Materials Today最新文献

The potential for directly converting CO₂ to valuable liquid fuels utilizing green and renewable electricity has sparked significant interest in CO₂ electroreduction (CO₂RR). In recent years, CO₂ conversion to formate/formic acid (HCOO⁻/HCOOH) has witnessed fast growth due to its economic and technological viability combined with the development of highly selective catalysts and practical electrolyzes. In this review, we summarize and discuss recent advances in HCOOH generation from CO₂ reduction in terms of (1) the rationale behind choosing HCOOH as a CO₂ electroreduction product, (2) mechanistic pathways to form HCOOH, (3) novel electrocatalyst developments for enhanced HCOOH production, and (4) electrolyzer designs that tackle practical challenges in scalability, reaction rate, and product impurities. Finally, a brief outlook on future opportunities in this field is offered to accelerate the industrialization of CO₂RR to HCOOH.

Few- to hundred-atom-composed metal nanoclusters (NCs) lie in the transition regime between molecular- and nanometer-scales and have attracted intensive attention for their emerging molecule-like properties that energetically serve various sectors of applications. We here deploy this review in a novel viewpoint, namely the emphasis on the diverse molecule-like properties of metal NCs. We start to clarify the uniqueness in size, precision in total structure, and diversity in species of the molecularly pure metal NCs. This poses the origin of their molecule-like performances. Specifically, it in sequence involves the reminiscent concepts coined in molecular science (i.e., chirality, isomerization, and total synthesis); the most impressive molecule-like optical properties; the emergence of DNA-like helical ensembles mimicking biomolecules and their assemblies. We also provide our perspectives on future molecule-like NCs research, focusing on their fundamental importance and practical value. This review is expected to provide a brand-new viewpoint to revisit the science of metal NCs, by deepening the concept of the metallic molecule and admiring the molecule-like features of metal NCs, which may feed the new vitality and flavors to the various sections of fundamentals and applications in the future.

Hypoxia induces the generation of immunosuppressive adenosine within the tumor microenvironment (TME) and further impedes the activation of antitumor immunity triggered by photothermal therapy (PTT). In this study, a photothermal microalgae system (PTA) based on Chlorella sorokiniana (C. soro) is developed to boost antitumor immune responses by targeting the hypoxia-adenosine axis. PTA is constructed by coating polydopamine (PDA), a promising photothermal agent with good biocompatibility, on the surface of C. soro. Due to the inherent photosynthetic capability of microalgae, PTA in situ generates O₂ within the tumor under irradiation at 660 nm for hypoxia alleviation, thereby downregulating the level of adenosine to reverse the immunosuppression in TME. Subsequently, this reshaped TME promotes the activation of antitumor immunity induced by PTT, which is realized by the coated PDA layer on C. soro under irradiation at 808 nm. In a mouse model of 4T1 tumors, PTA significantly weakens the immunosuppression in the TME, elicits robust antitumor immune responses, and suppresses tumor growth. Together, this strategy highlights the potential of leveraging living photosynthetic microalgae as an oxygenerator to boost cancer photothermal immunotherapy.

Metal halide perovskites, known for their outstanding optical properties such as high photoluminescence quantum yield, exceptional color purity, and tunable bandgap, have emerged as promising semiconductor materials for next-generation display technologies. Nonetheless, producing pure red emissions from ∼ 10 nm-sized CsPbI₃ perovskite nanocrystals (PeNCs) remains a significant challenge for perovskite light-emitting didoes (PeLEDs). Here, we present the facile surface bromination strategy of CsPbI₃ PeNCs for pure red PeLEDs. The mild post-ligand treatment on CsPbI₃ PeNCs produces surface-brominated PeNCs, denoted as CsPbI₃:Br, while preserving the original CsPbI₃ crystal structure intact. The resulting CsPbI₃:Br PeNCs exhibit bright pure red luminescence and significant improvements in electrical properties. The PeLEDs, fabricated with these PeNCs, achieve a remarkable external quantum efficiency (EQE) of 19.8 %, comparable to those of the best reported pure red PeLEDs. Finally, we have showcased the application of these PeLEDs as skin-attachable PeLEDs, showing stable operations under various mechanical deformations. This study not only provides a straightforward method for producing pure red PeNCs, but also highlights their potential in wearable electronic applications.

Lithium-ion batteries (LIBs) are insufficient for large-scale energy storage due to limited lithium resources. Sodium-ion batteries (SIBs) are considered the most promising alternative to LIBs due to their abundant resources and potential for broad industrialization. However, the rapid development of SIBs is hindered by the availability of suitable anode materials. Most reported anode materials for SIBs are either expensive or have inherent flaws, making them unsuitable for large-scale production. Carbon materials have gained significant attention due to their sample resources, low cost, and diverse structures. However, the lack of a systematic discussion on the various structural configurations of carbon materials is a challenging issue. This review comprehensively investigated the preparation processes for nearly all carbon-based materials, including graphite, soft carbon, and hard carbon. It also proposed optimization strategies by thoroughly exploring the sodium storage mechanism of various carbon materials. In addition, based on advanced in-situ characterization technology, the solid electrolyte interface and structural changes of carbon materials during the electrochemical process were summarized. A creative analysis was conducted to establish a correlation relationship between the long-range and short-range ordered structure of carbon materials and their impact on important performance metrics such as initial coulombic efficiency, capacity, rate, cycle stability, and other relevant factors. Finally, this review presented personal insights into the challenges and issues faced by carbon materials, aiming to drive the advancement of SIBs.

Hydrogen in materials has attracted tremendous interest as its incorporation leads to significant alterations in nanoscale structure, composition, and chemistry, impacting functional properties. It has also been integral to nuclear fusion reactors and is considered a future clean energy source. However, nanoscale characterization and manipulation of hydrogen in materials are challenging as only a selected few analytical techniques can readily detect hydrogen, among which time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a unique and powerful one due to its excellent detection limit along with decent depth and lateral resolutions. In this review, we discuss, using selected examples, how to detect and quantify hydrogen in materials by ToF-SIMS and its impact on revealing the hydrogenation/protonation-induced novel functional states in different classes of materials. In addition, we present our protocols on sample preparation and experimental conditions optimization, allowing us to achieve the best possible results. Finally, we highlight future research directions that can lead to the discovery of novel functional states and ultimately provide a deeper understanding of scientific questions in materials science.

High specific-strength lightweight titanium (Ti) alloys, in the absence of interstitial strengthening of oxygen (O) atoms to avoid O-embrittlement, are mainly strengthened via densely semi-coherent nanoprecipitates in the β-matrix that act as dislocation obstacles and often result in high-stress concentrations, contributing to their strength-ductility trade-off. Here, using a low cost Ti-2.8Cr-4.5Zr-5.2Al duplex alloy as a model material, we present a counterintuitive O-doping strategy to create topologically coherent, interstitial-O α′ nanotwinned nanomartensites (NTNMs) with good interfacial strain compatibilities. The interstitial atoms tailor the stress field of edge dislocation cores from planar to non-planar, facilitating multiple variants nucleate simultaneously along O-rich edge dislocations to construct interstitial-O NTNMs. The interstitial-O NTNMs endow our duplex Ti alloys with superior strength of 1.64 gigapascals and large uniform elongation of 11.5%, surpassing all previously reported bulk Ti alloys. This unprecedented combination of mechanical properties is conferred mainly by the interstitial NTNMs, which serve as a sustainable ductility source via a self-hardening deformation mechanism and utilize the pronounced interstitial strengthening of concentrated O atoms. As such, the coherent interstitial NTNMs engineering strategy efficiently combines interstitial solid solution strengthening, and coherent interface strengthening mechanisms, that provides new insights into designing high-strength and large ductility O-tolerant alloys for cost-effective and lightweight applications.

Constructing artificial solid electrolyte interfaces (SEIs) to shape dendrite-free lithium (Li)-metal anodes remains challenges. Herein, we designed dynamic physical network (DPN) with abundant lithiophilic/anionphilic groups through tripartite hydrogen bonds (H-bonds), serving as artificial SEIs in high-loading NCM811-Li metal batteries. The formation and dissociation of DPN endowed by tripartite H-bonds under tension release during Li plating/stripping cycling skillfully balance the contradiction between mechanical robustness and deformability. LiO bonds between lithiophilic sites and Li ions, and extra H-bonds between hydroxyl and electrolyte anions, endow DPN with functions of homogenizing Li-ion flux and accelerating its desolvation, synergistically achieving the uniform Li-ion deposition and weakening the charge shielding. The artificial SEI enhanced Li-anode (DPN@Li) withstood repeated Li ions plating/stripping processes for over 1000 h, which is 5 times longer than pure Li-anodes, and maintained low overpotential at a high current density of 10 mA cm⁻². DPN@Li-based NCM811 full cells deliver high specific capacities and outstanding cycle life over 3000 cycles. Further, DPN@Li possesses excellent electrochemical performance in the high active material loading (7.84 mg cm⁻²) and foldable pouch cells. This work provides a conceptual framework of DPN constructed by multiple weak intermolecular interaction for artificial SEI to shape anode performance, and achieves the idea with a facile manner and simple chemical substances to promote practical applications of LMBs.

Chemo-immunotherapy, in which chemotherapeutic drugs activate immune system to suppress tumor growth and metastases, has great potential for clinical application. However, insufficient immunogenic cell death and serious side effects caused by tumor multidrug resistance and non-specific drug distribution, as well as inadequate and dysfunctional immune cells, greatly impair the effectiveness of chemo-immunotherapy. Herein, taking advantage of the functional diversity and structural programmability of nucleic acids, a DNA-based bioorthogonal nanoagonist is constructed to initiate and augment immune responses for robust chemo-immunotherapy. Benefiting from polyvalent targeting and template effects of DNA, the tailor-made nanoagonist shows prior bioorthogonal catalytic performance. Chemotherapeutic drug is bioorthogonally synthesized in situ under the catalysis of the nanoagonist, maximizing immunogenic cell death and minimizing systemic toxicity. The large amount of antigen and damage-associated molecular patterns released from dying tumor cells effectively initiates antitumor immunity. Meanwhile, the integration of high density of immunologic adjuvant can more effectively stimulate immune cells. The combination of bioorthogonal catalytic drug synthesis and immunostimulatory effect of DNA adjuvant not only destroys local primary tumors, but also eliminates distal metastasis. Moreover, the nanoagonist triggered the immune memory effect. The work extends the application of bioorthogonal chemistry to immunotherapy and provides a safe and powerful strategy for cancer chemo-immunotherapy.

Blast furnace ironmaking produces abundant CO₂, and molten oxide electrolysis (MOE) attracts great interest in ironmaking due to its carbon-free emissions. However, the anodes are the key limiting factor, making them very challenging due to high temperature and the intensive oxidation atmosphere. In this respect, a non-consumable argon plasma anode for iron electrolysis is proposed as a new technological process. During electrolysis, argon ionizes anodically and forms Ar⁺, which will jet into the molten oxide electrolyte and react with the O^2– complex anion from the electrolyte. Metallic iron is obtained by cathodic reduction, while oxygen evolution and argon regeneration occur in the electrolyte through 2O^2–_(complex) + 4Ar⁺ = O₂ + 4Ar, demonstrating the workability of the argon plasma as a non-consumable anode for molten oxide electrolysis.