Topological Transformation Research Articles

Synchronous inverse valence modulation of Ni3+/Co2+ over metal/metal-oxide heterojunction catalyst to promote hydrodeoxygenation performance of lignin derivatives

The proper design of catalyst structure is crucial for highly selective hydrodeoxygenation. Here, a strategy of in-situ topological transformation was proposed to prepare a MOF/LDH composite self-sacrificial template mediated by NiCo-MOF template, and a metal-monomer/metal-oxide composite heterojunction catalyst was synthesized. The result indicated that the formation of Ni3+ species on the surface of t-NiCo-60 catalyst was generated through this unique structural transformation, which promoted the charge movement between Ni-Co and caused more Co2+ to be formed, and this simultaneous reverse valence modulation between Ni3+/Co2+ facilitated the generation of oxygen vacancies, which improved the hydrogen heterocleavage activation on the catalyst and enabled the t-NiCo-60 catalyst to remove oxygen-containing groups from lignin derivatives with high selectivity. Achieved complete conversion of lignin derivatives in a short duration of time and highly selective generation of the target products (92.5% selectivity for cyclohexanol and 99.9% selectivity for 2-methoxy-4-methylphenol). This research provides a new approach for the efficient upgrading of lignin derivatives.

Ultra-rapid Synthesis of High-entropy MAX Phases and Their Derivative MXenes for Battery Electrodes.

High-entropy materials hold immense promise for energy storage, owing to their varied compositions and unforeseen physicochemical properties, yet, which poses challenges in synthesis due to tendentious phase separation and extended sintering durations. Herein, an ultra-rapid strategy based on spark plasma sintering (SPS) techniques is proposed to synthesize high-entropy MAX phases within 15 minutes, including a new phase of (Ti0.2V0.2Cr0.2Nb0.2Mo0.2)4AlC3 and several phases of 413-type TiVNbMoAlC3, TiVCrMoAlC3 and (Ti0.2V0.2Cr0.2Nb0.2Ta0.2)4AlC3, achieving utmost purity level up to 99.54%. Under high temperature, the overfeed of Al with low melt point (~660°C) can foster a liquid environment, which remits the immiscibility among starting materials and benefits to diffusion dynamics to some extents. Theoretical calculations are employed to elucidate the thermodynamic preponderance of high-entropy MAX phases in the intricate multi-element systems. Meanwhile, the varied stacking modes among MX slabs in high-entropy MAX phases and the distinct topological transformations to their derivative MXenes can be observed directly at the atomic level. Moreover, four high-entropy MXenes as electrode materials were investigated for rechargeable batteries. Among them, TiVNbMoC3 electrode demonstrates superior lithium-ion storage capabilities with 725 mAh g-1 after 1000 cycles at 1 A g-1, triggering the edification to the application of high-entropy MXenes for energy domain.

Ultra‐rapid Synthesis of High‐entropy MAX Phases and Their Derivative MXenes for Battery Electrodes

High‐entropy materials hold immense promise for energy storage, owing to their varied compositions and unforeseen physicochemical properties, yet, which poses challenges in synthesis due to tendentious phase separation and extended sintering durations. Herein, an ultra‐rapid strategy based on spark plasma sintering (SPS) techniques is proposed to synthesize high‐entropy MAX phases within 15 minutes, including a new phase of (Ti0.2V0.2Cr0.2Nb0.2Mo0.2)4AlC3 and several phases of 413‐type TiVNbMoAlC3, TiVCrMoAlC3 and (Ti0.2V0.2Cr0.2Nb0.2Ta0.2)4AlC3, achieving utmost purity level up to 99.54%. Under high temperature, the overfeed of Al with low melt point (~660°C) can foster a liquid environment, which remits the immiscibility among starting materials and benefits to diffusion dynamics to some extents. Theoretical calculations are employed to elucidate the thermodynamic preponderance of high‐entropy MAX phases in the intricate multi‐element systems. Meanwhile, the varied stacking modes among MX slabs in high‐entropy MAX phases and the distinct topological transformations to their derivative MXenes can be observed directly at the atomic level. Moreover, four high‐entropy MXenes as electrode materials were investigated for rechargeable batteries. Among them, TiVNbMoC3 electrode demonstrates superior lithium‐ion storage capabilities with 725 mAh g−1 after 1000 cycles at 1 A g‐1, triggering the edification to the application of high‐entropy MXenes for energy domain.

Targeted Topological Routine Regulation of RuNiOx Precursors for Excellent Alkaline Overall Water Splitting

Designing efficient and stable electrocatalysts for the hydrogen and oxygen evolution reactions (HER and OER) is crucial for green hydrogen production via the water‐splitting system. The bifunctional electrocatalyst offers a promising strategy due to the simplified preparation process and reduced expenses. However, the single‐component bifunctional catalysts often struggle to match the redox potential of water and to achieve proper adsorption/desorption of Gibbs free energy for both H and O intermediates simultaneously. Herein, through precisely controlling the topological transformation path of the RuNiOx precursor, we successfully prepared high‐performance RuNi/Ni and Ru/NiO heterostructure electrocatalysts for the HER and OER, respectively. The energy level matching between the fabricated electrocatalyst and water oxidation/reduction potential confirms the feasibility of HER and OER. The synergistic effect between the active sites ensures rapid, intermediate adsorption/desorption kinetics. As a result, the assembled alkaline overall water splitting setup achieves a current density of 1 A cm‐2 at 2 V and maintains stable operation at 100 mA cm‐2 for 100 hours.

Energy efficient routing for improving lifetime in MWSN: A clustering approach

A Mobile wireless sensor network (MWSN) consists of mobile sensor nodes, which can be deployed in any specific environment, and due to its’ mobility it can perform with rapid topological transformations of a network. The sensor nodes having limited battery power are used to collect specific data and this raw data is sent to a static sink node of the network. Under such a scenario, to avoid frequent disconnections due to topological change in the network and can avail more reliable data transmissions in energy awareness perspective, an energy efficient routing protocol for MWSNs to improve its lifetime is proposed here by utilizing a clustering approach. A MWSN with random number of sensor nodes are initially considered and then, clustering algorithm K-means is used to determine a predefined number of clusters with their initial cluster heads (CHs) and centroid locations of these clusters is also determined. The role of these CHs is to elect our DDBLACH (distance to sink and cluster centroid with battery level aware cluster head) nodes from each cluster, by sending and receiving intra-cluster messages among other member sensor nodes. A DDBLACH node is determined by using three factors, such as minimum distance from cluster centroid location, minimum distance from sink and the maximum battery level of the node from each cluster. These DDBLACH nodes are used to collect data from intra-cluster sensors and thereafter, send those towards sink node for further processing using tree-based hierarchical routes. Finally, an energy efficient routing technique for MWSNs is proposed for data transmission from DDBLACH nodes of clusters to sink of the network. Simulation results indicate the superiority of our proposed scheme over other existing methods in various aspects, such as improving more data packet transmission by 14%-23%, presence of alive nodes and subsequently average network lifetime by 5%-24%.

Heterostructure Engineering of Biphase‐Coupled Ternary Transition Metal Phosphoselenide by Topological Transformation Enabling High Performance for Supercapacitors

AbstractThe exploration of promising electrode materials with structural stability and rapid interfacial reaction kinetics is highly desirable for supercapacitors toward large‐scale applications. Herein, the synthesis of biphase‐coupled CoPSe/NiP0.24Se1.76 with multiple in‐plane heterointerfaces using the in situ topological transformation approach is presented. As a novel ternary metal phosphoselenide (TMPSe) for supercapacitor cathode that is fabricated by synchronous phosphoselenization strategy, it realizes a superior lifespan with cycling compared to conventional transition metal selenides. The depleted anti‐bonding eg* orbitals of transition metal ions (Co/Ni) in the CoPSe/NiP0.24Se1.76, as proved by preliminary theoretical calculations, strengthens the chemical bonding between Co/Ni and coordinating atoms, thereby enhancing the chemical stability. Simultaneously, the CoPSe/NiP0.24Se1.76 in‐plane multi‐heterostructures can not only alleviate the volume change during the charge–discharge process but also expose more active sites, promoting the adsorption of OH− ions, which is conducive to the rapid redox reaction kinetics of the CoPSe/NiP0.24Se1.76, and consequently, it delivers a remarkable reversible capacity and excellent long‐term cycle stability with 97.7% initial capacitance retention over 16 000 cycles. Moreover, the asymmetric supercapacitors with this cathode demonstrate outstanding rate capability and high energy density. This strategy of constructing biphase‐coupled CoPSe/NiP0.24Se1.76 by topological transformation is of great potential application for the high‐performance electrode material.

Solvent- and Concentration-Induced Topological Transformation of a Ruthenium(II)-Based Trigonal Prism to a Triply Interlocked [2] Catenane.

Synthesis of interlocked supramolecular cages has been a growing field of interest due to their structural diversity. Herein, we report the template-free synthesis of a Ru(II) triply interlocked [2] catenane using coordination-driven self-assembly. The self-assembly of a triazine-based tripyridyl donor L (2,4,6-tris(5-(pyridin-4-yl)thiophen-3-yl)-1,3,5-triazine) with a dinuclear Ru(II) acceptor M (Ru2(dhnq)(η6-p-cymene)2)(CF3SO3)2) yielded two distinct structures depending on the solvent and concentration. In methanol, a triply interlocked metalla [2] catenane (MC2) was formed, whereas in nitromethane, a non-interlocked cage (MC1) was obtained. The non-interlocked cage MC1 was gradually converted to MC2 in nitromethane by the increase in the concentration of cage MC1 from 0.5 to 9 mM. The interlocked cage (MC2) was stable after formation and was unaffected by the change in concentration. Notably, the free cage (MC1) exhibited host-guest interactions with polycyclic aromatic aldehydes, stabilizing the non-interlocked structure even at higher concentrations. In contrast, the triply interlocked [2] catenane (MC2) remains stable due to self-penetration and does not encapsulate guest molecules. This work showcases the stimuli-induced irreversible structural transformation of a triangular prismatic cage to its triply interlocked [2] catenane by employing metal-ligand coordination chemistry.

A Family of Twisted Chiral Engineered Inorganic Nanoarchitectures.

Chiral inorganic materials possess unique asymmetric properties that could significantly impact various fields. However, their practical application has been hindered by challenges in creating structurally robust chiral materials. We report the synthesis of well-defined chiral-shaped hollow cobalt oxide nanostructures, extendable to a family of chalcogenides including sulfide, selenide, and telluride through topological transformations. Taking chiral cobalt oxide nanostructures as a representative material, we demonstrate precise control over their chiral architectures, enabling fine-tuning of parameters, such as twist degrees, handedness, and compositions. These chiral nanostructures exhibit high spin selectivity effects that influence the electron transfer processes in catalytic reactions. Leveraging this spin-selective behavior, the chiral cobalt oxide nanoarchitectures demonstrate enhanced electrocatalytic performance in the oxygen evolution reaction compared to their achiral counterparts. Our findings not only expand the library of chiral inorganic materials but also advance the application of chiral effects in fields such as catalysis, spintronics, and beyond.

Folds from fold: Exploring topological isoforms of a single-domain protein

Expanding the protein fold space beyond linear chains is of fundamental significance, yet remains largely unexplored. Herein, we report the creation of seven topological isoforms (i.e., linear, cyclic, knot, lasso, pseudorotaxane, and catenane) from a single protein fold precursor by rewiring the connectivity of secondary structure elements of the SpyTag-SpyCatcher complex and mutating the reactive residue on SpyTag to abolish the isopeptide bonding. These topological isoforms can be directly expressed in cells. Their topologies were confirmed by combined techniques of proteolytic digestion, fluorescence correlation spectroscopy (FCS), size-exclusion chromatography (SEC), and topological transformation. To study the effects of topology on their structures and properties, their biophysical properties were characterized by differential scanning calorimetry (DSC), heteronuclear single quantum coherence nuclear magnetic resonance spectroscopy (HSQC-NMR), and circular dichroism (CD) spectroscopy. Molecular dynamics (MD) simulations were further performed to reveal the atomic details of structural changes upon unfolding. Both experimental and simulation results suggest that they share a similar, well-folded hydrophobic core but exhibit distinct folding/unfolding dynamic behaviors. These results shed light onto the folding landscape of topological isoforms derived from the same protein fold. As a model system, this work improves our understanding of protein structure and dynamics beyond linear chains and suggests that protein folds are highly amenable to topological variation.

NiMo-MMO catalyst derived from LDHs precursors toward the deep hydrogenation of pyrene

A series of Ni-based catalysts were prepared via structural topological transformation from the Ni@Al2O3 layered double hydroxides (LDHs) precursors, and applied for the deep catalytic hydrogenation saturation of pyrene in a high-pressure reactor. The pore structures, active species dispersion, surface morphology, amount and type of acid of the prepared catalysts were characterized by BET, XRD, SEM, TEM, XPS, SEM, NH3-TPD and Py-IR. We studied the influence of physicochemical properties of Ni-based catalysts on the regularity and mechanism of deep hydrogenation of pyrene. Meanwhile, the synergy between Ni and Mo, and the interaction between active metals and support were discussed to further reveal the constitutive relationship during the hydrogenation reaction of pyrene. The results of the evaluation of the catalytic hydrogenation of pyrene show that the as-prepared NiMo mixed metal oxide (MMO) catalyst showed excellent catalytic activity: ∼95% pyrene conversion, 90.12% for the selectivity of deep hydrogenation products (hexahydropyrene, decahydropyrene and hexadecahydropyrene). It was expected that the successfully preparation and utilization of NiMo-MMO catalyst could provide a theoretical basis for the design of this kind of catalysts for deep catalytic hydrogenation of polycyclic aromatic hydrocarbons (PAHs).

Inductive Insights into Preserving Euler Characteristics in Topological Transformations

Inductive Insights into Preserving Euler Characteristics in Topological Transformations

Surface Catalytic Repair for the Efficient Regeneration of Spent Layered Oxide Cathodes.

Direct recycling is considered to be the next-generation recycling technology for spent lithium-ion batteries due to its potential economic benefits and environmental friendliness. For the spent layered oxide cathode materials, an irreversible phase transition to a rock-salt structure near the particle surface impedes the reintercalation of lithium ions, thereby hindering the lithium compensation process from fully restoring composition defects and repairing failed structures. We introduced a transition-metal hydroxide precursor, utilizing its surface catalytic activity produced during annealing to convert the rock-salt structure into a layered structure that provides fast migration pathways for lithium ions. The material repair and synthesis processes share the same heating program, enabling the spent cathode and added precursor to undergo a topological transformation to form the targeted layered oxide. This regenerated material exhibits a performance superior to that of commercial cathodes and maintains 88.4% of its initial capacity after 1000 cycles in a 1.3 Ah pouch cell. Techno-economic analysis highlights the environmental and economic advantages of surface catalytic repair over pyrometallurgical and hydrometallurgical methods, indicating its potential for practical application.

Isotropy group on some topological transformation group structures

This paper explores the topological properties of irresolute topological groups, their quotient maps, and the role of topology in normal subgroups. It provides a detailed analysis\linebreak using examples and counterexamples. The study focuses on the essential features of irresolute topological groups and their quotient groups, for understanding the topological aspects of isotropy groups. For a trans\-for\-ma\-tion group $(\mathsf{H}, \mathsf{Y}, \psi)$ and a point $y \in \mathsf{Y},$ the set \centerline{$\mathsf{H}_{y} = \{h \in \mathsf{H} \colon hy = y\}$} \noi consisting of elements of $\mathsf{H}$ that fix $y$, is called the isotropy group at $y$. The paper highlights the distinct topological characteristics of isotropy groups in transformation group structure. It demonstrates that if $(\mathsf{H}, \mathsf{Y}, \psi)$ is an Irr$^{*}$-topological transformation group, then $( \mathsf{H}/ \mathop{Ker} \psi, \mathsf{Y}, \overline{\psi})$ forms an effective Irr$^{*}$-topological transformation group. By investigating both irresolute topological groups and isotropy groups, the study provides a clear understanding of their topological features. This research improves our understanding of these groups by offering clear examples and counterexamples, leading to a thorough conclusion about their different topological features.

Confined Mo2C/MoC heterojunction nanocrystals-graphene superstructure anode for enhanced conversion kinetics in sodium-ion batteries

Heterostructure design and integration with conductive materials play a crucial role in enhancing the conversion kinetics of electrode materials for metal-ion batteries. However, integrating nanocrystal heterojunctions into a conductive layer to form a superstructure is a significant challenge, mainly due to the difficulty in maintaining the structural integrity. Here we report a unique glucose-induced heterogeneous nucleation method that enables the independent manipulation of nucleation and growth of Mo2C/MoC heterojunction nanocrystals within 2D layers. Our investigations reveal that the rGO-Mo2C/MoC-rGO superstructure is formed by a topological transformation induced by subsequent heat treatment of the initial hydrothermally prepared rGO-MoO2-rGO precursor. This novel structure embeds Mo2C/MoC heterojunction nanocrystals within a 2D graphene matrix, providing enhanced mechanical stability, accelerated Na+ transport, and improved electron conduction. Ex situ XRD and Raman spectroscopy analyses reveal that the rGO-Mo2C/MoC-rGO superstructure significantly enhances the stability and reversibility of anodes. Leveraging these unique characteristics, the newly developed superstructural anode exhibits remarkable long-term cycling stability and outstanding rate performance. As a result, superstructure anodes demonstrate superior electrochemical capabilities, delivering a specific capacity of 106 mAh/g after enduring 5000 cycles at 1 A/g. Our study underscores the critical importance of superstructure design in propelling the advancement of battery materials.

Shaping and Doping Metal-Organic Framework-Derived TiO2 to Steer the Selectivity of Photocatalytic CO2 Reduction toward CH4.

Steering selectivity in photocatalytic conversion of CO2, especially toward deep reduction products, is vital to energy and environmental goals yet remains a great challenge. In this work, we demonstrate a facet-dependent photocatalytic selective reduction of CO2 to CH4 in Cu-doped TiO2 catalysts exposed with different facets synthesized by a topological transformation from MIL-125 (Ti) precursors. The optimized round cake-like Cu/TiO2 photocatalyst mainly exposed with the (001) facet exhibited a high photocatalytic CO2 reduction performance with a CH4 yield of 40.36 μmol g-1 h-1 with a selectivity of 94.1%, which are significantly higher than those of TiO2 (001) (4.70 μmol g-1 h-1 and 52.6%, respectively), Cu/TiO2 (001 + 101) (18.95 μmol g-1 h-1 and 69.6%, respectively), and Cu/TiO2 (101) (14.73 μmol g-1 h-1 and 78.9%, respectively). The results of experimental and theoretical calculations demonstrate that the Cu doping dominating the promoted separation and migration efficiencies of photogenerated charges and the preferential adsorption on (001) facets synergistically contribute to the selective reduction of CO2 to CH4. This work highlights the significance of synergy between facet engineering and ion doping in the design of high-performance photocatalysts with respect to selective reduction of CO2 to multielectron products.

CoFe bimetallic phosphide fabricated by topological transformation strategy for efficient electrooxidation of benzyl alcohol

Rational design of effective non-precious metallic electrocatalysts is crucial for electrooxidation of benzyl alcohol (BA) producing benzoic acid (BAC). Herein, CoFe bimetallic phosphide (CoFeP-m) with bimetallic synergy, fully exposed active sites, and fast charge transfer was fabricated by topological transformation of CoFe-LDH for the efficient electrooxidation of BA to BAC under mild condition. Under the optimal conditions of starting voltage of 0.7 V vs. Ag/AgCl at 25oC, CoFeP-300 achieved 97.71% transformation of BA and 97.84% BAC's selectivity for 8 h. In addition, CoFeP-300 showed excellent stability which maintained 95.89% transform into BA and 95.37% BAC's selectivity at the sixth cycle.

Enhanced catalytic transfer hydrogenation of biomass-based furfural into furfuryl alcohol over Co3O4-based mixed oxide catalysts from hydrotalcite

Catalytic furfural (FF) into high value-added furfuryl alcohol (FOL) is a very important biomass improvement process and remains a challenging task. Herein, a series of Co-based composite oxide (CoMgAl-LDO) catalysts with highly dispersed Co3O4-based spinel oxide nanoparticles were synthesized by the topological transformation of Co-based ternary layered hydroxides (CoMgAl-LDH) under calcination conditions and tested for catalytic transfer hydrogenation of FF to FOL using isopropanol (2-PrOH) as hydrogen donor. The CoMgAl-LDO, especially Co1.5Mg1.5Al1-LDO calcinated at 500 °C (Co1.5Mg1.5Al1-LDO-500) offered the outstanding catalytic performance for the catalytic transfer hydrogenation of FF to FOL (99.7 % FF conversion and 95.9 % FOL selectivity), which was attributed to effectively dispersed active sites, abundant acid-base sites and mesoporous structure. Additionally, the Co1.5Mg1.5Al1-LDO-500 catalyst manifested good stability with wider universality to other carbonyl compounds, making the catalytic system extremely economical and practical in various biomass hydrogenation processes.

Topological Programmability of Isomerizable Polymers.

Topology isomerizable networks (TINs) can be programmed into numerous polymers exhibiting unique and spatially defined (thermo-) mechanical properties. However, capturing the dynamics in topological transformations and revealing the intrinsic mechanisms of mechanical property modulation at the microscopic level is a significant challenge. Here, we use a combination of coarse-grained molecular dynamics simulations and reaction kinetic theory to reveal the impact of dynamic bond exchange reactions on the topology of branched chains. We find that, the grafted units follow a geometric distribution with a converged uniformity, which depends solely on the average grafted units of branched chains. Furthermore, we demonstrate that the topological structure can lead to spontaneous modulation of mechanical properties. The theoretical framework provides a research paradigm for studying the topology and mechanical properties of TINs.

Unknots, knots, links and necklaces made of dislocations in cholesterics

ABSTRACT We deal with the genesis and decay of knots and links made of dislocations in a cholesteric layer confined in the gap between orthogonal cylindrical mica sheets. The genesis starts by nucleation of folded unknots driven by a compressive strain. The nucleation process of the trivial and folded unknots is studied and discussed in detail. We show that the expansion of the folded unknots leads to their lateral collisions followed by the coalescence into the torus knots, such as the trefoil knot, or into the links, such as the Hopf and Solomon links. The viscoelastic decays of knots and links follow well-defined paths involving topological and geometrical transformations. In particular, the symmetric configuration of the Hopf link is unstable with respect to the shrinking of one of its interlaced loops. The final asymmetric configuration, made of a minimal loop tethered on a large cargo loop, is called the Hopf necklace. Similarly, the double Hopf necklace is obtained by the elastic decay of the Solomon link. We emphasise that Hopf necklaces of various orders are quite ubiquitous.

Acid-base synergistic effect towards catalytic transfer hydrogenation reactions

Catalytic transfer hydrogenation (CTH) of aldehydes/ketones by using alcohols as hydrogen donors is an attractive and environmentally friendly hydrogenation technology, which has evoked widespread attention in synthesis of fine chemicals from biomass resources. In this work, a Co-Al mixed metal oxide catalyst (Co1Al2-MMO-200) was obtained through structural topological transformation process of layered double hydroxides, which was used in the CTH reaction of furfural with isopropanol. Notably, the reaction rate achieves 0.023 mol g−1 h−1, which is preponderate to acid-base catalysts earlier reported. The joint research based on CO2-TPD, NH3-TPD and poisoning experiment substantiates that the synergy effect of acid-base sites plays an essential role in this catalytic system. Isotopic labelling MS, in-situ FT-IR and DFT studies further verify that the CTH reaction of furfural occurs via the Meerwein-Ponndorf-Verley (MPV) route, in which the basic site promotes the deprotonation of isopropanol whilst the acid site facilitates the formation of a six-membered ring transition state. This work demonstrates an acid-base synergetic catalysis for the CTH reaction by revealing the structure-property correlation and exploring reaction route, which is instructive for designing high-performance heterogenous catalysts.