Reversible Evolution Research Articles

Amorphous MnO2 Lamellae Encapsulated Covalent Triazine Polymer-Derived Multi-Heteroatoms-Doped Carbon for ORR/OER Bifunctional Electrocatalysis.

The intelligent construction of non-noble metal materials that exhibit reversible oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with bifunctional electrocatalytic performance is greatly coveted in the realm of zinc-air batteries (ZABs). Herein, a crafted structure-amorphous MnO2 lamellae encapsulated covalent triazine polymer-derived N, S, P co-doped carbon sphere (A-MnO2/NSPC) is designed using a self-doped pyrolysis coupled with an in situ encapsulation strategy. The customized A-MnO2/NSPC-2 demonstrates a superior bifunctional electrocatalytic performance, confirmed by a small ΔE index of 0.64V for ORR/OER. Experimental investigations, along with density functional theory calculations validate that predesigned amorphous MnO2 surface defects and abundant heteroatom catalytic active sites collectively enhance the oxygen electrocatalytic performance. Impressively, the A-MnO2/NSPC-based rechargeable liquid ZABs show a large open-circuit potential of 1.54V, an ultrahigh peak power density of 181mW cm-2, an enormous capacity of 816 mAh g-1, and a remarkable stability for more than 1720 discharging/charging cycles. Additionally, the assembled flexible all-solid-state ZABs also demonstrate outstanding cycle stability, surpassing 140 discharging/charging cycles. Therefore, this highly operable synthetic strategy offers substantial understanding in the development of magnificent bifunctional electrocatalysts for various sustainable energy conversions and beyond.

Aluminum ion chemistry of Na4Fe3(PO4)2(P2O7) for all-climate full Na-ion battery

Na4Fe3(PO4)2(P2O7) (NFPP) is currently drawing increased attention as a sodium-ion batteries (SIBs) cathode due to the cost-effective and NASICON-type structure features. Owing to the sluggish electron and Na+ conductivities, however, its real implementation is impeded by the grievous capacity decay and inferior rate capability. Herein, multivalent cation substituted microporous Na3.9Fe2.9Al0.1(PO4)2(P2O7) (NFAPP) with wide operation-temperature is elaborately designed through regulating structure/interface coupled electron/ion transport. Greatly, the derived Na vacancy and charge rearrangement induced by trivalent Al3+ substitution lower the ions diffusion barriers, thereby endowing faster electron transport and Na+ mobility. More importantly, the existing Al—O—P bonds strengthen the local environment and alleviate the volume vibration during (de)sodiation, enabling highly reversible valence variation and structural evolution. As a result, remarkable cyclability (over 10,000 loops), ultrafast rate capability (200 C), and exceptional all-climate stability (−40–60 °C) in half/full cells are demonstrated. Given this, the rational work might provide an actionable strategy to promote the electrochemical property of NFPP, thus unveiling the great application prospect of sodium iron mixed phosphate materials.

Loewner Theory for Bernstein Functions I: Evolution Families and Differential Equations

AbstractOne-parameter semigroups of holomorphic functions appear naturally in various applications of Complex Analysis, and in particular, in the theory of (temporally) homogeneous branching processes. A suitable analogue of one-parameter semigroups in the inhomogeneous setting is the notion of a (reverse) evolution family. In this paper we study evolution families formed by Bernstein functions, which play the role of Laplace exponents for inhomogeneous continuous-state branching processes. In particular, we characterize all Herglotz vector fields that generate such evolution families and give a complex-analytic proof of a qualitative description equivalent to Silverstein’s representation formula for the infinitesimal generators of one-parameter semigroups of Bernstein functions. We also establish a sufficient condition for families of Bernstein functions, satisfying the algebraic part in the definition of an evolution family, to be absolutely continuous and hence to be described as solutions to the generalized Loewner–Kufarev differential equation. Most of these results are then applied in the sequel paper [35] to study continuous-state branching processes.

Efficient photo-thermal catalytic CO2 methanation and dynamic structural evolution over Ru/Mg-CeO2 single-atom catalyst

It is a promising green technology to reduce CO2 to CH4 by using renewable solar energy driving photo-thermal catalysis route. However, the efficiency of photo-thermal catalytic CO2 methanation remained to be improved, and the mechanism of this reaction still required further investigation. In this paper, a Ru/Mg-CeO2 catalyst was designed based on the concepts of single atom catalyst and photo-thermal catalysis concept. The catalyst achieved the CH4 formation rate of 469 mmol·gcat−1·h−1 at 400 °C under photo-thermal conditions with good catalytic stability. Besides, the superiority of the single-atom of Ru, Ru-O-Ce structure and doping of alkaline metals in catalytic process was proved by a series of physicochemical and optical characterization, and electron migration direction from Ce and Mg elements to Ru sites through Ru-O-Ce and Ru-O-Mg path under photo-thermal catalysis was determined by ISI-XPS experiment. Finally, the comprehensive reaction mechanism and reversible dynamic structural evolution process between Ru-O-Ce and Ru-Ov-Ce structures were investigated by in situ DRIFTs experiments, and the source of the excellent performance and structure-function relationship of the catalyst was explored, which provided the theoretical and practical basis for the development of catalyst and industrial application of the reaction.

Crystalline Dual-Porous Covalent Triazine Frameworks as a New Platform for Efficient Electrocatalysis.

Crystalline covalent triazine frameworks (CTFs) have gained considerable interest in energy and catalysis owing to their well-defined nitrogen-rich π-conjugated porosity and superior physicochemical properties, however, suffer from very limited molecular structures. Herein we report a novel solvent-free FeCl3 -catalyzed polymerization of 2, 6-pyridinedicarbonitrile (DCP) to achieve the first synthesis of crystalline, dual-porous, pyridine-based CTF (Fe-CTF). The FeCl3 could not only act as a highly active Lewis acid catalyst for promoting the two-dimensional ordered polymerization of DCP monomers, but also in situ coordinate with the tridentate chelators generated between pyridine and triazine groups to yield unique Fe-N3 single-atom active sites in Fe-CTF. Abundant few-layer crystalline nanosheets (Fe-CTF NSs) could be prepared through simple ball-milling exfoliation of the bulk layered Fe-CTF and exhibited remarkable electrocatalytic performance for oxygen reduction reaction (ORR) with a half-wave potential and onset potential up to 0.902 and 1.02 V respectively, and extraordinary Zn-air battery performance with an ultrahigh specific capacity and power density of 811 mAh g-1 and 230 mW cm-2 respectively. By combining operando X-ray absorption spectroscopy with density functional theory calculations, we revealed a dynamic and reversible evolution of Fe-N3 to Fe-N2 during the electrocatalytic process, which could further accelerate the electrocatalytic reaction.

Horizontal gene transfer facilitates the molecular reverse-evolution of antibiotic sensitivity in experimental populations of H. pylori.

Reversing the evolution of traits harmful to humans, such as antimicrobial resistance, is a key ambition of applied evolutionary biology. A major impediment to reverse evolution is the relatively low spontaneous mutation rates that revert evolved genotypes back to their ancestral state. However, the repeated re-introduction of ancestral alleles by horizontal gene transfer (HGT) could make reverse evolution likely. Here we evolve populations of an antibiotic-resistant strain of Helicobacter pylori in growth conditions without antibiotics while introducing an ancestral antibiotic-sensitive allele by HGT. We evaluate reverse evolution using DNA sequencing and find that HGT facilitates the molecular reverse evolution of the antibiotic resistance allele, and that selection for high rates of HGT drives the evolution of increased HGT rates in low-HGT treatment populations. Finally, we use a theoretical model and carry out simulations to infer how the fitness costs of antibiotic resistance, rates of HGT and effects of genetic drift interact to determine the probability and predictability of reverse evolution.

Reversible evolution phenomenon of particle during crystal growth: A phase-field study

The two-dimensional thermodynamically consistent phase field model, which consists of the anisotropic Allen-Cahn type equation and the heat equation, is used to study the morphological pattern of the particle in the initial stage of crystal growth. The results reveal the locally reversible growth of the particle in the initial stage of crystal growth. Specifically, some parts of the particle interface first grow inward, while others grow outward from the interface of critical nucleation, until the growth speed of the interface becomes zero. After this, the inward growth parts start to grow outward with other parts. The locally reversible growth of the particle leads to the development of a petal-like shape. The particle radius size dependence of the temperatures along the parts of the particle interface in different crystallographic directions at different time points is studied. By a series of results, the correlations between the morphological pattern selection of the particle and the model parameters, including undercooling and anisotropic strength, are analyzed. These results contribute to understanding the fundamental mechanism of the particle evolution during crystal growth.

Reversal mechanism of triboelectrification in steel-polymer frictional interface for in-situ monitoring of transfer films

The triboelectric behavior of metal sliding against polymer in triboelectric nanogenerators (TENGs) is highly affected by the friction condition. However, the electrification behavior of the friction interface and its evolutionary mechanism during friction are still unclear. Herein, the internal mechanism of the triboelectric behavior of the material transfer modulation interface when the steel slides against PTFE/PE/POM polymers is systematically investigated in a tribological way. Different from the electrification in the vertical contact-separation mode, the surface potential of the three polymers will evolve inversely with time during friction. The reason for the reverse evolution is classified as the induced effect after the transfer of the material with residual charge to the steel ball. The formation of the transfer film not only stabilizes and reduces friction but also induces the inversion of the potential of the substrate surface. By polishing the transfer film on the surface of the steel ball, the inversion of the surface potential can be repeated reproducibly. Furthermore, the existence of the transfer film is monitored in situ by monitoring the surface potential change of the steel ball. This work provides a vital reference for revealing the physical mechanism of interface triboelectrification and expanding the tribological characterization methods.

In Situ Formed Amorphous Bismuth Sulfide Cathodes with a Self-Controlled Conversion Storage Mechanism for High Performance Hybrid Ion Batteries.

Conversion-type electrodes offer a promising multielectron transfer alternative to intercalation hosts with potentially high-capacity release in batteries. However, the poor cycle stability severely hinders their application, especially in aqueous multivalence-ion systems, which can fundamentally impute to anisotropic ion diffusion channel collapse in pristine crystals and irreversible bond fracture during repeated conversion. Here, an amorphous bismuth sulfide (a-BS) formed in situ with unprecedentedly self-controlled moderate conversion Cu2+ storage is proposed to comprehensively regulate the isotropic ion diffusion channels and highly reversible bond evolution. Operando synchrotron X-ray diffraction and substantive verification tests reveal that the total destruction of the Bi─S bond and unsustainable deep alloying are fully restrained. The amorphous structure with robust ion diffusion channels, unique self-controlled moderate conversion, and high electrical conductivity discharge products synergistically boosts the capacity (326.7 mAh g-1 at 1 A g-1 ), rate performance (194.5 mAh g-1 at 10 A g-1 ), and long-lifespan stability (over 8000 cycles with a decay rate of only 0.02 ‰ per cycle). Moreover, the a-BS Cu2+ ‖Zn2+ hybrid ion battery can well supply a stable energy density of 238.6Wh kg-1 at 9760W kg-1 . The intrinsically high-stability conversion mechanism explored on amorphous electrodes provides a new opportunity for advanced aqueous storage.

Adaptive Differential Evolutionary Algorithm for Innovative Teaching and Learning in High School Project-Based Courses

Abstract In this paper, for the innovative teaching of high school project-based courses, an adaptive differential evolutionary algorithm is used as one of the tools of the project to help students solve complex problems. The traditional adaptive differential evolution algorithm has the problems of local optimum and low convergence accuracy; to overcome these limitations, this paper proposes an enhanced reverse learning adaptive differential evolution algorithm. The OL-ADE algorithm is improved by introducing the reverse learning strategy in machine learning to extract the reverse elite individual population from the original individual population and select the better-adapted individuals for mutation operation. After the project-based teaching, the students’ works have high scores in layout color matching, technical operation, organization, information awareness, and information social responsibility, and their scores are 8.6, 9.75, 9, 9.35, and 8.75, respectively. Therefore, this paper proves the Adaptive Difference Evolution algorithm’s effectiveness in innovative teaching of high school project-based courses.

Nickel pre-intercalated bilayer vanadium pentoxide hydrate for reversible structural evolution in Na-ion battery cathode

Layered vanadium oxides, due to their high specific capacity and the multiple oxidation states of vanadium, are attractive candidates as cathode materials for sodium-ion batteries (SIBs). To meet the requirements of increasing interlayer spacing and significantly improving structural stability, herein, nickel pre-intercalated bilayer vanadium pentoxide hydrate, Ni0.28V2O5∙0.62 H2O (referred to as NVO) is synthesized successfully. The interlayer water molecules significantly increase the interlayer distance of the bilayer vanadium pentoxide. At the same, by forming a stable interlayer NiO6 octahedron, the intercalated Ni atoms effectively relieve the big change of volume during the Na ions insertion/extraction process and effectively inhibit the interlayered water molecules escape in charge/discharge process. Due to the big interlayer distance and excellent structural stability, the NVO electrode exhibits an excellent electrochemical performance. Except for the first few cycles, a high reversible capacity of about 260 mAh g−1 is obtained and the mean fade is only 0.5% per cycle. In addition, the excellent Na storage mechanism of the NVO electrode is also explored in detail by in situ XRD.

Double-pinning effect assisting Na4VMn(PO4)3 with superior structural and electrochemical stabilization for sodium-ion batteries

The Na superionic conductor of (NASICON)-type Na4VMn(PO4)3 (NVMP) with a three-dimensional framework and high operating voltage has been extensively investigated for sodium-ion batteries (SIBs). However, unexpected Jahn-Teller effect and sluggish Na+ diffusion kinetics inevitably lead to rapid capacity fade and unfavorable structural distortion. Herein, the double-pinning effect of Al/F co-doping was adopted for the NVMP system to enhance structural stability and facilitate Na+ diffusion. The as-synthesized NVMP-Al&F presents a highly reversible capacity of 110 mAh g−1 at 0.1 C, accompanied with a long-term lifespan of 1000 cycles at 5 C (capacity retention of 86.1 %). Moreover, in situ X-ray diffraction affirms the reversible structural evolution and small volume variation (∼4.43 %) during the highly reversible sodiation/desodiation processes. Benefiting from the double-pinning effect, the lowered Na+ migration barrier effectively facilitates Na+ diffusion and increases to higher reversible capacity by combining theoretical calculation and kinetic analysis. The assembled NVMP-Al&F//hard carbon (HC) full cell manifests a high energy density of 353.9 Wh kg−1 and excellent cycling durability of 91.3 % at 1 C after 100 cycles. This work sheds light on the double-pinning as a novel strategy to boost the cycling stability of high-performance NASICON-type cathodes.

Reversible Multielectron Redox Chemistry in a NASICON-Type Cathode toward High-Energy-Density and Long-Life Sodium-Ion Full Batteries.

Na-superionic-conductor (NASICON)-type cathodes (e.g., Na3 V2 (PO4 )3 ) have attracted extensive attention due to their open and robust framework, fast Na+ mobility, and superior thermal stability. To commercialize sodium-ion batteries (SIBs), higher energy density and lower cost requirements are urgently needed for NASICON-type cathodes. Herein, Na3.5 V1.5 Fe0.5 (PO4 )3 (NVFP) is designed by an Fe-substitution strategy, which not only reduces the exorbitant cost of vanadium, but also realizes high-voltage multielectron reactions. The NVFP cathode can deliver extraordinary capacity (148.2mAhg-1 ), and decent cycling durability up to 84% after 10000 cycles at 100 C. In situ X-ray diffraction and ex situ X-ray photoelectron spectroscopy characterizations reveal reversible structural evolution and redox processes (Fe2+ /Fe3+ , V3+ /V4+ , and V4+ /V5+ ) during electrochemical reactions. The low ionic-migration energy barrier and ideal Na+ -diffusion kinetics are elucidated by density functional theory calculations. Combined with electron paramagnetic resonance spectroscopy, Fe with unpaired electrons in the 3d orbital is inseparable from the higher-valence redox activation. More competitively, coupling with a hard carbon (HC) anode, HC//NVFP full cells demonstrate high-rate capability and long-duration cycling lifespan (3000stable cycles at 50 C), along with material-level energy density up to 304Whkg-1 . The present work can provide new perspectives to accelerate the commercialization of SIBs.

Left-Right Reversal Recurrently Evolved Regardless of Diaphanous-Related Formin Gene Duplication or Loss in Snails.

Bilateria exhibit whole-body handedness in internal structure. This left-right polarity is evolutionarily conserved with virtually no reversed extant lineage, except in molluscan Gastropoda. Phylogenetically independent snail groups contain both clockwise-coiled (dextral) and counterclockwise-coiled (sinistral) taxa that are reversed from each other in bilateral handedness as well as in coiling direction. Within freshwater Hygrophila, Lymnaea with derived dextrality have diaphanous related formin (diaph) gene duplicates, while basal sinistral groups possess one diaph gene. In terrestrial Stylommatophora, dextral Bradybaena also have diaph duplicates. Defective maternal expression of one of those duplicates gives rise to sinistral hatchlings in Lymnaea and handedness-mixed broods in Bradybaena, through polarity change in spiral cleavage of embryos. These findings led to the hypothesis that diaph duplication was crucial for the evolution of dextrality by reversal. The present study discovered that diaph duplication independently occurred four times and its duplicate became lost twice in gastropods. The dextrality of Bradybaena represents the ancestral handedness conserved across gastropods, unlike the derived dextrality of Lymnaea. Sinistral lineages recurrently evolved by reversal regardless of whether diaph had been duplicated. Amongst the seven formin gene subfamilies, diaph has most thoroughly been conserved across eukaryotes of the 14 metazoan phyla and choanoflagellate. Severe embryonic mortalities resulting from insufficient expression of the duplicate in both of Bradybaena and Lymnaea also support that diaph duplicates bare general roles for cytoskeletal dynamics other than controlling spiralian handedness. Our study rules out the possibility that diaph duplication or loss played a primary role for reversal evolution.

Bifunctional Oxygen Electrocatalyst of Co4N and Nitrogen‐Doped Carbon Nanowalls/Diamond for High‐Performance Flexible Zinc–Air Batteries

AbstractRational design of heterogeneous catalysts with unique structural and electronic properties is one of the major challenges to improve the activity toward the reversible oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), the bottleneck in the construction of air cathodes for the next‐generation flexible zinc–air batteries (ZABs). Herein, density functional theory calculations are combined with experimental attempts to exploit the roles of the electronic effects at the interface between Co4N nanoparticles and nitrogen‐doped carbon nanowalls/diamond (d‐NCNWs/D) toward the ORR and OER activities. The vacancy defect‐induced Co‐pyridinic N─C bond optimizes the electronic structure of Co 3d orbitals and balances the adsorption energies of intermediates along the reaction pathways. Consequently, as‐synthesized Co4N@d‐NCNWs/D composites exhibit superior bifunctional oxygen catalytic activity. The overpotential of the OER is as low as 340 mV at 10 mA cm−2 and the high half‐wave potential reaches 0.83 V for the ORR. As a binder‐free and flexible ZABs cathode, this composite exhibits an open circuit voltage of 1.41 V and excellent bendable stability, proving its promising potential for the assembly of wearable devices. This work offers theoretical evidence and a controllable strategy to design high‐performance ZAB cathodes for their application in smart electronic devices.

A "thoughtful" Local Friendliness no-go theorem: a prospective experiment with new assumptions to suit

A recent paper by two of us and co-workers \cite{CQD20}, based on an extended Wigner's friend scenario, demonstrated that certain empirical correlations predicted by quantum theory (QT) violate inequalities derived from a set of metaphysical assumptions we called "Local Friendliness" (LF). These assumptions are strictly weaker than those used for deriving Bell inequalities. Crucial to the theorem was the premise that a quantum system with reversible evolution could be an observer (colloquially, a "friend"). However, that paper was noncommittal on what would constitute an observer for the purpose of an experiment. Here, we present a new LF no-go theorem which takes seriously the idea that a system's having thoughts is a sufficient condition for it to be an observer. Our new derivation of the LF inequalities uses four metaphysical assumptions, three of which are thought-related, including one that is explicitly called "Friendliness". These four assumptions, in conjunction, allow one to derive LF inequalities for experiments involving the type of system that "Friendliness" refers to. In addition to these four metaphysical assumptions, this new no-go theorem requires two assumptions about what is technologically feasible: Human-Level Artificial Intelligence, and Universal Quantum Computing which is fast and large scale. The latter is often motivated by the belief that QT is universal, but this is not an assumption of the theorem. The intent of the new theorem is to give a clear goal for future experimentalists, and a clear motivation for trying to achieve that goal. We review various approaches to QT in light of our theorem. The popular stance that "quantum theory needs no interpretation" does not question any of our assumptions and so is ruled out. Finally, we quantitatively discuss how difficult the experiment we envisage would be, and briefly discuss milestones on the paths towards it.

Reversible evolution of ferroelectric-antiferroelectric phase transition in lanthanum-modified NaNbO3-based ceramics

Sodium niobate (NN) lead-free perovskites have been concentrated on due to high performance and abundant phase structure. The complex structure evolution has become a hot topic of research for this kind of materials. In this work, antiferroelectric phase is recovered by introducing La3+ dopant from modified ferroelectric states, indicating reversible composition-induced antiferroelectric-ferroelectric (AFE-FE) phase transition in NN-based ceramics. Significantly, change tendency of decreasing first and then increasing appears for phase transition temperature with increasing La3+, which is different from general phenomenon for ions dopant. Antiferroelectric orthorhombic (Pbma) is induced from ferroelectric tetragonal (P4mm) with a transient state of paraelectric cubic (Pm3m) via enhancing La3+. Further, substitution on A-site and A/B-sites are revealed with low and high content of La3+, respectively, accompanied by decreased first and then increased oxygen vacancy. Moreover, obviously deteriorated piezoelectric response is observed along with poor domain switching due to the vanishing ferroelectric domain for FE-PE-AFE phase transition. Meanwhile, weak strain, piezoelectric and dielectric properties are observed for antiferroelectric phase with antiparallel dipoles, while enhanced strain and dielectric permittivity are gained around ferroelectric-paraelectric coexistence or paraelectric region originating from electric field-induced ferroelectric state from polar nanoregions. Thus, this work demonstrated an abnormal phase transition in NN-based ceramics, promoting the understanding of antiferroelectrics.

The Reversibility Paradox: Role of the Velocity Reversal Step

The reversibility, or Loschmidt paradox, is a thought experiment in which microscopic reversibility is exploited to generate an apparently spontaneous trajectory in which entropy decreases, thus violating the Second Law of Thermodynamics (SLT). To achieve this, the system is allowed to evolve from a low-entropy to a high-entropy configuration, at which point all velocities of its molecules are reversed, thus producing the desired effect. In this paper we focus on the velocity reversal step. Implementing this step requires the measurement of velocities and positions, which must be stored in a memory. Even in the case of a reversible measurement, the erasure of the stored information, necessary to reset the measuring device to its original state, has an entropy cost that offsets the entropy decrease during the reverse evolution of the system. This cost is sufficient to explain why the described procedure does not violate the SLT.

Study on reservoir optimal operation based on coupled adaptive ε constraint and multi strategy improved Pelican algorithm

The optimal operation of reservoir groups is a strongly constrained, multi-stage, and high-dimensional optimization problem. In response to this issue, this article couples the standard Pelican optimization algorithm with adaptive ε constraint methods, and further improves the optimization performance of the algorithm by initializing the population with a good point set, reverse differential evolution, and optimal individual t-distribution perturbation strategy. Based on this, an improved Pelican algorithm coupled with adaptive ε constraint method is proposed (ε-IPOA). The performance of the algorithm was tested through 24 constraint testing functions to find the optimal ability and solve constraint optimization problems. The results showed that the algorithm has strong optimization ability and stable performance. In this paper, we select Sanmenxia and Xiaolangdi reservoirs as the research objects, establish the maximum peak-cutting model of terrace reservoirs, apply the ε-IPOA algorithm to solve the model, and compare it with the ε-POA (Pelican algorithm coupled with adaptive ε constraint method) and ε-DE (Differential Evolution Algorithm) algorithms, the results indicate that ε. The peak flow rate of the Huayuankou control point solved by the IPOA algorithm is 12,319 m3/s, which is much lower than the safe overflow flow rate of 22,000 m3/s at the Huayuankou control point, with a peak shaving rate of 44%, and other algorithms do not find effective solutions meeting the constraint conditions. This paper provides a new idea for solving the problem of flood control optimal operation of cascade reservoirs.

Temperature/pH dual-responsive reversible morphology evolution of block copolymer microparticles under three-dimensional confinement

Temperature/pH dual-responsive reversible morphology evolution of block copolymer microparticles under three-dimensional confinement