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NanoManufacturing

Michael De Volder, Engineering Department - IfM
 

Gold‐Autocatalyzed Synthesis of Multi‐Element Nanoparticles

This work develops a simple and controllable gold-autocatalyzed synthesis method to incorporate multiple metal elements into a single-phase multi-element nanoparticle regardless of its immiscibility at room temperature. This reaction occurs among molecules and can be predicted according to frontier molecular orbital theory.


Abstract

The incorporation of multiple metal elements into a nanoparticle without phase separation holds promise for versatile applications, yet a facile synthetic strategy is lacking. Herein, a simple and facile approach is presented, i.e., gold-autocatalyzed synthesis, in which multiple miscible or immiscible metal elements are incorporated into single-phase nanoparticles at atmospheric pressure and temperature. This study reveals the autocatalytic reduction behavior of gold and the corresponding growth process of multi-element alloy nanoparticles. The mechanism of autocatalytic synthetic reactions is revealed on the basis of molecular orbitals. Furthermore, quinary multi-element nanoparticles were prepared and applied as high-performance electrocatalysts for the hydrogen evolution reaction in alkaline electrolytes (with overpotentials of 24 and 42 mV to deliver 10 and 100 mA cm−2, respectively) to demonstrate the application of this strategy. This strategy enables the synthesis of multi-element materials with high tolerance of synthetic conditions for versatile applications.

Bioxolography Using Diphenyliodonium Chloride and N‐Vinylpyrrolidone Enables Rapid High‐Resolution Volumetric 3D Printing of Spatially Encoded Living Matter

Bioxolography, a novel volumetric 3D-bioprinting technique, enables rapid and high-resolution fabrication of >1 cm3 engineered living materials. A newly developed three-component photoinitiator system significantly enhances the photoreactivity of gelatin methacryloyl-based bioresins, allowing for precise xolographic bioprinting. This platform supports multimaterial printing, concentration-controlled molecular patterning, and grayscale-mediated mechanical modulation to create complex, biomimetic, and spatially controlled architectures.


Abstract

Light-based volumetric bioprinting enables fabrication of cubic centimeter-sized living materials with micrometer resolution in minutes. Xolography is a light sheet-based volumetric printing technology that offers unprecedented volumetric generation rates and print resolutions for hard plastics. However, the limited solubility and reactivity of current dual-color photoinitiators (DCPIs) in aqueous media have hindered their application for high-resolution bioprinting of living matter. Here, we present a novel three-component formulation that drastically improves photoreactivity and thereby enables high-resolution, rapid, and cytocompatible Xolographic biofabrication of intricately architected yet mechanically robust living materials. To achieve this, various relevant additives are systematically explored, which revealed that diphenyliodonium chloride and N-vinylpyrrolidone strongly enhance D-mediated photoreactivity, as confirmed by dual-color photo-rheology. This enables Xolographic bioprinting of gelatin methacryloyl-based bioresins, producing >1 cm3 constructs at ≈20 µm positive and 125 µm negative resolution within minutes. Multimaterial printing, molecular patterning, and grayscale-mediated mechanical patterning are explored to programmably create intricate, biomimetic, and concentration-controlled architectures. We demonstrate the Bioxolographic printing of various cell types, showing excellent cell viability, compatibility with long-term culture, and ability for nascent protein deposition. These results position Bioxolography as a transformative platform for rapid, scalable, high-resolution fabrication of functional living materials with encoded chemical and mechanical properties.

Hybrid Additive Manufacturing of Shear‐Stiffening Elastomer Composites for Enhanced Mechanical Properties and Intelligent Wearable Applications

To achieve anisotropic structural design of shear stiffening materials, a novel hybrid additive manufacturing strategy is proposed to create a lattice-structured soft-hard phase elastomer composite (TPR-SSE composite) with enhanced mechanical properties. Based on this, an intelligent sports shoe is developed, demonstrating the potential application of the TPR-SSE composite material in wearable smart protective equipment.


Abstract

Shear-stiffening materials, renowned for their rate-dependent behavior, hold immense potential for impact-resistant applications but are often constrained by limited load-bearing capacity under extreme conditions. In this study, a novel hybrid additive manufacturing strategy that successfully achieves anisotropic structural design of shear-stiffening materials is proposed. In this strategy, fused deposition modeling (FDM) is synergistically combined with direct ink writing (DIW) to fabricate lattice-structured soft-hard phase elastomer composites (TPR-SSE composites) with enhanced mechanical properties. Through quasistatic characterization and dynamic impact experiments, complemented by noncontact optical measurement and finite element simulation, the mechanical enhancement mechanisms imparted by the lattice architecture are systematically uncovered. The resulting composites exhibit exceptional load-bearing capacity under quasistatic conditions and superior energy dissipation under dynamic impacts, making them ideal for advanced protective systems. Building on this, smart sports shoes featuring a deep-learning-based smart sensing module that integrates structural customizability, buffering capacity, and gait recognition, are developed. This work provides a transformative structure design approach to shear-stiffening materials systems, paving the way for next-generation intelligent wearable protection applications.

Self‐Assembled Multilayered Concentric Supraparticle Architecture

This study introduces Self-Assembled Multilayered Supraparticle (SAMS), the first concentric lamellar spherical structures formed from synergistic interactions between gold nanoparticles, lipidoid, and gelatin. SAMS exhibits unique interlayer spacing, enabling efficient environment responsive delivery of labile payloads like siRNA and mRNA. This work advances complex supraparticle design leveraging self-limiting self-assembly and demonstrates potential applications in nanomedicine.


Abstract

Supraparticles (SPs) with unique properties are emerging as versatile platforms for applications in catalysis, photonics, and medicine. However, the synthesis of novel SPs with complex internal structures remains a challenge. Self-Assembled Multilayered Supraparticles (SAMS) presented here are composed of concentric lamellar spherical structures made from metallic nanoparticles, formed from a synergistic three-way interaction phenomenon between gold nanoparticles, lipidoid, and gelatin, exhibiting interlayer spacing of 3.5  ± 0.2 nm within a self-limited 156.8  ± 56.6 nm diameter. The formation is critically influenced by both physical (including nanoparticle size, lipidoid chain length) and chemical factors (including elemental composition, nanoparticle cap, and organic material), which collectively modulate the surface chemistry and hydrophobicity, affecting interparticle interactions. SAMS can efficiently deliver labile payloads such as siRNA, achieving dose-dependent silencing in vivo, while also showing potential for complex payloads such as mRNA. This work not only advances the field of SP design by introducing a new structure and interaction phenomenon but also demonstrates its potential in nanomedicine.

Rational Ligand Design of Conjugated Coordination Polymers for Efficient and Selective Nitrate Electroreduction to Ammonia

A conjugated coordination polymer (CoN4-pyrr) of single-atom cobalt coordinated with the nitrogen atom of pyrrole ligand can work as an electrocatalyst for efficient and selective nitrate (NO3 −) reduction to ammonia (NH3), where a fast transfer of hydrogen (*H) radicals is induced to accelerate the hydrogenation kinetics of *NO intermediate on the cobalt active site of CoN4-pyrr at the rate-determining step.


Abstract

Electrocatalytic nitrate reduction to ammonia (NRA) offers an attractive route for converting nitrate pollutants to ammonia under mild conditions. Among other catalysts, single-atom catalysts (SACs) with high metal-atom-utilization efficiency and low-coordinated metal sites hold immense potential to be extensively applied, which unfortunately encounter a formidable challenge to obtain simultaneous improvement of NRA activity and selectivity. Here, a novel and general strategy is reported to achieve efficient and selective NRA catalysis on conjugated coordination polymers featuring with high-density and well-defined nitrogen (N)-coordinated single-atom metal sites via precise regulation of N‑heterocyclic ligands toward accelerating the hydrogenation kinetics necessitated in the NRA pathway. Taking cobalt (Co) as an example, two CoN4-centered conjugated coordination polymer electrocatalysts (CoN4-pyrr and CoN4-pyri) are synthesized with pyrrole and pyridine ligands are investigated as a proof-of-concept study. As revealed, the CoN4-pyrr can markedly outperform the CoN4-pyri toward NRA electrocatalysis. Experimental and theoretical results suggest that, relative to the N atoms of pyridine ligand in CoN4-pyri, the N atoms of pyrrole ligand in CoN4-pyrr can enable a faster transfer of hydrogen radicals to the Co active sites for accelerating the hydrogenation kinetics of *NO intermediate at the rate-determining step of NRA pathway.

Microbial Photosynthetic Oxygenation and Radiotherapeutic Sensitization Enables Pyroptosis Induction for Combinatorial Cancer Therapy

This study reports the preparation of lanthanum oxide nanoparticles (La2O3 NPs) via a solid-phase synthesis method, combined with cyanobacteria (Cyan) to effectively alleviate hypoxia. These components are confined within the tumor microenvironment using a thermosensitive hydrogel, enhancing the sensitivity of radiotherapy for colorectal and lung cancers. By alleviating hypoxia through cyanobacteria-mediated photosynthetic oxygenation, La2O3 NPs not only promote reactive oxygen species (ROS) generation, triggering pyroptosis via GSDMD activation, but also amplify radiotherapy-induced pyroptosis mediated by GSDME. This dual mechanism provides a powerful strategy to overcome hypoxia-induced radiotherapy resistance in colorectal and lung cancers.


Abstract

Rectal cancer surgery is challenging due to the complex anatomy, making it difficult to achieve clear surgical margins. Radiotherapy (RT) plays a crucial role, especially in treating locally recurrent rectal cancer and preserving anal function. However, its effectiveness is often limited by tumor hypoxia, particularly prevalent in hypoxic regions near the bowel wall in colorectal cancer. Hypoxia contributes to both radiation resistance and apoptosis resistance, compromising RT outcomes. To overcome hypoxia-driven radiotherapy resistance, this work designs and engineers a radiotherapy-sensitizing bioplatform for efficient cancer RT. It combines lanthanum oxide nanoparticles (La2O3 NPs) with cyanobacteria, which produces oxygen through photosynthesis. This bioplatform uniquely reduces tumor hypoxia, enhances radiation deposition, and improves RT efficacy. La2O3 NPs further enhance reactive oxygen species (ROS) production induced by radiation, triggering pyroptosis via the ROS-NLRP3-GSDMD pathway, while RT amplifies pyroptosis through GSDME, circumventing tumor apoptosis resistance. The further integrated thermosensitive hydrogels ensure precise localization of the bioplatform, reducing systemic toxicity and improving therapeutic specificity. Compared to conventional therapies, this dual-action system addresses hypoxia, RT resistance, and apoptosis resistance more effectively. In vivo and in vitro hypoxia models validate its potent anti-tumor efficacy, offering valuable insights for refining clinical treatment paradigms.

Biomimetic Dynamics of Nanoscale Groove and Ridge Topography for Stem Cell Regulation

Dynamic nanoscale groove-ridge structures are engineered by flexibly conjugating RGD-magnetic nanoparticles to nanogroove templates with variable groove widths at the molecular scale. Magnetic control enables cyclic switching between nanoscale groove and ridge states that modulates ligand accessibility of cellular integrins. The ligands in the ridge state reversibly promote integrin recruitment, adhesion, and differentiation of stem cells in vivo.


Abstract

Native extracellular matrix exhibits multiscale groove and ridge structures that continuously change, such as collagen fibril-based nanogrooves in bone tissue, and regulate cellular responses. However, dynamic switching between groove and ridge nanostructures at the molecular level has not been demonstrated. Herein, materials capable of dynamic groove-ridge switching at tens-of-nanometers scale are developed by flexibly conjugating RGD-magnetically activatable nanoridges (MANs) to non-magnetic nanogrooves with independently tuned widths comparable to the sizes of integrin-presenting filopodia by modulating hydrophobicity in bicontinuous microemulsion, allowing for cyclic modulation of RGD accessibility and cellular adhesion. Nanogrooves with medium width restrict RGD accessibility in the “groove” state in which the RGD-MANs are buried, which is reversed by magnetically raising them to protrude and form the “ridge” state that fully exposes the RGDs. This reversibly stimulates integrin recruitment, focal adhesion complex assembly, mechanotransduction, and differentiation of stem cells in vivo. This is the first demonstration of molecular-level groove and ridge nanostructures that exhibit unprecedented switchability between groove and ridge nanostructures. Versatile tuning of the width, height, pitch, and shape of intricate nanogroove structures with remote manipulability can enlighten the understanding of molecular-scale cell–ligand interactions for stem cell engineering-based treatment of aging, injuries, and stress-related diseases.

Halogenated Volatile Additive Strategy for Regulating Crystallization Kinetics and Enabling 20.40% Efficiency Polymer Solar Cells with Low Non-Radiative Recombination Energy Loss

http://feeds.rsc.org/rss/ee - Sat, 26/04/2025 - 07:41
Energy Environ. Sci., 2025, Accepted Manuscript
DOI: 10.1039/D5EE01368B, PaperChangjiang Li, Min Deng, Haonan Chen, Yuwei Duan, Chentong Liao, Zeqin Chen, Qiang Peng
Halogenated volatile additives play an important role in well regulating blend morphology in polymer solar cells (PSCs). However, the mismatched crystallization rate between the donor and acceptor often leads to...
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Significantly Enhanced Density and Mechanical Strength of Carbon/Graphite Blocks by Waste Gas Pressurized Sintering

The waste gas generated during carbonization in an enclosed space forms a high internal pressure, thereby effectively promoting the polymerization and densification of the carbon block. This self-generated pressure, known as waste gas pressurization (WGP), ensures tighter bonding between carbon particles, lower porosity, and obviously higher mechanical strength without the participation of external gas or mechanical compression.


Abstract

Carbonization under pressure is crucial for enhancing carbon/graphite materials. However, conventional pressure sintering, relying on mechanical or external gas pressure, often results in incomplete densification and structural defects due to uncontrolled volatile gas release. Herein, high-density and high-strength self-sintered carbon block in enclosed-space (SCB-E) are produced using waste gas pressurization (WGP) derived from green petroleum coke (GPC). This method can enhance the formation of C─O─C and C═O bonds by promoting dehydration polymerization reaction, which induces interfacial bonding in the carbonization process. Consequently, a decreased mass loss, increased volume shrinkage, and reduced porosity are observed, thereby endowing the obtained SCB-E with significantly improved density and mechanical strength. Specifically, the compressive and flexural strengths of SCB-E are 6.36 and 5.77 times higher than SCB-O sintered in open-space, respectively, while the corresponding graphite block (SG-E) achieves 7.74 and 4.58 times greater compressive and flexural strengths than SG-O. Notably, WGP not only enhances the yield of crack-free carbon blocks and supports scale-up production but also integrates seamlessly with traditional kneading processes to produce high-density, high-strength carbon blocks (CB-E). The current approach offers an innovative and important platform for enhancing the density and mechanical properties of bulk materials.

Solid Polymer Electrolyte with Dual Lewis‐Acid Filler for Ultra‐Stable Lithium Metal Batteries

The study reveals that Li+ transference number (t +), concentration (C 0), and diffusion coefficient (D) critically influence dendrite growth in SPEs. By developing dual-Lewis-acid fillers, these parameters are simultaneously enhanced, and constructed a stable inorganic SEI layer. The optimized electrolyte enables high-performance Li-metal batteries with NCM811/NCM622/LFP cathodes under demanding operating conditions.


Abstract

Solid polymer electrolytes (SPEs) are regarded as promising candidates that could address the safety concerns associated with liquid electrolytes. Nonetheless, SPEs are still confronting serious lithium dendrite issues, and there is a lack of systematic studies regarding the formation of lithium dendrites within SPEs. Herein, Sand equation is employed to elucidate the determinants of dendrite growth in SPEs, revealing that three factors including the Li+ transference number, Li+ diffusion coefficient, and Li+ concentration are positively correlated with Sand's time (τ) which determine the plating/striping behaviors of Li anode. More importantly, an effective and universal approach is proposed to construct dendrite-free polymer lithium metal batteries with dual-Lewis-acid materials such as Zinc Borate (ZB). Endowed with ZB materials, the PVDF-HFP based electrolyte possesses sufficient Li+ supply and swift transport channel and thus achieves an impressively high Li+ transference number of 0.9 and outstanding ionic conductivity at 30 °C (9.2 × 10−4 S cm−1), outperforming the polymer electrolytes with single Lewis-acid fillers. The electrolyte imparts the LFP//Li cell with exceptional capacity retention, showing almost no decay in discharge capacity even after 700, 500, and 300 cycles at 2 C, 3 C, and 5 C, respectively. Additionally, it capacitates the LiNi0.6Mn0.2Co0.2O2//Li cell to outperform by achieving over 1900 cycles at 1C and stably cycling under a cut-off voltage of 4.5V.

In-situ molecular compensation in wide-bandgap perovskite for efficient all-perovskite tandem solar cells

http://feeds.rsc.org/rss/ee - Sat, 26/04/2025 - 03:41
Energy Environ. Sci., 2025, Accepted Manuscript
DOI: 10.1039/D5EE01369K, PaperSheng Fu, Nannan Sun, Shuaifeng Hu, Hao Chen, Xingxing Jiang, Yunfei Li, Xiaotian Zhu, Xuemin Guo, Wenxiao Zhang, Xiaodong Li, Andrey S. Vasenko, Junfeng Fang
Substantial VOC loss and halide segregation in wide-bandgap (WBG) perovskite sub-cells pose significant challenges for advancing all-perovskite tandem solar cells (APTSCs). Regarding this, one of the most impactful developments is...
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Wed 14 May 16:30: Statistics Clinic Easter 2025 II

http://talks.cam.ac.uk/show/rss/5408 - Fri, 25/04/2025 - 17:57
Statistics Clinic Easter 2025 II

This free event is open only to members of the University of Cambridge (and affiliated institutes). Please be aware that we are unable to offer consultations outside clinic hours.

If you would like to participate, please sign up as we will not be able to offer a consultation otherwise. Please sign up through the following link: https://forms.gle/yCMudg1CrjUbFe2Q9. Sign-up is possible from May 8 midday (12pm) until May 8 midday or until we reach full capacity, whichever is earlier. If you successfully signed up, we will confirm your appointment by May 14 midday.

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Fri 02 May 16:00: Instabilities in viscoelastic fluids: a long story

http://talks.cam.ac.uk/show/rss/5408 - Fri, 25/04/2025 - 17:30
Instabilities in viscoelastic fluids: a long story

Many real-life fluids are not Newtonian and have to be modelled with something more complex than a single scalar viscosity. In this talk we will look specifically at dilute polymer solutions. We’ll see some simple models that capture the essential features of their behaviour, and then investigate how the properties of these models affect the stability of channel flow.

The story spans my whole research career so far, from an early theoretical prediction which was later observed in experiments, to a more recent realisation that there is still quite a lot we don’t understand. If time permits I will also discuss the latest place the research has taken me, which is neither viscoelastic nor unstable.

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Unraveling Structure-performance Relationship in Hard Carbon for Sodium-ion Battery by Coupling Key Structural Parameters

http://feeds.rsc.org/rss/ee - Fri, 25/04/2025 - 16:41
Energy Environ. Sci., 2025, Accepted Manuscript
DOI: 10.1039/D5EE00278H, PaperChun Wu, Yunrui Yang, Yifan Li, Xiangxi He, Yinghao Zhang, Wenjie Huang, Qinghang Chen, Xiaohao Liu, Shuangqiang Chen, Qinfen Gu, Lin Li, Sean C. Smith, Xin Tan, Yan Yu, Xingqiao Wu, Shulei Chou
The electrochemical performance of hard carbon anode for sodium-ion batteries is primarily determined by the microstructure of materials, and the challenge lies in establishing structure-performance relationship at molecular level. So...
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Fri 16 May 16:00: Title to be confirmed

http://talks.cam.ac.uk/show/rss/5408 - Fri, 25/04/2025 - 14:16
Title to be confirmed

Abstract not available

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Mannosylated MOF Encapsulated in Lactobacillus Biofilm for Dual‐Targeting Intervention Against Mammalian Escherichia coli Infections

This study develops a dual-targeting nano-system (Zn-MOF@Man/LRB) against Escherichia coli infection. Mannosylated Zn-MOF aggregates bacteria via FimH recognition and disrupts biofilms, while Lactobacillus biofilm encapsulation enables gut-targeted immunomodulation and sustains nanomaterial release. The system restores microbiota equilibrium and promotes stem cell differentiation and barrier stability. This approach demonstrates cross-species anti-diarrheal efficacy, advancing safe and effective treatment that restores intestinal homeostasis for potential applications in both human medicine and animal husbandry.


Abstract

Pathogenic bacterial infections pose a major concern, especially concerning mammalian enteritis and diarrhea. Compared to conventional antibiotic intervention, metal–organic frameworks (MOFs) exhibit superior antibacterial properties and lower cytotoxicity, demonstrating great promise in the treatment of pathogen-induced diarrhea. However, the achievement of their precise targeted delivery is still a significant challenge. Herein, a novel precision nano-system with a dual-targeting approach for treating intestinal infections caused by Escherichia coli (E. coli) is designed. First, Zn-MOF was synthesized based on ZnO, which possessed enhanced elimination of planktonic bacteria and biofilms. Through mannosylation, Zn-MOF@Man specifically recognized the FimH pili of E. coli, leading to its aggregation and subsequent eradication. Second, guided by whole genome sequencing, the encapsulation of Lactobacillus biofilm exertd immunomodulatory function, overcomed challenges related to intestinal targeting, and facilitated sustained drug release. Furthermore, Zn-MOF@Man/LRB maintaind microbiota equilibrium and promoted stem cell differentiation and barrier stability, ensuring consistent anti-diarrheal and anti-inflammatory efficacy in mice, piglets, and humans. This approach represents a novel dual-targeting antimicrobial strategy, combining probiotic biofilms and E. coli-oriented delivery, advancing safe and effective treatment that restores intestinal homeostasis for potential applications in both human medicine and animal husbandry.

High‐Energy‐Density Aqueous Zinc‐Ion Batteries: Recent Progress, Design Strategies, Challenges, and Perspectives

Strategies achieving high-energy-density aqueous zinc-ion batteries are summarized and analyzed from both their separate advancements and the integrated effectiveness in this review. Then, perspectives are given for valuable guidance for further development of high-energy-density aqueous zinc-ion batteries.


Abstract

Aqueous zinc-ion batteries (AZIBs) are emerging as a promising energy storage technique supplementary to Li-ion batteries, attracting much research attention owing to their intrinsic safety, cost economy, and environmental friendliness. However, energy densities for AZIBs still do not fulfill practical requirements because of the low specific and areal capacity, limited working potential, and excessive negative-to-positive electrode capacity (N/P) ratio. In this review, a comprehensive overview of basic requirements and major challenges for achieving high-energy-density AZIBs is provided. Following that, recent progress in the optimization of each component and the overall configuration is summarized, and crucial design principles are discussed. Apart from conventional emphasis on each part, especially cathode materials, separately, the comprehensive discussion about the synergistic interactions among all components is conducted. Finally, the outlook and research direction are given to provide valuable guidance for the further holistic development of high-energy-density aqueous zinc-ion batteries.

Biophysical‐Inspired Interpenetrated Fibrillar and Reticular Collagen Scaffold with Vascular Endothelial Cell Membrane Incorporation for Guided In Situ Spleen Tissue Regeneration

The spleen's complex structure limits its regenerative capacity after injury, significantly impacting patient quality of life. This work develops an inducible scaffold mimicking spleen parenchyma, enhancing in situ regeneration. This scaffold reduces oxidative stress, recruits cells, and promotes tissue integration, while proteomics reveal activation of key metabolic pathways, enhancing splenic function and blood vessel regeneration.


Abstract

The spleen's complex structure and limited regenerative ability hinder its regrowth at the site of injure, affecting patient quality of life and risk severe complications. The spleen's stroma primarily consists of reticular and fibrillar collagen, supporting its microvascular network. Inspired by such biophysical environment, this work develops an inducible scaffold featuring an interpenetrating network structure of fibrous and reticular collagen, which is loaded with vascular endothelial cell membranes to facilitate in situ regeneration. The regenerated parenchyma includes red pulp, white pulp, and a vascular system. The scaffold effectively reduces oxidative stress at the injury site, recruits cells to degrade the scaffold, and promotes tissue integration, thereby accelerating spleen regeneration. Additionally, the regenerated tissue compensates for the spleen's functions, enhancing its ability to clear abnormal red blood cells and platelets. Proteomics and RNA sequencing analyses reveal that the scaffold induced the upregulation of key pathways, including the Wnt signalling pathway, Statin pathway, and amino acid metabolism pathway. This activation mobilizes splenic cells metabolism, enhances immune cell activity, and facilitates the remodeling of the extracellular matrix. Moreover, the incorporated cell membrane components promote splenic blood vessels regeneration by upregulating the neural crest cell differentiation pathway within the tissue.

Upcycling Spent Lithium‐Ion Batteries: Constructing Bifunctional Catalysts Featuring Long‐Range Order and Short‐Range Disorder for Lithium‐Oxygen Batteries

In this work, for the first time, an interesting strategy is proposed for upcycling Ni, Co, and Mn valuable metals from spent lithium-ion batteries into a bifunctional catalyst for lithium-oxygen batteries by a rapid Joule-heated thermal shock method. This is a well-defined catalyst combining both features of long-range order L12 face-centered cubic structure and short-range disorder in M sites. Benefiting from the unique atomic arrangement, the long-range order L12 structure significantly enhances the long-term stability of the catalyst, while the short-range disorder character of the M site triggers the cocktail effect and further activates the Pt catalytic kinetics. Experiments and theoretical results disclose that the local coordination environment and electronic distribution of Pt are both fundamentally modulated via surrounding disordered Ni, Co, and Mn atoms, which greatly optimize the affinity toward oxygen-containing intermediates and facilitate the deposition/decomposition kinetics of the thin-film Li2O2 discharge products. This distinctly lowers both the energy barriers of the oxygen reduction reaction and oxygen evolution reaction.


Abstract

Upcycling of high-value metals (M = Ni, Co, Mn) from spent ternary lithium-ion batteries to the field of lithium-oxygen batteries is highly appealing, yet remains a huge challenge. In particular, the alloying of the recovered M components with Pt and applied as cathode catalysts have not yet been reported. Herein, a fresh L12-type Pt3 M medium-entropy intermetallic nanoparticle is first proposed, confined on N-doped carbon matrix (L12-Pt3(Ni1/3Co1/3Mn1/3)@N-C) based on spent 111 typed LiNi1-x-yMnxCoyO2 cathode. This well-defined catalyst combines both features of long-range order L12 face-centered cubic structure and short-range disorder in M sites. The former contributes to enhancing the structural stability, and the latter further facilitates deeply activating the catalytic activity of Pt sites. Experiments and theoretical results demonstrate that the local coordination environment and electronic distribution of Pt are both fundamentally modulated via surrounding disordered Ni, Co, and Mn atoms, which greatly optimize the affinity toward oxygen-containing intermediates and facilitate the deposition/decomposition kinetics of the thin-film Li2O2 discharge products. Specifically, the L12-Pt3(Ni1/3Co1/3Mn1/3)@N-C catalyst exhibits an ultra-low overpotential of 0.48 V and achieves 220 cycles at 400 mA g−1 under 1000 mAh g−1. The work provides important insights for the recycling of spent lithium-ion batteries into advanced catalyst-related applications.

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