Electronic Structure Manipulation of the Mott Insulator RuCl3 via Single-Crystal to Single-Crystal Topotactic Transformation

The core task for Mott insulators includes how rigid distributions of electrons evolve and how these induce exotic physical phenomena. However, it is highly challenging to chemically dope Mott insulators to tune properties. Herein, we report how to tailor electronic structures of the honeycomb Mott insulator RuCl₃ employing a facile and reversible single-crystal to single-crystal intercalation process. The resulting product (NH₄)_0.5RuCl₃⋅1.5 H₂O forms a new hybrid superlattice of alternating RuCl₃ monolayers with NH₄⁺ and H₂O molecules. Its manipulated electronic structure markedly shrinks the Mott–Hubbard gap from 1.2 to 0.7 eV. Its electrical conductivity increases by more than 10³ folds. This arises from concurrently enhanced carrier concentration and mobility in contrary to the general physics rule of their inverse proportionality. We show topotactic and topochemical intercalation chemistry to control Mott insulators, escalating the prospect of discovering exotic physical phenomena.     

Synergistic Interplay of Dual-Active-Sites on Metallic Ni-MOFs Loaded with Pt for Thermal-Photocatalytic Conversion of Atmospheric CO2 under Infrared Light Irradiation

Infrared light driven photocatalytic reduction of atmospheric CO₂ is challenging due to the ultralow concentration of CO₂ (0.04 %) and the low energy of infrared light. Herein, we develop a metallic nickel-based metal–organic framework loaded with Pt (Pt/Ni-MOF), which shows excellent activity for thermal-photocatalytic conversion of atmospheric CO₂ with H₂ even under infrared light irradiation. The open Ni sites are beneficial to capture and activate atmospheric CO₂, while the photogenerated electrons dominate H₂ dissociation on the Pt sites. Simultaneously, thermal energy results in spilling of the dissociated H₂ to Ni sites, where the adsorbed CO₂ is thermally reduced to CO and CH₄. The synergistic interplay of dual-active-sites renders Pt/Ni-MOF a record efficiency of 9.57 % at 940 nm for converting atmospheric CO₂, enables the procurement of CO₂ to be independent of the emission sources, and improves the energy efficiency for trace CO₂ conversion by eliminating the capture media regeneration and molecular CO₂ release.     

Light Triggered Pore Size Tuning in Photoswitching Covalent Triazine Frameworks for Low Energy CO2 Capture

Recently, photo switching porous materials have been widely reported for low energy costed CO₂ capture and release via simply remoted light controlling method. However, most reported photo responsive CO₂ adsorbents relied on metal organic framework (MOFs) functionalisation with photochromic moieties, and MOF adsorbents still suffered from chemically and thermally unstable issues. Thus, further metal free and highly stable organic photoresponsive adsorbents are necessary to be developed. CTFs, because of their high porosity and stability, have attracted great attention for CO₂ capture. Considering the high CO₂ uptake capacity and structural tunability of CTFs, it suggests high potential to fabricate the photoswitching CTF materials by the same functionalisation method as MOFs. Herein, the first series of photo switching CTFs were developed for low energy CO₂ capture and release. Apart from that, the CO₂ switching efficiency could be doubled either through the azobenzene numbers adjusting method or through the previously reported structural alleviation strategy. Furthermore, the pore size distribution of azobenzene functionalised PCTFs also could be tuned under UV exposure, which may contribute to the UV light induced decrease of CO₂ uptake capacity. These photoswitching CTFs represented a new kind of porous polymers for low energy costed CO₂ capture.     

Synergic Electron and Defect Compensation Minimizes Voltage Loss in Lead-Free Perovskite Solar Cells

Sn perovskite solar cells have been regarded as one of the most promising alternatives to the Pb-based counterparts due to their low toxicity and excellent optoelectronic properties. However, the Sn perovskites are notorious to feature heavy p-doping characteristics and possess abundant vacancy defects, which result in under-optimized interfacial energy level alignment and severe nonradiative recombination. Here, we reported a synergic “electron and defect compensation” strategy to simultaneously modulate the electronic structures and defect profiles of Sn perovskites via incorporating a traced amount (0.1 mol %) of heterovalent metal halide salts. Consequently, the doping level of modified Sn perovskites was altered from heavy p-type to weak p-type (i.e. up-shifting the Fermi level by ∼0.12 eV) that determinately reducing the barrier of interfacial charge extraction and effectively suppressing the charge recombination loss throughout the bulk perovskite film and at relevant interfaces. Pioneeringly, the resultant device modified with electron and defect compensation realized a champion efficiency of 14.02 %, which is ∼46 % higher than that of control device (9.56 %). Notably, a record-high photovoltage of 1.013 V was attained, corresponding to the lowest voltage deficit of 0.38 eV reported to date, and narrowing the gap with Pb-based analogues (∼0.30 V).     

Enhancing Carrier Transport via σ-Linkage Length Modulation in D-σ-A Semiconductors for Photocatalytic Oxidation

Carrier transport is an equally decisive factor as carrier separation for elevating photocatalytic efficiency. However, limited by indefinite structures and low crystallinities, studies on enhancing carrier transport of organic photocatalysts are still in their infancy. Here, we develop an σ-linkage length modulation strategy to enhance carrier transport in imidazole-alkyl-perylene diimide (IMZ-alkyl-PDI, corresponding to D-σ-A) photocatalysts by controlling π–π stacking distance. Ethyl-linkage can shorten π–π stacking distance (3.19 Å) the most among IMZ-alkyl-PDIs (where alkyl=none, ethyl, and n-propyl) via minimizing steric hindrance between D and A moieties, which leads to the fastest carrier transport rates. Thereby, IMZ-ethyl-PDI exhibits remarkable enhancement in phenol degradation with 32-fold higher rates than IMZ-PDI, as well as the oxygen evolution rate (271-fold increased). In microchannel reactors, IMZ-ethyl-PDI also presents 81.5 % phenol removal with high-flux surface hydraulic loading (44.73 L m⁻² h⁻¹). Our findings provide a promising molecular design guideline for high-performance photocatalysts and elucidate crucial internal carrier transport mechanisms.