Rate Of Evolution Research Articles

Hydrogen generation by hydrolysis of alkaline NaBH4 solution doped with amorphous catalyst Co–Y2O3–B/CNTs

This investigation enhances the catalytic efficiency of Co–B/CNTs for hydrogen production via sodium borohydride hydrolysis by doping with 5%Y2O3. Such doping significantly boosts hydrogen evolution rates, with Co–Y2O3–B/CNTs achieving a production rate of 1083.43 ml g−1·min−1—surpassing Co–B/CNTs by 1.5 times and tripling that of Co–B catalysts. SEM and XRD analyses show Y2O3 doping reduces particle aggregation and maintains the catalyst's amorphous state, thereby increasing the active surface area. Furthermore, XPS analysis demonstrates that introducing yttrium into Co–B/CNTs catalysts improves their surface elemental composition and valence states. This improvement boosts catalyst performance and stability by enhancing electron transfer and particle size optimization. Optimal hydrolysis is achieved at an NaOH concentration of 2.5 mol/L, with higher concentrations diminishing hydrogen production due to increased viscosity from by-product formation. Additionally, Co–Y2O3–B/CNTs catalysts exhibit commendable durability, maintaining more than two-thirds of their initial activity after five reuse cycles, outperforming comparable catalysts to a moderate extent. These findings underscore the beneficial role of Y2O3 in the Co–B/CNTs framework, promoting Y2O3-doped catalysts for their enhanced efficiency, sustainability, and hydrogen production capabilities.

Covalently Linking Reduced Graphene Oxide Facilitated Electrodeposition of MoS2 on Silicon Pyramidal Photocathode To Enhance Hydrogen Evolution.

In recent years, increasing attention has been paid to photoelectrochemical (PEC) hydrogen production owing to the utilization of sustainable solar energy and its promising performance. Silicon-based composites are generally considered ideal materials for PEC hydrogen production. However, slow reaction kinetics and poor stability are still key factors hindering the development of silicon-based photoelectrocatalysts. Herein, we present an n+-p Si pyramidal photocathode assembly method to load reduced graphene oxide (rGO) onto the surface of the n+-p Si pyramid by covalently linking (Si/rGO). rGO is utilized as a conductive layer to reduce the interfacial charge-transfer resistance. Then, MoS2 can be successfully electrodeposited on the surface of Si/rGO to form the Si/rGO/MoS2 composite, which possesses excellent PEC hydrogen evolution performance with a high and stable photocurrent of -41.6 mA cm-2 and a hydrogen evolution rate of about 18.1 μmol min-1 cm-2 under 0 V (vs RHE). The covalently linking rGO layer effectively enhances the transfer of photogenerated carriers between the Si substrate and MoS2. MoS2 provides abundant hydrogen evolution active sites, which accelerate the surface reaction kinetics, as well as a protective layer for the Si pyramidal array structure. This work provides a low-cost, convenient, and efficient way of preparing silicon-based photocathodes.

Shifts in evolutionary lability underlie independent gains and losses of root-nodule symbiosis in a single clade of plants

Root nodule symbiosis (RNS) is a complex trait that enables plants to access atmospheric nitrogen converted into usable forms through a mutualistic relationship with soil bacteria. Pinpointing the evolutionary origins of RNS is critical for understanding its genetic basis, but building this evolutionary context is complicated by data limitations and the intermittent presence of RNS in a single clade of ca. 30,000 species of flowering plants, i.e., the nitrogen-fixing clade (NFC). We developed the most extensive de novo phylogeny for the NFC and an RNS trait database to reconstruct the evolution of RNS. Our analysis identifies evolutionary rate heterogeneity associated with a two-step process: An ancestral precursor state transitioned to a more labile state from which RNS was rapidly gained at multiple points in the NFC. We illustrate how a two-step process could explain multiple independent gains and losses of RNS, contrary to recent hypotheses suggesting one gain and numerous losses, and suggest a broader phylogenetic and genetic scope may be required for genome-phenome mapping.

Hollow g-C3N4@Ag3PO4 Core-Shell Nanoreactor Loaded with Au Nanoparticles: Boosting Photothermal Catalysis in Confined Space.

Low solar energy utilization efficiency and serious charge recombination remain major challenges for photocatalytic systems. Herein, a hollow core-shell Au/g-C3N4@Ag3PO4 photothermal nanoreactor is successfully prepared by a two-step deposition method. Benefit from efficient spectral utilization and fast charge separation induced by the unique hollow core-shell heterostructure, the H2 evolution rate of Au/g-C3N4@Ag3PO4 is 16.9 times that of the pristine g-C3N4, and the degradation efficiency of tetracycline is increased by 88.1%. The enhanced catalytic performance can be attributed to the ordered charge movement on the hollow core-shell structure and a local high-temperature environment, which effectively accelerates the carrier separation and chemical reaction kinetics. This work highlights the important role of the space confinement effect in photothermal catalysis and provides a promising strategy for the development of the next generation of highly efficient photothermal catalysts.

Detection and Genetic Characterization of Bovine Torovirus in Uruguay

Bovine torovirus (BToV) is an enteric pathogen that may cause diarrhea in calves and adult cattle, which could result in economic losses due to weight loss and decreased milk production. This study aimed to report the presence, the genetic characterization and the evolution of BToV in calves in Uruguay. BToV was detected in 7.9% (22/278) of fecal samples, being identified in dairy (9.2%, 22/239) but not beef (0.0%, 0/39) calves. BToV was detected in both diarrheic (14%, 6/43) and non-diarrheic (13.2%, 5/38) dairy calves. In addition, BToV was detected in the intestinal contents of 14.9% (7/47) of naturally deceased dairy calves. A complete genome (28,446 nucleotides) was obtained, which was the second outside Asia and the first in Latin America. In addition, partial S gene sequences were obtained to perform evolutionary analyses. Nucleotide and amino acid substitutions within and between outbreaks/farms were observed, alerting the continuous evolution of the virus. Through Bayesian analysis using BEAST, a recent origin (mid-60s) of BToV, possibly in Asia, was estimated, with two introductions into Uruguay from Asia and Europe in 2004 and 2013, respectively. The estimated evolutionary rate was 1.80 × 10−3 substitutions/site/year. Our findings emphasize the importance of continued surveillance and genetic characterization for the effective management and understanding of BToV’s global epidemiology and evolution.

Radiating diversification and niche conservatism jointly shape the inverse latitudinal diversity gradient of Potentilla L. (Rosaceae)

BackgroundThe latitudinal diversity gradient (LDG), characterized by an increase in species richness from the poles to the equator, is one of the most pervasive biological patterns. However, inverse LDGs, in which species richness peaks in extratropical regions, are also found in some lineages and their causes remain unclear. Here, we test the roles of evolutionary time, diversification rates, and niche conservatism in explaining the inverse LDG of Potentilla (ca. 500 species). We compiled the global distributions of ~ 90% of Potentilla species, and reconstructed a robust phylogenetic framework based on whole-plastome sequences. Next, we analyzed the divergence time, ancestral area, diversification rate, and ancestral niche to investigate the macroevolutionary history of Potentilla.ResultsThe genus originated in the Qinghai-Tibet Plateau during the late Eocene and gradually spread to other regions of the Northern Hemisphere posterior to the late Miocene. Rapid cooling after the late Pliocene promoted the radiating diversification of Potentilla. The polyploidization, as well as some cold-adaptive morphological innovations, enhanced the adaptation of Potentilla species to the cold environment. Ancestral niche reconstruction suggests that Potentilla likely originated in a relatively cool environment. The species richness peaks at approximately 45 °N, a region characterized by high diversification rates, and the environmental conditions are similar to the ancestral climate niche. Evolutionary time was not significantly correlated with species richness in the latitudinal gradient.ConclusionsOur results suggest that the elevated diversification rates in middle latitude regions and the conservatism in thermal niches jointly determined the inverse LDG in Potentilla. This study highlights the importance of integrating evolutionary and ecological approaches to explain the diversity pattern of biological groups on a global scale.

Enhancing Photocatalytic Activities for Sustainable Hydrogen Evolution on Structurally Matched CuInS2/ZnIn2S4 Heterojunctions

Effective charge separation and migration pose a critical challenge in the field of solar-driven hydrogen production. In this work, a Z-scheme structured CuInS2/ZnIn2S4 heterojunction was successfully fabricated through a two-step hydrothermal synthesis method to significantly enhance the efficiency of solar-to-hydrogen energy conversion. Structural characterization revealed that the lattice-matched CuInS2/ZnIn2S4 heterojunction exhibits an enlarged interfacial contact area, which facilitates the transfer and separation of photogenerated charges. Microscopic analysis indicated that the CuInS2/ZnIn2S4 composite material has a tightly interwoven interface and a morphology resembling small sugar cubes. Photoelectrochemical spectroscopy analysis demonstrated that the heterojunction structure effectively enhances visible light absorption and charge separation efficiency, leading to an improvement in photocatalytic activity. Hydrogen production experimental data indicated that the CuInS2/ZnIn2S4 heterojunction photocatalyst prepared with a CuInS2 content of 20 wt% exhibits the highest hydrogen evolution rate, reaching 284.9 μmol·g−1·h−1. Moreover, this photocatalyst maintains robust photocatalytic stability even after three consecutive usage cycles. This study demonstrated that the Z-scheme CuInS2/ZnIn2S4 heterojunction photocatalyst exhibits enhanced hydrogen evolution efficiency, offering an effective structural design for harnessing solar energy to obtain hydrogen fuel. Therefore, this heterojunction photocatalyst is a promising candidate for practical applications in solar hydrogen production.

A new abelisaurid dinosaur from the end Cretaceous of Patagonia and evolutionary rates among the Ceratosauria.

Gondwanan dinosaur faunae during the 20 Myr preceding the Cretaceous-Palaeogene (K/Pg) extinction included several lineages that were absent or poorly represented in Laurasian landmasses. Among these, the South American fossil record contains diverse abelisaurids, arguably the most successful groups of carnivorous dinosaurs from Gondwana in the Cretaceous, reaching their highest diversity towards the end of this period. Here we describe Koleken inakayali gen. et sp. n., a new abelisaurid from the La Colonia Formation (Maastrichtian, Upper Cretaceous) of Patagonia. Koleken inakayali is known from several skull bones, an almost complete dorsal series, complete sacrum, several caudal vertebrae, pelvic girdle and almost complete hind limbs. The new abelisaurid shows a unique set of features in the skull and several anatomical differences from Carnotaurus sastrei (the only other abelisaurid known from the La Colonia Formation). Koleken inakayali is retrieved as a brachyrostran abelisaurid, clustered with other South American abelisaurids from the latest Cretaceous (Campanian-Maastrichtian), such as Aucasaurus, Niebla and Carnotaurus. Leveraging our phylogeny estimates, we explore rates of morphological evolution across ceratosaurian lineages, finding them to be particularly high for elaphrosaurine noasaurids and around the base of Abelisauridae, before the Early Cretaceous radiation of the latter clade. The Noasauridae and their sister clade show contrasting patterns of morphological evolution, with noasaurids undergoing an early phase of accelerated evolution of the axial and hind limb skeleton in the Jurassic, and the abelisaurids exhibiting sustained high rates of cranial evolution during the Early Cretaceous. These results provide much needed context for the evolutionary dynamics of ceratosaurian theropods, contributing to broader understanding of macroevolutionary patterns across dinosaurs.

Efficient Charge Separation in Ag/PCN/UPDI Ternary Heterojunction for Optimized Photothermal-Photocatalytic Performance via Tandem Electric Fields.

Charge separation driven by the internal electric field is a research hotspot in photocatalysis. However, it remains challenging to accurately control the electric field to continuously accelerate the charge transfer. Herein, a strategy of constructing a tandem electric field to continuously accelerate charge transfer in photocatalysts is proposed. The plasma electric field, interface electric field, and intramolecular electric field are integrated into the Ag/g-C3N4/urea perylene imide (Ag/PCN/UPDI) ternary heterojunction to achieve faster charge separation and longer carrier lifetime. The triple electric fields function as three accelerators on the charge transport path, promoting the separation of electron-hole pairs, accelerating charge transfer, enhancing light absorption, and increasing the concentration of energetic electrons on the catalyst. The H2 evolution rate of Ag/PCN/UPDI is 16.8 times higher than that of pristine PDI, while the degradation rate of oxytetracycline is increased by 4.5 times. This new strategy will provide a groundbreaking idea for the development of high-efficiency photocatalysts.

Does Phenotypic Integration Promote Convergent Evolution?

Phenotypic integration is often perceived as being able to produce convergent evolution in the absence of selection, but specific mechanisms for this process are lacking and a connection has never been empirically demonstrated. A new model of the effect of integration on convergence provides such a mechanism, along with other predictions about the influence of integration on evolutionary patterns. I use simulations and data from three empirical systems-turtle shells, characiform fishes, and squirrel mandibles-to investigate the degree to which evolutionary integration is associated with high levels of convergent evolution. Levels of integration were varied in Brownian motion simulations and the resulting amounts of stochastic convergent evolution were quantified. Each empirical system was divided into modules, and the strength of integration, average amount of convergence, phenotypic disparity, and rate of evolution in each module was measured. Results from the simulations and from all three empirical systems converge on a common result: higher levels of phenotypic integration are indeed associated with higher levels of convergence. This is despite a lack of consistent association between the strength of phenotypic integration and evolutionary rate or disparity. The results here are only correlational. Further studies which more closely examine the influence of within-population drivers of evolutionary integration-for example, genetic or developmental integration-on convergence are required before it is possible to definitively establish when phenotypic integration can cause evolutionary convergence. Until then, however, the results of this study strongly suggest that phenotypic integration will often promote convergent evolution.

Wiring between close nodes in molecular networks evolves more quickly than between distant nodes.

As species diverge, a wide range of evolutionary processes lead to changes in protein-protein interaction networks and metabolic networks. The rate at which molecular networks evolve is an important question in evolutionary biology. Previous empirical work has focused on interactomes from model organisms to calculate rewiring rates, but this is limited by the relatively small number of species and sparse nature of network data across species. We present a proxy for variation in network topology: variation in drug-drug interactions (DDIs), obtained by studying drug combinations (DCs) across taxa. Here, we propose the rate at which DDIs change across species as an estimate of the rate at which the underlying molecular network changes as species diverge. We computed the evolutionary rates of DDIs using previously published data from a high throughput study in gram-negative bacteria. Using phylogenetic comparative methods, we found that DDIs diverge rapidly over short evolutionary time periods, but that divergence saturates over longer time periods. In parallel, we mapped drugs with known targets in protein-protein interaction and co-functional networks. We found that the targets of synergistic DDIs are closer in these networks than other types of DCs and that synergistic interactions have a higher evolutionary rate, meaning that nodes that are closer evolve at a faster rate. Future studies of network evolution may use DC data to gain larger-scale perspectives on the details of network evolution within and between species.

Changeable Active Sites by Pr Doping CuSA-TiO2 Photocatalyst for Excellent Hydrogen Production.

Photocatalytic water splitting for clean hydrogen production has been a very attractive research field for decades. However, the insightful understanding of the actual active sites and their impact on catalytic performance is still ambiguous. Herein, a Pr-doped TiO2-supported Cu single atom (SA) photocatalyst is successfully synthesized (noted as Cu/Pr-TiO2). It is found that Pr dopants passivate the formation of oxygen vacancies, promoting the density of photogenerated electrons on the CuSAs, and optimizing the electronic structure and H* adsorption behavior on the CuSA active sites. The photocatalytic hydrogen evolution rate of the obtained Cu/Pr-TiO2 catalyst reaches 32.88mmolg-1h-1, 2.3 times higher than the Cu/TiO2. Innovatively, the excellent catalytic activity and performance is attributed to the active sites change from O atoms to CuSAs after Pr doping is found. This work provides new insight for understanding the accurate roles of single atoms in photocatalytic water splitting.

Selenium doping to improve internal electric field for excellent photocatalytic efficiency of g-C3N4 nanosheets

Graphitic carbon nitride is a promising photocatalyst to address environmental issues and energy applications. Herein, we develop an efficient defect-containing functionalized system of 2D selenium doped g-C3N4 porous nanosheets via one pot with two-step temperature for the first time. During heat treatment, Se-infused g-C3N4 nanosheets loosen stacking and form thinner nanosheets, which could effectively shorten the electronic path of charge migration. The introduction of nitrogen vacancies creates a midgap energy state below the CB, which improves the light-harvesting efficiency. Moreover, the dual effect of N vacancy and Se doping provides a driving force for the dissociation of excitons and achieves an effective spatial charge separation. High specific surface area (104.1 m2/g), suitable bandgap (2.65 eV), and good photocurrent response (0.45 µA cm−2) help to enhance the photocatalytic efficiency of 1-SeCN remarkably. Henceforth, high photocatalytic H2 production rate of 5441 µmol g−1 h−1 and CO evolution rate of 31.5 µmol g−1 h−1 verifies the effective Se doping enhances the photocatalytic efficiency of g-C3N4. Furthermore, DFT calculations are consistent with experimental results and this facile engineering strategy provides a scalable way to develop a novel, efficient g-C3N4-based photocatalyst for H2 production and CO2 reduction.

Limits on the evolutionary rates of biological traits

This paper focuses on the maximum speed at which biological evolution can occur. I derive inequalities that limit the rate of evolutionary processes driven by natural selection, mutations, or genetic drift. These rate limits link the variability in a population to evolutionary rates. In particular, high variances in the fitness of a population and of a quantitative trait allow for fast changes in the trait’s average. In contrast, low variability makes a trait less susceptible to random changes due to genetic drift. The results in this article generalize Fisher’s fundamental theorem of natural selection to dynamics that allow for mutations and genetic drift, via trade-off relations that constrain the evolutionary rates of arbitrary traits. The rate limits can be used to probe questions in various evolutionary biology and ecology settings. They apply, for instance, to trait dynamics within or across species or to the evolution of bacteria strains. They apply to any quantitative trait, e.g., from species’ weights to the lengths of DNA strands.

Phylogenomics, Lineage Diversification Rates, and the Evolution of Diadromy in Clupeiformes (Anchovies, Herrings, Sardines, and Relatives).

Migration independently evolved numerous times in animals, with a myriad of ecological and evolutionary implications. In fishes, perhaps the most extreme form of migration is diadromy, the migration between marine and freshwater environments. Key and longstanding questions are: how many times has diadromy evolved in fishes, how frequently do diadromous clades give rise to non-diadromous species, and does diadromy influence lineage diversification rates? Many diadromous fishes have large geographic ranges with constituent populations that use isolated freshwater habitats. This may limit gene flow among some populations, increasing the likelihood of speciation in diadromous lineages relative to non-diadromous lineages. Alternatively, diadromy may reduce lineage diversification rates if migration is associated with enhanced dispersal capacity that facilitates gene flow within and between populations. Clupeiformes (herrings, sardines, shads and anchovies) is a model clade for testing hypotheses about the evolution of diadromy because it includes an exceptionally high proportion of diadromous species and several independent evolutionary origins of diadromy. However, relationships among major clupeiform lineages remain unresolved and existing phylogenies sparsely sampled diadromous species, limiting the resolution of phylogenetically-informed statistical analyses. We assembled a phylogenomic dataset and used multi-species coalescent and concatenation-based approaches to generate the most comprehensive, highly-resolved clupeiform phylogeny to date, clarifying associations among several major clades and identifying recalcitrant relationships needing further examination. We determined that variation in rates of sequence evolution (heterotachy) and base-composition (non-stationarity) had little impact on our results. Using this phylogeny, we characterized evolutionary patterns of diadromy and tested for differences in lineage diversification rates between diadromous, marine, and freshwater lineages. We identified thirteen transitions to diadromy, all during the Cenozoic Era (ten origins of anadromy, two origins of catadromy, and one origin of amphidromy), and seven losses of diadromy. Two diadromous lineages rapidly generated non-diadromous species, demonstrating that diadromy is not an evolutionary dead-end. We discovered considerably faster transition rates out of diadromy than to diadromy. The largest lineage diversification rate increase in Clupeiformes was associated with a transition to diadromy, but we uncovered little statistical support for categorically faster lineage diversification rates in diadromous versus non-diadromous fishes. We propose that diadromy may increase the potential for accelerated lineage diversification, particularly in species that migrate long distances. However, this potential may only be realized in certain biogeographic contexts, such as when diadromy allows access to ecosystems in which there is limited competition from incumbent species.

Enhanced H2 Generation via Piezoelectric Reforming of Waste Sugars and Fruits Using Au-Decorated g-C3N4

The food industry is responsible for generating considerable amounts of waste, such as excess fruits and leftover sugars, which contribute to resource depletion and pose environmental challenges. This research delves into the application of gold-modified graphitic carbon nitride nanosheets (Au/CN) as a potent catalyst for the transformation of these food wastes into H2 via piezoelectric reforming during sonication. Au/CN demonstrated a superior rate of H2 evolution compared to pristine g-C3N4 (i.e., 1533.3 vs. 364.9 µmol/g/h) and it maintained its efficiency through multiple cycles of use. The catalytic activity was found to be optimal at a neutral pH level and with increased sugar concentrations. The enhanced catalytic performance of Au/CN was ascribed to the efficient segregation of charge carriers as well as the reduced charge transfer distance. This study underscores the viability of using Au/CN as a means for converting food wastes into a sustainable source of H2 energy.

Strategically designing and fabricating nitrogen and sulfur Co-doped g-C3N4 for accelerating photocatalytic H2 evolution

Doping engineering is an effective strategy for graphitic carbon nitride (g-C3N4) to improve its photocatalytic hydrogen evolution reaction (HER) performance. In this work, a novel nitrogen and sulfur co-doped g-C3N4 (N, S-g-C3N4) is elaborately designed on the basis of theoretical predictions of first-principle density functional theory (DFT). The calculated Gibbs free energy of adsorbed hydrogen (ΔGH*) for N, S-g-C3N4 at the N-doping active sites is extremely close to zero (0.01 eV). Inspired by the theoretical predictions, the N, S-g-C3N4 is successfully fabricated through ammonia-rich pyrolysis synthesis strategy, in which ammonia is in-situ obtained by pyrolyzing melamine. Subsequent characterizations indicate that the N, S-g-C3N4 possesses high specific surface area, outstanding light utilization, good hydrophilicity, and efficient carrier transfer efficiency. Consequently, the N, S-g-C3N4 displays an extremely high H2 evolution rate of 8269.9 µmol g−1 h−1, achieves an apparent quantum efficiency (AQE) of 3.24%, and also possesses outsatnding durability. Theoretical calculations further demonstrate that N and S dopants can not only introduce doping energy level to reduce the band gap, but also induce charge redistribution to facilitate hydrogen adsorption, thus promoting the photocatalytic HER process. Moreover, femtosecond transient absorption (fs-TA) spectroscopy further corroborates the efficient photogenerated carrier transport of N, S-g-C3N4. This research highlights a promising and reliable strategy to achieve superior photocatalytic activity, and exhibits significant guidance for precise designing high-efficiency photocatalysts.

Hydrophilic Photocrosslinkers as a Universal Solution to Endow Water Affinity to a Polymer Photocatalyst for an Enhanced Hydrogen Evolution Rate.

A universal approach for enhancing water affinity in polymer photocatalysts by covalently attaching hydrophilic photocrosslinkers to polymer chains is presented. A series of bisdiazirine photocrosslinkers, each comprising bisdiazirine photophores linked by various aliphatic (CL-R) or ethylene glycol-based bridge chains (CL-TEG), is designed to prevent crosslinked polymer photocatalysts from degradation through a safe and efficient photocrosslinking reaction at a wavelength of 365nm. When employing the hydrophilic CL-TEG as a photocrosslinker with polymer photocatalysts (F8BT), the hydrogen evolution reaction (HER) rate is considerably enhanced by 2.5-fold compared to that obtained using non-crosslinked F8BT photocatalysts, whereas CL-R-based photocatalysts yield HER rates comparable to those of non-crosslinked counterparts. Photophysical analyses including time-resolved photoluminescence and transient absorption measurements reveal that adding CL-TEG accelerates exciton separation, forming long-lived charge carriers. Additionally, the in-depth study using molecular dynamics simulations elucidates the dual role of CL-TEG: it enhances water penetration into the polymer matrix and stabilizes charge carriers after exciton generation against undesirable recombination. Therefore, the strategy highlights endowing a high-permittivity environment within polymer photocatalyst in a controlled manner is crucial for enhancing photocatalytic redox reactivity. Furthermore, this study shows that this hydrophilic crosslinker approach has a broad applicability in general polymer semiconductors and their nanoparticulate photocatalysts.

Symmetry‐breaking of Dibenzo[b,d]thiophene Sulfone Enhancing Polaron Generation for Boosted Photocatalytic Hydrogen Evolution

The current bottleneck in the development of efficient photocatalysts for hydrogen evolution is the limited availability of high‐performance acceptor units. Over the past nine years, dibenzo[b,d]thiophene sulfone (DBS) has been the preferred choice for the acceptor unit. Despite extensive exploration of alternative structures as potential replacements for DBS, a superior substitute remains elusive. In this study, a symmetry‐breaking strategy was employed on DBS to develop a novel acceptor unit, BBTT‐1SO. The asymmetric structure of BBTT‐1SO proved beneficial for increasing multiple moment and polarizability. BBTT‐1SO‐containing polymers showed higher efficiencies for hydrogen evolution than their DBS‐containing counterparts by up to 166%. PBBTT‐1SO exhibited an excellent hydrogen evolution rate (HER) of 222.03 mmol g−1 h−1 and an apparent quantum yield of 27.5% at 500 nm. Transient spectroscopic studies indicated that the BBTT‐1SO‐based polymers facilitated electron polaron formation, which explains their superior HERs. PBBTT‐1SO also showed 14% higher HER in natural seawater splitting than that in deionized water splitting. Molecular dynamics simulations highlighted the enhanced water‐PBBTT‐1SO polymer interactions in salt‐containing solutions. This study presents a pioneering example of a substitute acceptor unit for DBS in the construction of high‐performance photocatalysts for hydrogen evolution.

Π‐Bridge Modulations in D–π–A Conjugated Microporous Polymers to Facilitate Charge Separation and Transfer Kinetics for Efficient Photocatalysis

AbstractThe burgeoning field of conjugated microporous polymers (CMPs) has generated widespread interest due to their potential as photocatalysts for hydrogen production from water. Nevertheless, their photocatalytic performance is sometimes hindered by inadequate charge separation and transfer, coupled with rapid charge recombination. Herein, a strategy to enhance photocatalytic performance via the customization of π‐bridges through the modulation of heteroatoms in a series of donor‐π‐acceptor (D‐π‐A) CMPs is proposed. This affords optimized energy levels and improved charge separation and transfer, thus boosting photocatalytic efficiency. Among various heteroatom substitutions, S‐doped CMP (10 mg) demonstrates the highest photocatalytic hydrogen evolution rate of 203 µmol h−1 (AQY450nm = 7.4%) under visible light irradiation. Subsequent experimental analysis reveals its superior photocatalytic performance can be largely related to its minimized exciton binding energy, facilitated charge transfer efficiency, and impeded charge recombination among these heteroatom‐doped D‐π‐A CMPs. This research paves the way for the rational design and modification of organic semiconductors for advanced solar‐driven photocatalysis by promoting charge separation and transfer.