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.

Layered Double Hydroxide Derivatives for Polyolefin Upcycling.

While Ru-catalyzed hydrogenolysis holds significant promise in converting waste polyolefins into value-added alkane fuels, a major constraint is the high cost of noble metal catalysts. In this work, we propose, for the first time, that Co-based catalysts derived from CoAl-layered double hydroxide (LDH) are alternatives for efficient polyolefin hydrogenolysis. Leveraging the chemical flexibility of the LDH platform, we reveal that metallic Co species serve as highly efficient active sites for polyolefin hydrogenolysis. Furthermore, we introduced Ni into the Co framework to tackle the issue of restricted hydrogenation ability associated with contiguous Co-Co sites. In-situ analysis indicates that the integration of Ni induces electron transfer and facilitates hydrogen spillover. This dual effect synergistically enhances the hydrogenation/desorption of olefin intermediates, resulting in a significant reduction in the yield of low-value CH4 from 27.1 to 12.6%. Through leveraging the unique properties of LDH, we have developed efficient and cost-effective catalysts for the sustainable recycling and valorization of waste polyolefin materials.

The Role of Bismuth in Suppressing the CO Poisoning in Alkaline Methanol Electrooxidation: Switching the Reaction from the CO to Formate Pathway.

While tuning the electronic structure of Pt can thermodynamically alleviate CO poisoning in direct methanol fuel cells, the impact of interactions between intermediates on the reaction pathway is seldom studied. Herein, we contrive a PtBi model catalyst and realize a complete inhibition of the CO pathway and concurrent enhancement of the formate pathway in the alkaline methanol electrooxidation. The key role of Bi is enriching OH adsorbates (OHad) on the catalyst surface. The competitive adsorption of CO adsorbates (COad) and OHad at Pt sites, complementing the thermodynamic contribution from alloying Bi with Pt, switches the intermediate from COad to formate that circumvents CO poisoning. Hence, 8% Bi brings an approximately 6-fold increase in activity compared to pure Pt nanoparticles. This notion can be generalized to modify commercially available Pt/C catalysts by a microwave-assisted method, offering opportunities for the design and practical production of CO-tolerance electrocatalysts in an industrial setting.

Seed-Mediated Growth for High-Efficiency Perovskite Solar Cells: The Important Role of Seed Surface.

Additive engineering has emerged as one of the most promising strategies to improve the performance of perovskite solar cells (PSCs). Among additives, perovskite nanocrystals (NCs) have a similar chemical composition and matched lattice structure with the perovskite matrix, which can effectively enhance the efficiency and stability of PSCs. However, relevant studies remain limited, and most of them focus on bromide-involved perovskite NCs, which may undergo dissolution and ion exchange within the FAPbI3 host, potentially resulting in an enlarged band gap. In this work, we employ butylamine-capped CsPbI3 NCs (BPNCs) as additives in PSCs, which can be well maintained and serve as seeds for regulating the crystallization and growth of perovskite films. The resultant perovskite film exhibits larger domain sizes and fewer grain boundaries without compromising the band gap. Moreover, BPNCs can alleviate lattice strain and reduce defect densities within the active layer. The PSCs incorporating BPNCs show a champion power conversion efficiency (PCE) of up to 25.41 %, well over both Control of 22.09 % and oleic acid/oleylamine capped CsPbI3 NC (PNC)-based devices of 23.11 %. This work illustrates the key role of nanosized seed surfaces in achieving high-performance photovoltaic devices.

3D/2D Core/Shell Perovskite Nanocrystals for High-Performance Solar Cells.

All-inorganic lead halide perovskite nanocrystals (NCs) emerge as a rising star in photovoltaic fields on account of their excellent optoelectronic properties. However, it still remains challenging to further promote photovoltaic efficiency due to the susceptible surface and inevitable vacancies. Here, this work reports a 3D/2D core/shell perovskite heterojunction based on CsPbI3 NCs and its performance in solar cells. The guanidinium (GA+ ) rich 2D nanoshells can significantly passivate surface trap states and lower the capping ligand density, resulting in improved photoelectric properties and carrier transport and diminished nonradiative recombination centers via the hydrogen bonds from amino groups in GA+ ions. Consequently, an outstanding power conversion efficiency (PCE) of up to 15.53% is realized, substantially higher than the control device (13.77%). This work highlights the importance of surface chemistry and offers a feasible avenue to achieve high-performance perovskite NCs-based optoelectronic devices.

Entropy Confinement Promotes Hydrogenolysis Activity for Polyethylene Upcycling.

Chemical upcycling that catalyzes waste plastics back to high-purity chemicals holds great promise in end-of-life plastics valorization. One of the main challenges in this process is the thermodynamic limitations imposed by the high intrinsic entropy of polymer chains, which makes their adsorption on catalysts unfavorable and the transition state unstable. Here, we overcome this challenge by inducing the catalytic reaction inside mesoporous channels, which possess a strong confined ability to polymer chains, allowing for stabilization of the transition state. This approach involves the synthesis of p-Ru/SBA catalysts, in which Ru nanoparticles are uniformly distributed within the channels of an SBA-15 support, using a precise impregnation method. The unique design of the p-Ru/SBA catalyst has demonstrated significant improvements in catalytic performance for the conversion of polyethylene into high-value liquid fuels, particularly diesel. The catalyst achieved a high solid conversion rate of 1106 g ⋅ gRu -1 ⋅ h-1 at 230 °C. Comparatively, this catalytic activity is 4.9 times higher than that of a control catalyst, Ru/SiO2 , and 14.0 times higher than that of a commercial catalyst, Ru/C, at 240 °C. This remarkable catalytic activity opens up immense opportunities for the chemical upcycling of waste plastics.

Breaking the Size Limitation of Directly-Synthesized PbS Quantum Dot Inks Toward Efficient Short-wavelength Infrared Optoelectronic Applications.

PbS quantum dots (QDs) are promising building blocks for solution-processed short-wavelength infrared (SWIR) devices. The recently developed direct synthesis of semi-conductive PbS QD inks has substantially simplified the preparation processing and reduced the material cost, while facing the challenge to synthesize large-size QDs with absorption covering the SWIR region. Herein, we for the first time realize a low-cost, scalable synthesis of SWIR PbS QD inks after an extensive investigation of the reaction kinetics. Finally, based on these PbS SWIR QD inks, the solar cell demonstrates a record-high power conversion efficiency (PCE) of 1.44 % through an 1100 nm cutoff silicon filter and the photodetector device shows a low dark current density of 2×10-6  A cm-2 at -0.8 V reverse bias with a high external quantum efficiency (EQE) of 70 % at ≈1300 nm. Our results realize the direct synthesis of low-cost and scalable SWIR QD inks and may accelerate the industrialization of consumer SWIR technologies.

Ultra-Stable CsPbX3 @Pyrophosphate Nanoparticles in Water over One Year.

All-inorganic lead halide perovskite (CsPbX3 , X = Cl, Br, I, or their mixture) nanocrystals (NCs) have achieved inspiring advancements in optoelectronic fields but still suffer from poor durability when exposed to environmental stimuli such as water, irradiation and heat. Herein, a strategy of employing pyrophosphate as the inert shell for CsPbX3 NCs is reported. The strong binding between pyrophosphate and CsPbBr3 surface can stabilize the perovskite structure well. The as-obtained core@shell CsPbBr3 @NH4 AlP2 O7 NCs exhibit impressive stability against water and maintain the initial optical properties with negligible change in 400 days. Furthermore, significant improvement of irradiation/thermal resistance is realized due to the protecting role of pyrophosphate. The NCs can retain 100% and ≈90% of the original PL after hundreds of heating/cooling cycles and several hundred hours of UV light irradiation, respectively. As a result, the core@shell products can be directly used for high-resolution inkjet printing, enabling the printed fluorescent information to be resistant under harsh environmental conditions. This work provides a promising way for the synthesis of highly stable encapsulated perovskite NCs and demonstrates a great potential in practical applications.

Fabricating MAPbI3/MoS2 Composites for Improved Photocatalytic Performance.

Although lead halide perovskites are demonstrated to be promising photocatalysts for hydrogen evolution from hydrogen halide splitting, it still remains challenging to fabricate efficient and stable catalysts. Here MoS2 nanoflowers with abundant active sites are assembled with methylammonium lead iodide (MAPbI3) microcrystals to form a new heterostructure. Its hydrogen evolution rate can reach up to about 30 000 µmol g-1 h-1, which is more than 1000-fold higher than pristine MAPbI3 under visible light irradiation (λ ≥ 420 nm). Importantly, the solar HI splitting efficiency reaches 7.35%, one of the highest efficiencies so far. The introduction of MoS2 with proper band alignment and unsaturated species can efficiently promote the charge separation and afford more active sites for H2 production. This finding not only provides a highly efficient and stable photocatalyst for hydrogen evolution but also offers a useful modification strategy on lead halide perovskites.

Interfacial Manganese-Doping in CsPbBr3 Nanoplatelets by Employing a Molecular Shuttle.

Mn-doping in cesium lead halide perovskite nanoplatelets (NPls) is of particular importance where strong quantum confinement plays a significant role towards the exciton-dopant coupling. In this work, we report an immiscible bi-phasic strategy for post-synthetic Mn-doping of CsPbX3 (X=Br, Cl) NPls. A systematic study shows that electron-donating oleylamine acts as a shuttle ligand to transport MnX2 through the water-hexane interface and deliver it to the NPls. The halide anion also plays an essential role in maintaining an appropriate radius of Mn2+ and thus fulfilling the octahedral factor required for the formation of perovskite crystals. By varying the thickness of parent NPls, we can tune the dopant incorporation and, consequently, the exciton-to-dopant energy transfer process in doped NPls. Time-resolved optical measurements offer a detailed insight into the exciton-to-dopant energy transfer process. This new approach for post-synthetic cation doping paves a way towards exploring the cation exchange process in several other halide perovskites at the polar-nonpolar interface.

Revealing the Correlation between Catalytic Selectivity and the Local Coordination Environment of Pt Single Atom.

Single atom catalysts (SACs) have recently attracted great attention in heterogeneous catalysis and have been regarded as ideal models for investigating the strong interaction between metal and support. Despite the huge progress over the past decade, the deep understanding on the structure-performance correlation of SACs at a single atom level still remains to be a great challenge. In this study, we demonstrate that the variation in the coordination number of the Pt single atom can significantly promote the propylene selectivity during propyne semihydrogenation (PSH) for the first time. Specifically, the propylene selectivity greatly increases from 65.4% to 94.1% as the coordination number of Pt-O increases from ∼3.4 to ∼5, whereas the variation in the coordination number of Pt-O slightly influences the turnover frequency values of SACs. We anticipate that the present work may deepen the understanding on the structure-performance of SACs and also promote the fundamental research in single atom catalysis.

L-Type Ligand-Assisted Acid-Free Synthesis of CsPbBr3 Nanocrystals with Near-Unity Photoluminescence Quantum Yield and High Stability.

X-type ligands, for example, the pair of oleylamine (OAm) and oleic acid (OA), have been widely used to prepare CsPbX3 nanocrystals (NCs). However, the proton exchange between coordinated OAm and OA may induce the detachment of ligands, resulting in poor performance after cleaning or long-time storage. Herein, density functional theory calculations predict that primary amines (L-type ligands) can stabilize a PbBr x-rich surface and yield a trap-free material with fully delocalized valence band maximum and conduction band minimum states, which can significantly improve the photophysical properties and stability of CsPbBr3 NCs. Along this prediction, a room-temperature reprecipitation method using L-type ligands (OAm, n-octylamine, or undecylamine) as the sole capping ligand has been developed to synthesize high-quality CsPbBr3 NCs with near-unity photoluminescence quantum yield and dramatically improved stability against purification and water treatment. The enhancement can be attributed to the strong binding of unprotonated amines to lead atoms and the effective surface passivation provided by the resulted PbBr x-rich surface, which are highly consistent with the theoretical predictions. This work not only offers an approach to synthesize high-quality perovskite NCs but also provides an in-depth understanding of the surface modification of CsPbX3 NCs for practical applications.

Bi(OH)3/PdBi Composite Nanochains as Highly Active and Durable Electrocatalysts for Ethanol Oxidation.

Developing high-performance electrocatalysts for the ethanol oxidation reaction (EOR) is critical to the commercialization of direct ethanol fuel cells. However, current EOR catalysts suffer from high cost, low activity, and poor durability. Here we report the preparation of PdBi-Bi(OH)3 composite nanochains with outstanding EOR activity and durability. The incorporation of Bi can tune the electronic structure and downshift the d-band center of Pd while the surface decoration of Bi(OH)3 can facilitate the oxidative removal of CO and other carbonaceous intermediates. As a result, the nanochains manifest an exceptional mass activity (5.30 A mgPd-1, 4.6-fold higher than that of commercial Pd/C) and outstanding durability (with a retained current density of ∼1.00 A mgPd-1 after operating for 20 000 s). More importantly, the nanochain catalyst can be reactivated, and negligible activity loss has been observed after operating for 200 000 s with periodic reactivation, making it one of the best EOR catalysts.

Hydrochromic CsPbBr3 Nanocrystals for Anti-Counterfeiting.

Hydrochromic materials that can reversibly change color upon water treatment have attracted much attention owing to their potential applications in diverse fields. Herein, for the first time, we report that space-confined CsPbBr3 nanocrystals (NCs) are hydrochromic. When CsPbBr3 NCs are loaded into a porous matrix, reversible transition between luminescent CsPbBr3 and non-luminescent CsPb2 Br5 can be achieved upon the exposure/removal of water. The potential applications of hydrochromic CsPbBr3 NCs in anti-counterfeiting are demonstrated by using CsPbBr3 NCs@mesoporous silica nanospheres (around 100 nm) as the starting material. Owing to the small particle size and negatively charged surface, the as-prepared particles can be laser-jet printed with high precision and high speed. We demonstrate the excellent stability over repeated transformation cycles without color fade. This new discovery may not only deepen the understanding of CsPbX3 , but also open a new way to design CsPbX3 materials for new applications.

Improving the Stability and Size Tunability of Cesium Lead Halide Perovskite Nanocrystals Using Trioctylphosphine Oxide as the Capping Ligand.

Recently, all-inorganic cesium lead halide (CsPbX3, X = Cl, Br, and I) nanocrystals (NCs) have drawn wide attention because of their excellent optoelectronic properties and potential applications. However, one of the most significant challenges of such NCs is their low stability against protonic solvents. In this work, we demonstrate that by incorporating a highly branched capping ligand, trioctylphosphine oxide (TOPO), into the traditional oleic acid/oleylamine system, monodisperse CsPbX3 NCs with excellent optoelectronic properties can be achieved at elevated temperatures (up to 260 °C). The size of such NCs can be varied in a relatively wide range. The capping of TOPO on NCs has been verified through Fourier transform infrared spectroscopy measurement. More importantly, the presence of TOPO can dramatically improve the stability of CsPbX3 NCs against ethanol treatment. After ethanol treatment for 100 min, the emission intensity of the TOPO-capped sample dropped only 5%, whereas that of non-TOPO-capped NCs dropped up to 86%. This work may shed some light on the preparation and application of CsPbX3 NCs with higher stability.

The Synergy between Metal Facet and Oxide Support Facet for Enhanced Catalytic Performance: The Case of Pd-TiO2.

The demand for catalyst with higher activity and higher selectivity is still a central issue in current material science community. On the basis of first-principles calculations, we demonstrate that the catalytic performance of the Pd-TiO2 hybrid nanostructures can be selectively promoted or depressed by choosing the suitable shaped Pd and TiO2 nanocrystals. To be more specific, the catalytic activities of Pd nanoparticles enclosed by (100) or (111) facets can be promoted more significantly when dosed on the TiO2(001) than on TiO2(101) under irradiation. Such theoretical prediction has then been further verified by the experimental observations in which the Pd(100)-TiO2(001) composites exhibit the highest catalytic performance toward the activation of oxygen among all the other shaped hybrid nanostructures. As a result, the selection of facets of support materials can provide an extra tuning parameter to control the catalytic activities of metal nanoparticles. This research opened up a new direction for designing and preparing catalysts with enhanced catalytic performance.

Photocatalytic Upcycling of Different Types of Plastic Wastes: A Mini Review.

With the escalating demand and utilization of plastics, considerable attention has been given to controlling plastic pollution. Among these methodologies, photocatalytic upcycling of plastic has emerged as a promising method for plastic management due to its energy-saving and eco-friendly properties. In the past several years, great efforts have been devoted to the photocatalytic conversion of a variety of commercial plastic types. These encouraging endeavors foreshadow the continued progression and application in this field. In this review, recent advancements in the photocatalytic upcycling of plastics are reviewed. The fundamentals and principles of photocatalytic deconstruction of plastics are first introduced. Then, we summarize the works on the reforming of different types of plastic, including polyolefins, polyesters, and other types. Finally, some challenges and possible solutions are provided for the development of photocatalytic upcycling of plastics.

Ligand Engineering for Mitigating Exciton-Phonon Coupling in Mixed Halide Perovskite Nanocrystals.

The vulnerability of mixed halide perovskite nanocrystals (NCs) remains challenging because of the weak interaction between commonly employed ligands, oleic acid/oleylamine (OAm/OA) and halide anions, coupled with substantial surface phonon energy. Here, we introduce 3-aminopropyltriethoxysilane (APTES) as a capping ligand to modify CsPbBrI2 NCs to enhance the interactions between them. The optical properties have been significantly enhanced, and halide segregation has been suppressed, both of which can be attributed to the reduced phonon energy and exciton-phonon coupling strength. Moreover, these APTES-CsPbBrI2 NCs exhibit a broad color gamut and sustained color stability during long-term operation, indicating their promising potential in display technologies. This work may offer insights into surface engineering to enhance the properties and band stability of mixed halide perovskite NCs.

Advances in solar-driven, electro/photoelectrochemical, and microwave-assisted upcycling of waste polyesters.

Plastic waste in the environment causes significant environmental pollution. The potential of using chemical methods for upcycling plastic waste offers a dual solution to ensure resource sustainability and environmental restoration. This article provides a comprehensive overview of the latest technologies driven by solar-driven, electro/photoelectrochemical-catalytic, and microwave-assisted methods for the conversion of plastics into various valuable chemicals. It emphasizes selective conversion during the plastic transformation process, elucidates reaction pathways, and optimizes product selectivity. Finally, the article offers insights into the future developments of chemical upcycling of polyesters.

Hydrogen Bubbles: Harmonizing Local Hydrogen Transfer for Efficient Plastic Hydro-Depolymerization.

Hydro-depolymerization presents a promising avenue for transforming plastic waste into high-value hydrocarbons, offering significant potential for value-added recycling. However, a major challenge in this method arises from kinetic limitations due to insufficient hydrogen concentration near the active sites, requiring optimal catalytic performance only at higher hydrogen pressures. In this study, we address this hurdle by developing "hydrogen bubble catalysts" featuring Ru nanoparticles within mesoporous SBA-15 channels (Ru/SBA). The distinctive feature of Ru/SBA catalysts lies in their capacity for physical hydrogen storage and chemically reversible hydrogen spillover, ensuring a timely and ample hydrogen supply. Under identical reaction conditions, the catalytic activity of Ru/SBA surpassed that of Ru/SiO2 (no hydrogen storage capacity) by over 4-fold. This substantial enhancement in catalytic performance provides significant opportunities for near atmospheric pressure hydro-depolymerization of plastic waste.