Dopant-free hole transporting materials (HTMs) is significant to the stability of perovskite solar cells (PSCs). Here, we developed a novel star-shape arylamine HTM, termed Py-DB, with a pyrene core and carbon-carbon double bonds as the bridge units. Compared to the reference HTM (termed Py-C), the extension of the planar conjugation backbone endows Py-DB with typical intermolecular π-π stacking interactions and excellent solubility, resulting in improved hole mobility and film morphology. In addition, the lower HOMO energy level of the Py-DB HTM provides efficient hole extraction with reduced energy loss at the perovskite/HTM interface. Consequently, an impressive power conversion efficiency (PCE) of 24.33 % was achieved for dopant-free Py-DB-based PSCs, which is the highest PCE for dopant-free small molecular HTMs in n-i-p configured PSCs. The dopant-free Py-DB-based device also exhibits improved long-term stability, retaining over 90 % of its initial efficiency after 1000â h exposure to 25 % humidity at 60 °C. These findings provide valuable insights and approaches for the further development of dopant-free HTMs for efficient and reliable PSCs.
Perovskite solar cells (PSCs) are among the most promising photovoltaic technologies owing to their exceptional optoelectronic properties1,2. However, the lower efficiency, poor stability and reproducibility issues of large-area PSCs compared with laboratory-scale PSCs are notable drawbacks that hinder their commercialization3. Here we report a synergistic dopant-additive combination strategy using methylammonium chloride (MACl) as the dopant and a Lewis-basic ionic-liquid additive, 1,3-bis(cyanomethyl)imidazolium chloride ([Bcmim]Cl). This strategy effectively inhibits the degradation of the perovskite precursor solution (PPS), suppresses the aggregation of MACl and results in phase-homogeneous and stable perovskite films with high crystallinity and fewer defects. This approach enabled the fabrication of perovskite solar modules (PSMs) that achieved a certified efficiency of 23.30% and ultimately stabilized at 22.97% over a 27.22-cm2 aperture area, marking the highest certified PSM performance. Furthermore, the PSMs showed long-term operational stability, maintaining 94.66% of the initial efficiency after 1,000 h under continuous one-sun illumination at room temperature. The interaction between [Bcmim]Cl and MACl was extensively studied to unravel the mechanism leading to an enhancement of device properties. Our approach holds substantial promise for bridging the benchtop-to-rooftop gap and advancing the production and commercialization of large-area perovskite photovoltaics.
Solid-state proton conductors based on the use of metal-organic framework (MOF) materials as proton exchange membranes are being investigated as alternatives to the current state of the art. This study reports a new family of proton conductors based on MIL-101 and protic ionic liquid polymers (PILPs) containing different anions. By first installing protic ionic liquid (PIL) monomers inside the hierarchical pores of a highly stable MOF, MIL-101, then carrying out polymerization in situ, a series of PILP@MIL-101 composites was synthesized. The resulting PILP@MIL-101 composites not only maintain the nanoporous cavities and water stability of MIL-101, but the intertwined PILPs provide a number of opportunities for much-improved proton transport compared to MIL-101. The PILP@MIL-101 composite with HSO4 - anions shows superprotonic conductivity (6.3 × 10-2 S cm-1 ) at 85 °C and 98% relative humidity. The mechanism of proton conduction is proposed. In addition, the structures of the PIL monomers were determined by single crystal X-ray analysis, which reveals many strong hydrogen bonding interactions with O/NH···O distances below 2.6 Å.
The stabilization of uranyl(v) (UO2 1 + ) by Fe(ii) in natural systems remains an open question in uranium chemistry. Stabilization of UVO2 1+ by Fe(ii) against disproportionation was also demonstrated in molecular complexes. However, the relation between the Fe(ii) induced stability and the change of the bonding properties have not been elucidated up to date. We demonstrate that U(v) - oaxial bond covalency decreases upon binding to Fe(ii) inducing redirection of electron density from the U(v) - oaxial bond towards the U(v) - equatorial bonds thereby increasing bond covalency. Our results indicate that such increased covalent interaction of U(v) with the equatorial ligands resulting from iron binding lead to higher stability of uranyl(v). For the first time a combination of U M4,5 high energy resolution X-ray absorption near edge structure (HR-XANES) and valence band resonant inelastic X-ray scattering (VB-RIXS) and ab initio multireference CASSCF and DFT based computations were applied to establish the electronic structure of iron-bound uranyl(v).
The reconstitution of [Mn]-hydrogenases using a series of MnI complexes is described. These complexes are designed to have an internal base or pro-base that may participate in metal-ligand cooperative catalysis or have no internal base or pro-base. Only MnI complexes with an internal base or pro-base are active for H2 activation; only [Mn]-hydrogenases incorporating such complexes are active for hydrogenase reactions. These results confirm the essential role of metal-ligand cooperation for H2 activation by the MnI complexes alone and by [Mn]-hydrogenases. Owing to the nature and position of the internal base or pro-base, the mode of metal-ligand cooperation in two active [Mn]-hydrogenases is different from that of the native [Fe]-hydrogenase. One [Mn]-hydrogenase has the highest specific activity of semi-synthetic [Mn]- and [Fe]-hydrogenases. This work demonstrates reconstitution of active artificial hydrogenases using synthetic complexes differing greatly from the native active site.
Coordination Complexes/chemistry , Hydrogenase/chemistry , Ligands , Manganese/chemistry , Biomimetic Materials/chemistry , Biomimetic Materials/metabolism , Catalysis , Catalytic Domain , Hydrogen/chemistry , Hydrogenase/metabolism , Molecular Conformation
The intramolecular [4+2] cycloaddition between arenes and allenes first reported by Himbert gives rapid access to rigid polycyclic scaffolds. Herein, we report a one-pot oxyalkynylation/cycloaddition reaction proceeding under mild conditions (23-90 °C) and providing complex polycyclic architectures with high efficiency, and atom and step economy. The bicyclo[2.2.2]octadiene products were obtained with a wide variety of useful functional groups and were successfully applied as chiral ligands for metal catalysis. Computational studies gave a first rationalization of the low activation energy for the cycloaddition based on counter-intuitive favorable dispersive interactions in the transition state.
Despite the excellent photovoltaic properties achieved by perovskite solar cells at the laboratory scale, hybrid perovskites decompose in the presence of air, especially at high temperatures and in humid environments. Consequently, high-efficiency perovskites are usually prepared in dry/inert environments, which are expensive and less convenient for scale-up purposes. Here, a new approach based on the inclusion of an in situ polymerizable ionic liquid, 1,3-bis(4-vinylbenzyl)imidazolium chloride ([bvbim]Cl), is presented, which allows perovskite films to be manufactured under humid environments, additionally leading to a material with improved quality and long-term stability. The approach, which is transferrable to several perovskite formulations, allows efficiencies as high as 17% for MAPbI3 processed in air % relative humidity (RH) ≥30 (from an initial 15%), and 19.92% for FAMAPbI3 fabricated in %RH ≥50 (from an initial 17%), providing one of the best performances to date under similar conditions.
A novel nickel pincer cofactor was recently discovered in lactate racemase. Reported here are three synthetic nickel pincer complexes that are both structural and functional models of the pincer cofactor in lactate racemase. DFT computations suggest the ipso-carbon atom of the pyridinium pincer ligands act as a hydride acceptor for lactate isomerization, whereas an organometallic pathway involving nickel-mediated ß-hydride elimination is less favored.
Bacterial Proteins/metabolism , Nickel/metabolism , Nucleotides/metabolism , Racemases and Epimerases/metabolism , Biocatalysis , Crystallography, X-Ray , Models, Molecular , Nickel/chemistry , Nucleotides/chemistry
Nature carefully selects specific metal ions for incorporation into the enzymes that catalyse the chemical reactions necessary for life. Hydrogenases, enzymes that activate molecular H2, exclusively utilize Ni and Fe in [NiFe]-, [FeFe]- and [Fe]-hydrogeanses. However, other transition metals are known to activate or catalyse the production of hydrogen in synthetic systems. Here, we report the development of a biomimetic model complex of [Fe]-hydrogenase that incorporates a Mn, as opposed to a Fe, metal centre. This Mn complex is able to heterolytically cleave H2 as well as catalyse hydrogenation reactions. The incorporation of the model into an apoenzyme of [Fe]-hydrogenase results in a [Mn]-hydrogenase with an enhanced occupancy-normalized activity over an analogous semi-synthetic [Fe]-hydrogenase. These findings demonstrate a non-native metal hydrogenase that shows catalytic functionality and that hydrogenases based on a manganese active site are viable.
Biomimetic Materials/chemistry , Coordination Complexes/chemistry , Hydrogenase/chemistry , Iron-Sulfur Proteins/chemistry , Manganese/chemistry , Biomimetic Materials/chemical synthesis , Catalysis , Catalytic Domain , Coordination Complexes/chemical synthesis , Density Functional Theory , Hydrogen/chemistry , Hydrogenase/genetics , Hydrogenation , Iron-Sulfur Proteins/genetics , Methanocaldococcus/enzymology , Models, Chemical , Mutation
The dinuclear SmII complex, [Sm2L4(dme)] (L = OSi(OtBu)3), is easily obtained from the protonolysis reaction of [Sm{N(SiMe3)2}(thf)2] with HOSi(OtBu)3. This complex reacts slowly with toluene, resulting in the isolation of the triple-decker arene-bridged SmII complex, [{Sm2L3}2(µ-η6:η6-C7H8)], in 44% yield. This reactivity provides the first example of unambiguous arene reduction by an isolated SmII species. In contrast, reduction of [SmL3]2 afforded the inverse sandwich complex, [{KSmL3}2(µ-η6:η6-C7H8)].
Covalent adducts of imidazole-based mesoionic carbenes and nitrous oxide (N2 O, "laughing gas") can be converted into azo dyes by reaction with arenes in the presence of AlCl3 or HCl. The azo coupling can be achieved with electron-rich aromatic compounds such as mesitylene, trimethoxybenzene, azulene, or dibenzo-18-crown-6. The latter coupling reaction allows for the easy preparation of a colorimetric sensor for potassium or sodium ions. As a putative intermediate of the reaction with acid, we were able to isolate and structurally characterize a rare diazohydroxide. Using imidazolium compounds with two N2 O groups, it was possible to prepare amine-substituted azo dyes or dyes with two azoarene groups attached to the heterocycle. A triazole-based mesoionic carbene was also found to form a stable covalent adduct with N2 O. The adduct could be used to prepare novel azo triazolium dyes in good yields.
Functionalized imidazolium iodide salts (ionic liquids) modified with CH2 CHCH2 , CH2 CCH, or CH2 CN groups are applied as dopants in the synthesis of CH3 NH3 PbI3 -type perovskites together with a fumigation step. Notably, a solar cell device prepared from the perovskite film doped with the salt containing the CH2 CHCH2 side-chain has a power conversion efficiency of 19.21%, which is the highest efficiency reported for perovskite solar cells involving a fumigation step. However, doping with the imidazolium salts with the CH2 CCH and CH2 CN groups result in perovskite layers that lead to solar cell devices with similar or lower power conversion efficiencies than the dopant-free cell.
