and (semi-)conductive polymer layers is essential to control the (opto-)electronic properties of such hybrid materials. Current approaches that achieve a conjugated binding of organic (semi-)conductive ligands to metal nanoparticles demonstrated promising functional properties, but are based on tedious multi-step organic synthesis to incorporate the required binding moieties at the chain ends of targeted macromolecular species. Herein, we explore the pre-functionalization of gold nanoparticles with p-aminothiophenol and subsequent surfactant-assisted formation of a poly(aniline) (PANI) shell as a means to access gold/PANI core–shell-type nanoparticles with enhanced conductive properties. Controlled surface deposition of these hybrid nanoparticles is achieved via template-assisted self-assembly. For these surface-deposited nanoparticles, charge transport properties are characterized at the nanoscale by conductive atomic force microscopy measurements and show a significant conductivity increase of our core–shell particles as compared to reference particles formed by conventional surfactant-assisted PANI-shell formation. Graphical Abstract

The Inorganic Ligand‐Supported Copper Catalyst Catalyzing Alkyne Coupling Reactions

AbstractGlaser‐coupled synthesized 1,3‐diyne can participate in the generation of conjugated polymers and is now widely used in organic and polymer synthesis. Currently, the catalyst in coupling are mostly based on the complexation of noble metals with complex organic ligands, which inevitably increases the research cost and storage difficulty. However, polyoxometalates (POMs), with acidic and redox properties, can be used as an excellent inorganic ligands with low cost and easy storage. In this work, we have synthesized copper catalyst 1, (NH4)4[CuMo6O18(OH)6] with polyoxometalates as inorganic ligands in a facile way and applied them in the coupling of alkynes to obtain (non)symmetrical conjugated 1,3‐diynes in high yields without bases, finally proposing a reasonable reaction path. In addition, the catalyst showed good tolerance to a variety of different groups, further demonstrating its excellent catalytic activity. It is worth mentioning that the catalyst maintained its good structure and activity after six cycles, demonstrating its promising potential for industrial applications. Thus, this paper provides a new strategy for the preparation of (un)symmetrical diynes using polyoxometalates of Cu as catalyst, and also demonstrates the potential of multi‐acid catalyst for organocatalytic applications.

Effect of the nitrogen/carbon ratio in the organic ligand of a nickel single-atom catalyst on its electrochemical activity in CO2 reduction

Simple, large-scale synthesis of metal single-atom catalysts (SACs) is limited by the aggregation of metal atoms on the support material surface. The N atoms in small organic ligands (SOLs) can anchor single metal atoms, affording abundant surface-active sites. In this study, we investigated the effect of the nitrogen/carbon ratio (N/C) in SOLs on the properties of the resultant Ni single-atom confined nitrogen-doped carbon black (Ni-NCB). The N/C ratio affected the thermal stability of Ni-NCB_N/Cs during carbonization, and the optimal Ni-NCB (Ni-NCB_0.5) was synthesized with the SOL 2-methylimidazole. Ni-NCB_0.5 achieved a CO partial current density of > 500 mA cm–2 and high CO Faradaic efficiency (96.4 %) in the CO2 reduction reaction. The 3- and 4-cell stack systems with Ni-NCB_0.5 (25 cm2 area per unit cell) exhibited an overall current of 10 A, high CO selectivity (> 96.0 %), and long-term stability (50 h). This synthetic strategy for SACs can be commercialized and even extended to other industrial electrocatalysts.

Enhanced Charge Transfer in Quasi-2D Perovskite by Formamidinium Cation Gradient Incorporation for Efficient and Stable Solar Cells.

Quasi-2D perovskites have attracted much attention in perovskite photovoltaics due to their excellent stability. However, their photoelectric conversion efficiency (PCE) still lags 3D counterparts, particularly with high short-circuit current (JSC) loss. The quantum confinement effect is pointed out to be the sole reason, which introduces widened bandgap and poor exciton dissociation, and undermines the light capture and charge transport. Here, the gradient incorporation of formamidinium (FA) cations into quasi-2D perovskite is proposed to address this issue. It is observed that FA prefers to incorporate into the larger n value phases near the film surface compared to the smaller n value phases in the bulk, resulting in a narrow bandgap and gradient structure within the film. Through charge dynamic analysis using in situ light-dark Kelvin probe force microscopy and transient absorption spectroscopy, it is demonstrated that incorporating 10% FA significantly facilitates efficient charge transfer between low n-value phases in the bulk and high n-value nearby film surface, leading to reduced charge accumulation. Ultimately, the device based on (AA)2(MA0.9FA0.1)4Pb5I16, where AA represents n-amylamine renowned for its exceptional environmental stability as a bulky organic ligand, achieves an impressive power conversion efficiency (PCE) of 18.58% and demonstrates enhanced illumination and thermal stability.