Stable Interfacial Ruthenium Species for Highly Efficient Polyolefin Upcycling.

The present polyolefin hydrogenolysis recycling cases acknowledge that zerovalent Ru exhibits high catalytic activity. A pivotal rationale behind this assertion lies in the propensity of the majority of Ru species to undergo reduction to zerovalent Ru within the hydrogenolysis milieu. Nonetheless, the suitability of zerovalent Ru as an optimal structural configuration for accommodating multiple elementary reactions remains ambiguous. Here, we have constructed stable Ru0-Ruδ+ complex species, even under reaction conditions, through surface ligand engineering of commercially available Ru/C catalysts. Our findings unequivocally demonstrate that surface-ligated Ru species can be stabilized in the form of a Ruδ+ state, which, in turn, engenders a perturbation of the σ bond electron distribution within the polyolefin carbon chain, ultimately boosting the rate-determining step of C-C scission. The optimized catalysts reach a solid conversion rate of 609 g·gRu-1·h-1 for polyethylene. This achievement represents a 4.18-fold enhancement relative to the pristine Ru/C catalyst while concurrently preserving a remarkable 94% selectivity toward valued liquid alkanes. Of utmost significance, this surface ligand engineering can be extended to the gentle mixing of catalysts in ligand solution at room temperature, thus rendering it amenable for swift integration into industrial processes involving polyolefin degradation.

Local Built-In Field at the Sub-nanometric Heterointerface Mediates Cascade Electrochemical Conversion of Lithium-sulfur Batteries.

Heterogeneous catalytic mediators have been proposed to play a vital role in enhancing the multiorder reaction and nucleation kinetics in multielectron sulfur electrochemistry. However, the predictive design of heterogeneous catalysts is still challenging, owing to the lack of in-depth understanding of interfacial electronic states and electron transfer on cascade reaction in Li-S batteries. Here, a heterogeneous catalytic mediator based on monodispersed titanium carbide sub-nanoclusters embedded in titanium dioxide nanobelts is reported. The tunable catalytic and anchoring effects of the resulting catalyst are achieved by the redistribution of localized electrons caused by the abundant built-in fields in heterointerfaces. Subsequently, the resulting sulfur cathodes deliver an areal capacity of 5.6 mAh cm-2 and excellent stability at 1 C under sulfur loading of 8.0 mg cm-2 . The catalytic mechanism especially on enhancing the multiorder reaction kinetic of polysulfides is further demonstrated via operando time-resolved Raman spectroscopy during the reduction process in conjunction with theoretical analysis.

Integrated Photochromic-Photothermal Processes for Catalytic Plastic Upcycling.

Incorporating high-energy ultraviolet (UV) photons into photothermal catalytic processes may enable photothermal-photochemical synergistic catalysis, which represents a transformative technology for waste plastic recycling. The major challenge is avoiding side reactions and by-products caused by these energetic photons. Here, we break through the limitation of the existing photothermal conversion mechanism and propose a photochromic-photothermal catalytic system based on polyol-ligated TiO2 nanocrystals. Upon UV or sunlight irradiation, the chemically bonded polyols can rapidly capture holes generated by TiO2 , enabling photogenerated electrons to reduce Ti4+ to Ti3+ and produce oxygen vacancies. The resulting abundant defect energy levels boost sunlight-to-heat conversion efficiency, and simultaneously the oxygen vacancies facilitate polyester glycolysis by activating the nucleophilic addition-elimination process. As a result, compared to commercial TiO2 (P25), we achieve 6-fold and 12.2-fold performance enhancements under thermal and photothermal conditions, respectively, while maintaining high selectivity to high-valued monomers. This paradigm-shift strategy directs energetic UV photons for activating catalysts and avoids their interaction with reactants, opening the possibility of substantially elevating the efficiency of more solar-driven catalysis.

Analyzing Near-Infrared Electrochemiluminescence of Graphene Quantum Dots in Aqueous Media.

Mechanisms of emissions, especially electrochemiluminescence (ECL), for graphene quantum dots (GQDs) are poorly understood, which makes near-infrared (NIR)-emitting GQDs difficult to create. To explore this poorly understood NIR ECL, two GQDs, nitrogen-doped GQDs (GQD-1) and nitrogen- and sulfur-doped ones (GQD-2), were prepared by a simple one-step solvothermal reaction with similar core structures but different surface states. The GQDs were analyzed by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. Photoluminescence results, with a comparable quantum efficiency of 13% to strong luminophores in aqueous media, suggested a mechanism that the emission mainly depends on the core structure while slightly adjusted by the heteroatom doping. ECL of GQD-2 dispersed in aqueous media with K2S2O8 as the coreactant was measured by means of ECL-voltage curves and ECL spectroscopy, demonstrating strong NIR emissions between 680 and 870 nm, with a high ECL efficiency of 13% relative to that of the Ru(bpy)32+/K2S2O8 system. Interestingly, ECL is generated by surface excited states emitting light at a much longer wavelength in the NIR region. The easily prepared GQD-2 has several advantages such as low cost and quite strong NIR-ECL in aqueous media, with which wide applications in biodetection are anticipated.

Suppressing Dehydroisomerization Boosts n-Butane Dehydrogenation with High Butadiene Selectivity.

Butadiene (BD) is a critical raw material in chemical industry, which is conventionally produced from naphtha cracking. The fast-growing demand of BD and the limited oil reserve motivate chemists to develop alternative methods for BD production. Shale gas, which mainly consists of light alkanes, has been considered as cheap raw materials to replace oil for BD production via n-butane direct dehydrogenation (n-BDH). However, the quest for highly-efficient catalysts for n-BDH is driven by the current drawback of low BD selectivity. Here, we demonstrate a strategy for boosting the selectivity of BD by suppressing dehydroisomerization, an inevitable step in the conventional n-BDH process which largely reduces the selectivity of BD. Detailed investigations show that the addition of alkali-earth metals (e. g., Mg and Ca) into Pt-Ga2 O3 /S10 catalysts increases Pt dispersity, suppresses coke deposition and dehydroisomerization, and thus leads to the significant increase of BD selectivity. The optimized catalyst displays an initial BD selectivity of 34.7 % at a n-butane conversion of 82.1 % at 625 °C, which outperforms the reported catalysts in literatures. This work not only provides efficient catalysts for BD production via n-BDH, but also promotes the researches on catalyst design in heterogeneous catalysis.

Metal Halide Perovskite Nanocrystals in Metal-Organic Framework Host: Not Merely Enhanced Stability.

As an emerging optical material, perovskite nanocrystals (NCs) exhibit excellent optoelectronic properties and show great potential for various optoelectronic applications. However, the inherent inferior stability against moisture, oxygen, light and heat limit their practical application. As well, the exploration and development of perovskite NCs with novel properties and functions are new challenges. To achieve these goals, the integration and encapsulation of perovskite NCs with multifunctional metal-organic frameworks (MOFs) to form perovskite NC@MOF composites, is a promising strategy for enhancing the stability and broadening the application scope. In this minireview, we summarize and discuss the synthesis strategies and functional mechanisms of perovskite NC@MOF composites, along with applications of light emitting diodes (LED), information security, photocatalysis, sensing, and detection. We further briefly point out the current challenges as well as the future opportunities for the emerged composite materials.

Metal-Organic Framework/PVDF Composite Membranes with High H2 Permselectivity Synthesized by Ammoniation.

Herein we report a new ammoniation-based chemical modification strategy for synthesis of continuous and uniform metal-organic framework (MOF)/polyvinylidene fluoride (PVDF) membranes with attractive performance. Ammoniation can promote the support PVDF membrane to produce amino groups, form a nanoparticle structure, and be well cross-linked; therefore, the high-density heterogeneous nucleation sites for MOFs growth were provided and the thermal stability and chemical resistance of composite membranes can be greatly improved. The high-quality layers of representative Cu-BTC and ZIF-8 were synthesized on the chemically modified PVDF membranes. By ammoniation, ZIF-7 can even be grown under harsh synthetic conditions such as in DMF precursor solutions at 403 K. The fabricated MOF/PVDF composite membranes with excellent hollow fiber structures and enhanced structural stability exhibited high H2 permselectivities for H2 /CO2 and H2 /N2 .

Enhancing corannulene chemiluminescence, electrochemiluminescence and photoluminescence by means of an azabora-helicene to slow down its bowl inversion.

Aromatic system extension of corannulene (Cor) is a synthetic challenge to access non-planar polyaromatic hydrocarbons (PAHs). Herein, we report the design and synthesis of azaborahelicene corannulene 1 through hybridization of an azabora[5] helical structure and subsequent luminescence studies. Significant enhancement in chemiluminescence (CL), electroluminescence (ECL) and photoluminescence (PL) is achieved compared to those of pristine Cor. Specifically, hybrid 1 shows a notable augmentation in absolute luminescence quantum efficiencies: 25-fold for CL, up to 23-fold for ECL with BPO as a coreactant, and 30-fold for PL, respectively, compared to those of pristine Cor. Intriguingly, the blue light emission observed in all three luminescence types suggests the presence of a single excited state. As revealed by variable-temperature (VT) 1H NMR experiments, the bowl inversion frequency apparently decelerates by the steric effect of the helix motif in 1, which could contribute to the enhanced luminescent properties by reducing excited energy losses non-radiatively through fewer molecular motions; these enhanced luminescence observations could be categorized alongside the aggregation induced emission (AIE) and crystallization-induced emission (CIE) phenomena. This work not only provides fundamental insights into improved luminescence quantum efficiencies via strategic modulation of the molecular structure and geometry, but the work also reveals Cor's inherent potential to build efficient blue-light emitting materials and devices.

Spectroscopy and absolute quantum efficiency of near-infrared electrochemiluminescence for a macrocyclic palladium complex.

Electrochemiluminescence (ECL) is widely applied as a reliable tool in clinical diagnosis, including immunoassays, cancer biomarker detection, etc. Metal complexes with emission in the near-infrared (NIR) range possess distinct features such as high transmission and minimal tissue auto-absorption, making them versatile for applications in biosensing and other fields. Through ECL spectral studies of an O-linked nonaromatic benzitripyrrin (C^N^N^N) macrocyclic palladium complex (Pd1) with multiple pyrrole structures, we observed emission peaks from the Qx(0,0) and its vibronic Qx(0,1) bands during both photoluminescence (PL) and ECL. Notably, the emission from the Qx(0,1) band was significantly enhanced in the ECL spectrum, demonstrating higher selectivity for near-infrared light at 743 nm. In the ECL annihilation pathway, the appearance of ECL signals showed a strong correlation with the redox processes of the tri-pyrrin structure, revealing a cyclic tri-pyrrin ligand-centered nature with contributions from the metal center. Upon the introduction of tripropylamine (TPrA) and benzoyl peroxide (BPO) coreactants, the ECL signals exhibited enhancements ranging from several hundred to tens of times. Various reaction routes within different coreactant systems are extensively discussed. Additionally, the absolute quantum efficiencies of the Pd1/TPrA coreactant system were determined, showing efficiencies of 0.0032% ± 0.0005% and 0.000074% ± 0.000016% during pulsing and CV scan processes, respectively. This work addresses gaps in the study of palladacycle complexes in ECL and provides insights into the design of NIR luminescent structures that contribute to the fast screening and deep tissue penetration bioimaging techniques.

Mitigating the Trade-Off between Non-Radiative Recombination and Charge Transport to Enable Efficient Ternary Organic Solar Cells.

Ternary organic solar cells (OSCs) have attracted intensive studies due to their promising potential for attaining high-performing photovoltaics, whereas there has been an opening challenge in minimizing the open circuit voltage (Voc) loss while retaining the optimal carrier extraction in the multiple mixture absorbers. Here, we systemically investigate a ternary absorber comprised of two acceptors and a donor, in which the resultant Voc and fill factor are varied and determined by the ratios of acceptor components as a result of the unbalance of non-radiative recombination rates and charge transport. The transient absorption spectroscopy and electroluminescence techniques verify two distinguishable charge-transfer (CT) states in the ternary absorber, and the mismatch of non-radiative recombination rates of those two CT states is demonstrated to be associated with the Voc deficit, whilst the high-emissive acceptor molecule delivers inferior electron mobility, resulting in poor charge transport and a subpar fill factor. These findings enable us to optimize the mixture configuration for attaining the maximal-performing devices. Our results not only provide insight into maximizing the photovoltage of organic solar cells but can also motivate researchers to further unravel the photophysical mechanisms underlying the intermolecular electronic states of organic semiconductors.

Inverted semitransparent perovskite nanocrystal light-emitting diodes with a conjugated polymer as an electron transport layer.

Perovskite nanocrystals have attracted much attention due to their unique optical and electronic properties. Much progress has also been made in the development of light-emitting diodes based on perovskite nanocrystals in the past years. However, compared with the widely reported opaque perovskite nanocrystal light-emitting diodes, semitransparent perovskite nanocrystal light-emitting diodes are rarely studied, which affects the potential application of perovskite nanocrystals in the translucent display field in the future. Here, poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN), a conjugated polymer, was used as an electron transport layer to fabricate the inverted opaque and semitransparent perovskite light-emitting diodes. The maximum external quantum efficiency and luminance were improved from 0.13% and 1041 cd m-2 to 2.07% and 12 540 cd m-2, respectively, through device optimization in opaque light-emitting diodes. The corresponding semitransparent device also demonstrated high transmittance (average 61% from 380 to 780 nm) and high brightness of 1619 and 1643 cd m-2 for the bottom and top sides, respectively.

Site-Selective Polyolefin Hydrogenolysis on Atomic Ru for Methanation Suppression and Liquid Fuel Production.

Catalytic hydrogenolysis of end-of-life polyolefins can produce value-added liquid fuels and therefore holds great promises in plastic waste reuse and environmental remediation. The major challenge limiting the recycling economic benefit is the severe methanation (usually >20%) induced by terminal C-C cleavage and fragmentation in polyolefin chains. Here, we overcome this challenge by demonstrating that Ru single-atom catalyst can effectively suppress methanation by inhibiting terminal C-C cleavage and preventing chain fragmentation that typically occurs on multi-Ru sites. The Ru single-atom catalyst supported on CeO2 shows an ultralow CH4 yield of 2.2% and a liquid fuel yield of over 94.5% with a production rate of 314.93 gfuels gRu -1 h-1 at 250 °C for 6 h. Such remarkable catalytic activity and selectivity of Ru single-atom catalyst in polyolefin hydrogenolysis offer immense opportunities for plastic upcycling.

Graphene-Like Conjugated Molecule as Hole-Selective Contact for Operationally Stable Inverted Perovskite Solar Cells and Modules.

Further enhancing the operational lifetime of inverted-structure perovskite solar cells (PSCs) is crucial for their commercialization, and the design of hole-selective contacts at the illumination side plays a key role in operational stability. In this work, the self-anchoring benzo[rst]pentaphene (SA-BPP) is developed as a new type of hole-selective contact toward long-term operationally stable inverted PSCs. The SA-BPP molecule with a graphene-like conjugated structure shows a higher photostability and mobility than that of the frequently-used triphenylamine and carbazole-based hole-selective molecules. Besides, the anchoring groups of SA-BPP promote the formation of a large-scale uniform hole contact on ITO substrate and efficiently passivate the perovskite absorbers. Benefiting from these merits, the champion efficiencies of 22.03% for the small-sized cells and 17.08% for 5 × 5 cm2 solar modules on an aperture area of 22.4 cm2 are achieved based on this SA-BPP contact. Also, the SA-BPP-based device exhibits promising operational stability, with an efficiency retention of 87.4% after 2000 h continuous operation at the maximum power point under simulated 1-sun illumination, which indicates an estimated T80 lifetime of 3175 h. This novel design concept of hole-selective contacts provides a promising strategy for further improving the PSC stability.

Suppressing thermal quenching of lead halide perovskite nanocrystals by constructing a wide-bandgap surface layer for achieving thermally stable white light-emitting diodes.

Lead halide perovskite nanocrystals as promising ultrapure emitters are outstanding candidates for next-generation light-emitting diodes (LEDs) and display applications, but the thermal quenching behavior of light emission has severely hampered their real-world applications. Here, we report an anion passivation strategy to suppress the emission thermal quenching behavior of CsPbBr3 perovskite nanocrystals. By treating with specific anions (such as SO4 2-, OH-, and F- ions), the corresponding wide-bandgap passivation layers, PbSO4, Pb(OH)2, and PbF2, were obtained. They not only repair the surface defects of CsPbBr3 nanocrystals but also stabilize the phase structure of the inner CsPbBr3 core by constructing a core-shell like structure. The photoluminescence thermal resistance experiments show that the treated sample could preserve 79% of its original emission intensity up to 373 K, far superior to that (17%) of pristine CsPbBr3. Based on the thermally stable CsPbBr3 nanocrystals, we achieved temperature-stable white LED devices with a stable electroluminescence spectrum, color gamut and color coordinates in thermal stress tests (up to 373 K).

High-Efficiency Semitransparent Light-Emitting Diodes with Perovskite Nanocrystals.

Artificial intelligence offers new opportunities for translucent displays. However, achieving translucent light-emitting diodes (LEDs) with high efficiency and high color purity remains a challenge. Here, we propose a strategy of using an alkali metal/inert metal (calcium/silver) bilayer metal electrode as a top electrode and perovskite nanocrystals as an emitter layer in the device structure, which allows us to not only fabricate excellent opaque LEDs but also manufacture highly efficient semitransparent LEDs with high color purity, total brightness (over 7000 cd m-2), total external quantum efficiency (over 12%), and 56% transmittance around 520 nm. This is the highest external quantum efficiency report about semitransparent LED based on perovskite materials or inorganic quantum dots so far, which presents great application potential in the field of translucent display with high color purity and wide color gamut.

Synthesis of lead halide perovskite nanocrystals by melt crystallization in halide salts.

CsPbBr3 nanocrystals (NCs) are successfully prepared by using SrBr2 salt as a growth medium in a melt crystallization process. The obtained CsPbBr3 NCs exhibit a photoluminescence peak of 524 nm with a narrow emission linewidth of 25 nm, which can offer a wide color gamut display. This study can be extended to other alkali metal and alkali earth metal halides and may become a general method for the synthesis of perovskite NCs.

High-efficiency perovskite nanocrystal light-emitting diodes via decorating NiOx on the nanocrystal surface.

Nickel oxides exhibit a great potential as hole transport layers for the fabrication of efficient perovskite light-emitting diodes (LEDs) due to their high carrier mobility and good energy band matching with perovskite nanocrystals. In this work, nickel oxides were directly decorated on the CsPbBr3 nanocrystal surface through adsorption and a sequential oxidation treatment. The resulting sample shows a high photoluminescence quantum-yield of 82%. The LED using CsPbBr3 nanocrystals with nickel oxides achieves a high external quantum efficiency (EQE) of up to 16.8% with a low turn-on voltage of 2.8 V, which is much superior to that of the counterpart LED based on pristine CsPbBr3 nanocrystals (EQE = 0.7%, turn-on voltage = 5.6 V). The excellent performance of the nickel oxide decorated CsPbBr3 nanocrystal device could be attributed to the better energy level matching between the decorated nanocrystals and the transport layers of the device and more balanced charge carrier injection. Furthermore, the operational lifetime of the nickel oxide decorated CsPbBr3 nanocrystal device is 40 times longer than that of the pristine CsPbBr3 nanocrystal device.

Ceramic-like stable CsPbBr3 nanocrystals encapsulated in silica derived from molecular sieve templates.

Achieving good stability while maintaining excellent properties is one of the main challenges for enhancing the competitiveness of luminescent perovskite CsPbX3 (X=Cl, Br, I) nanocrystals (NCs). Here, we propose a facile strategy to synthesize ceramic-like stable and highly luminescent CsPbBr3 NCs by encapsulating them into silica derived from molecular sieve templates at high temperature (600-900 oC). The obtained CsPbBr3-SiO2 powders not only show high photoluminescence quantum yield (~71%), but also show an exceptional stability comparable to the ceramic Sr2SiO4:Eu2+ green phosphor. They can maintain 100% of their photoluminescence value under illumination on blue light-emitting diodes (LEDs) chips (20 mA, 2.7 V) for 1000 h, and can also survive in a harsh hydrochloric acid aqueous solution (1 M) for 50 days. We believe that the above robust stabilities will significantly enhance the potential of perovskite CsPbX3 NCs to be practically applied in LEDs and backlight displays.

Critical role of metal ions in surface engineering toward brightly luminescent and stable cesium lead bromide perovskite quantum dots.

The highly dynamic binding ligands on the surface of all-inorganic cesium lead halide perovskite quantum dots (PQDs), which can be easily lost or detached leading to a deterioration in the optical properties and stability, are one of the greatest challenges for the practical storage and application of PQDs. Herein, we report a facile metal ion-assisted ligand surface engineering strategy to synchronously boost the photoluminescence quantum yield and stability of CsPbBr3 PQDs by a sequential short-chain ligand (didodecyl dimethylammonium sulfide, DDA+-S2-) exchange and subsequent metal salt (In(Ac)3) treatment. From detailed characterization of the critical role of the metal ions, these enhancements were found to originate from the promoted ligand capping induced by the metal ions attached on the surface of the PQDs. Considering the shortened ligands and robust surface passivation, the modified CsPbBr3 PQDs exhibit drastically enhanced performance in an electroluminescent device. Our results have provided an insightful understanding of surface ligand engineering for high-quality and stable perovskite QDs and their effective optoelectronic applications.

Sacrificial oxidation of a self-metal source for the rapid growth of metal oxides on quantum dots towards improving photostability.

Growth of metal oxide layers on quantum dots (QDs) has been regarded as a good way to improve the photostability of QDs. However, direct growth of metal oxides on individual QD remains a great challenge. Here we report a novel approach to rapidly anchor metal oxides on QD surfaces through a sacrificial oxidation of a self-metal source strategy. As typical core/shell QDs, CdSe/CdS or aluminum doped CdSe/CdS (CdSe/CdS:Al) QDs were chosen and treated with peroxide (benzoyl peroxide). Self-metal sources (cadmium or/and aluminum) can be easily sacrificially oxidized, leading to the quick growth of cadmium oxide (CdO) or aluminum/cadmium hybrid oxides (Al2O3/CdO) on the surface of individual QD for improved photostability. Compared with CdO, Al2O3 possesses excellent barrier properties against moisture and oxygen. Therefore, CdSe/CdS QDs with the protection of an Al2O3/CdO hybrid layer show much superior photostability. Under strong illumination with blue light, the QDs coated with the Al2O3/CdO hybrid layer retained 100% of the original photoluminescence intensity after 70 h, while that of the untreated CdSe/CdS:Al, the treated CdSe/CdS and the CdSe/CdS QDs dropped to 65%, 45%, and 5%, respectively. Furthermore, we demonstrate that this method can be extended to other metal-doped QD systems, even including some inactive metals difficult to be oxidized spontaneously in an ambient atmosphere, which provides a new way to stabilize QDs for diverse optoelectronic applications.