Rate Of Evolution Research Articles

Full-length transcriptome analysis of Ophioglossum vulgatum: effects of experimentally identified chloroplast gene clusters on expression and evolutionary patterns.

Genes with similar or related functions in chloroplasts are often arranged in close proximity, forming clusters on chromosomes. These clusters are transcribed coordinated to facilitate the expression of genes with specific function. Our previous study revealed a significant negative correlation between the chloroplast gene expression level of the rare medicinal fern Ophioglossum vulgatum and its evolutionary rates as well as selection pressure. Therefore, in this study, we employed a combination of SMRT and Illumina sequencing technology to analyze the full-length transcriptome sequencing of O. vulgatum for the first time. In particular, we experimentally identified gene clusters based on transcriptome data and investigated the effects of chloroplast gene clustering on expression and evolutionary patterns. The results revealed that the total sequenced data volume of the full-length transcriptome of O. vulgatum amounted to 71,950,652,163bp, and 110 chloroplast genes received transcript coverage. Nine different types of gene clusters were experimentally identified in their transcripts. The chloroplast cluster genes may cause a decrease in non-synonymous substitution rate and selection pressure, as well as a reduction in transversion rate, transition rate, and their ratio. While expression levels of chloroplast cluster genes in leaf, sporangium, and stem would be relatively elevated. The Mann-Whitney U test indicated statistically significant in the selection pressure, sporangia and leaves groups (P < 0.05). We have contributed novel full-length transcriptome data resources for ferns, presenting new evidence on the effects of chloroplast gene clustering on expression land evolutionary patterns, and offering new theoretical support for transgenic research through gene clustering.

Genomic insights into the evolution, pathogenicity, and extensively drug-resistance of emerging pathogens Kluyvera and Phytobacter.

Kluyvera is a Gram-negative, flagellated, motile bacillus within the Enterobacteriaceae. The case reports of clinical infections shed light on the importance of this organism as an emerging opportunistic pathogen. The genus Phytobacter, which often be misidentified with Kluyvera, is also an important clinically relevant member of the Enterobacteriaceae. However, the identification of Kluyvera and Phytobacter is problematic, and their phylogenetic relationship remains unclear. Here, 81 strains of Kluyvera and 16 strains of Phytobacter were collected. A series of comparative genomics approaches were applied to the phylogenetic relationship reconstruction, virulence related genes profiles description, and antibiotic resistance genes prediction. Using average nucleotide identity (ANI) and in silico DNA-DNA hybridization (isDDH), we offered reliable species designations of 97 strains, in which 40 (41.24%) strains were incorrectly labeled. A new Phytobacter genomospecies-1 were defined. Phytobacter and Kluyvera show great genome plasticity and inclusiveness, which may be related to their diverse ecological niches. An intergenomic distances threshold of 0.15875 was used for taxonomy reassignments at the phylogenomic-group level. Further principal coordinates analysis (PCoA) revealed 11 core genes of Kluyvera (pelX, mdtL, bglC, pcak-1, uhpB, ddpA-2, pdxY, oppD-1, cptA, yidZ, csbX) that could be served as potential identification targets. Meanwhile, the Phytobacter specific virulence genes clbS, csgA-C, fliS, hsiB1_vipA and hsiC1_vipB, were found to differentiate from Kluyvera. We concluded that the evolution rate of Kluyvera was 5.25E-6, approximately three times higher than that of Phytobacter. Additionally, the co-existence of ESBLs and carbapenem resistance genes were present in approximately 40% strains, suggesting the potential development of extensively drug-resistant or even fully drug-resistant strains. This work provided a better understanding of the differences between closely related species Kluyvera and Phytobacter. Their genomes exhibited great genome plasticity and inclusiveness. They not only possess a potential pathogenicity threat, but also a risk of multi-drug resistance. The emerging pathogens Kluyvera and Phytobacter warrant close attention.

The Effect of Global Spread, Epidemiology, and Control Strategies on the Evolution of the GI-19 Lineage of Infectious Bronchitis Virus.

The GI-19 lineage of infectious bronchitis virus (IBV) has emerged as one of the most impactful, particularly in the "Old World". Originating in China several decades ago, it has consistently spread and evolved, often forming independent clades in various areas and countries, each with distinct production systems and control strategies. This study leverages this scenario to explore how different environments may influence virus evolution. Through the analysis of the complete S1 sequence, four datasets were identified, comprising strains of monophyletic clades circulating in different continents or countries (e.g., Asia vs. Europe and China vs. Thailand), indicative of single introduction events and independent evolution. The population dynamics and evolutionary rate variation over time, as well as the presence and intensity of selective pressures, were estimated and compared across these datasets. Since the lineage origin (approximately in the mid-20th century), a more persistent and stable viral population was estimated in Asia and China, while in Europe and Thailand, a sharp increase following the introduction (i.e., 2005 and 2007, respectively) of GI-19 was observed, succeeded by a rapid decline. Although a greater number of sites on the S1 subunit were under diversifying selection in the Asian and Chinese datasets, more focused and stronger pressures were evident in both the European (positions 2, 52, 54, 222, and 379 and Thai (i.e., positions 10, 12, 32, 56, 62, 64, 65, 78, 95, 96, 119, 128, 140, 182, 292, 304, 320, and 323) strains, likely reflecting a more intense and uniform application of vaccines in these regions. This evidence, along with the analysis of control strategies implemented in different areas, suggests a strong link between effective, systematic vaccine implementation and infection control. However, while the overall evolutionary rate was estimated at approximately 10-3 to 10-4, a significant inverse correlation was found between viral population size and the rate of viral evolution over time. Therefore, despite the stronger selective pressure imposed by vaccination, effectively constraining the former through adequate control strategies can efficiently prevent viral evolution and the emergence of vaccine-escaping variants.

New Caledonian rovers and the historical biogeography of a hyper‐diverse endemic lineage of South Pacific leaf beetles

AbstractSouth Pacific archipelagos are central in the biogeographic debate on the relative importance of vicariance and dispersal in shaping the distribution of species. However, each taxonomic group was subject to different processes and histories, and here, we reveal the historical biogeography of the diverse Eumolpinae leaf beetles, widely distributed in the region. Extensive taxon sampling focusing on South Pacific Eumolpinae was used to infer the first molecular phylogeny of the group using three single‐copy protein‐coding nuclear and two mitochondrial markers. Upon assessing the clade of interest for lineage‐specific variation in substitution rates, the age of the most recent common ancestors was estimated using out‐group calibration and multi‐gamma site models (MGSMs). Biogeographic analyses used standard event‐based inferences also incorporating phylogenetic uncertainty. Zealandian Eumolpinae are monophyletic and appear to have split from their global relatives in the transition from the Cretaceous to the Paleogene. Variation in the rates of molecular evolution affected the in‐group stem branch, with a significant drop in the substitution rate, and the MGSM correction recovered the crown age of Zealandian Eumolpinae during the Late Eocene–Oligocene transition. Biogeographic inference resolved the origin of the radiation in New Caledonia, favouring a null model without island age constraints, and repeated dispersal events to the other islands, including three independent but synchronous colonisations of New Zealand during the Miocene. New Caledonia, with a highly diverse Eumolpinae fauna of uncertain origin, acted as a hub and pump of biodiversity of these beetles in the entire South Pacific region, sending migrants to other islands through long‐distance dispersal with lineages establishing when land became available.

Development of high‐resolution monthly precipitation datasets for geomorphological applications in the Tianshan Mountains from 2000 to 2050

AbstractPrecipitation has a fundamental influence on landscape evolution and erosion rates. Accurate predictions of precipitation changes are crucial for landscape evolution modelling and erosion modelling. The Tianshan Mountains are known as the ‘Water Tower in Central Asia’, where precipitation is the main water supply for the surrounding lakes and rivers and also supports the population and economic development in the plain areas. This study developed a global climate model (GCM) and digital elevation model (DEM)‐based downscaling method and simulated high‐resolution monthly precipitation in Tianshan from 2000 to 2050, with a resolution of 90 m. The datasets developed from 30 surface observation stations had a high degree of precision and simulated the precipitation processes well in the historical period. The simulation results indicated that precipitation will increase at a rate of 11 mm/decade under the SSP245 scenario and 5 mm/decade under the RCP4.5 scenario from 2022 to 2050. Spatially, precipitation was projected to increase in the central and eastern regions and decrease in the western region. In the Kaidu, Urumqi and Manas river basins in the central Tianshan Mountains, precipitation was projected to increase at a rate of 20 mm/decade. The datasets developed here have important theoretical and practical implications for water resource management, and sustainable development in Central Asia.

The evolution of the gliotoxin biosynthetic gene cluster in Penicillium fungi.

Fungi biosynthesize diverse secondary metabolites, small organic bioactive molecules with key roles in fungal ecology. Fungal secondary metabolites are often encoded by physically clustered genes known as biosynthetic gene clusters (BGCs). Fungi in the genus Penicillium produce a cadre of secondary metabolites, some of which are useful (e.g. the antibiotic penicillin and the cholesterol-lowering drug mevastatin) and others harmful (e.g. the mycotoxin patulin and the immunosuppressant gliotoxin) to human affairs. Fungal genomes often also encode resistance genes that confer protection against toxic secondary metabolites. Some Penicillium species, such as Penicillium decumbens, are known to produce gliotoxin, a secondary metabolite with known immunosuppressant activity. To investigate the evolutionary conservation of homologs of the gliotoxin BGC and of genes involved in gliotoxin resistance in Penicillium, we analyzed 35 Penicillium genomes from 23 species. Homologous, lesser fragmented gliotoxin BGCs were found in 12 genomes, mostly fragmented remnants of the gliotoxin BGC were found in 21 genomes, whereas the remaining 2 Penicillium genomes lacked the gliotoxin BGC altogether. In contrast, broad conservation of homologs of resistance genes that reside outside the BGC across Penicillium genomes was observed. Evolutionary rate analysis revealed that BGCs with higher numbers of genes evolve slower than BGCs with few genes, suggestive of constraint and potential functional significance or more recent decay. Gene tree-species tree reconciliation analyses suggested that the history of homologs in the gliotoxin BGC across the genus Penicillium likely involved multiple duplications, losses, and horizontal gene transfers. Our analyses suggest that genes encoded in BGCs can have complex evolutionary histories and be retained in genomes long after the loss of secondary metabolite biosynthesis.

Adjusting photocatalytic hydrogen production of TiO2 hollow nanospheres through nitrogen-induced shallow trapping levels

N-doped titanium dioxide (TiO[Formula: see text] hollow nanospheres with abundant oxygen vacancies were successfully synthesized by coupling urea treatment and annealing in an N2 atmosphere. The pristine TiO2 hollow nanospheres exhibit a shallow donor level for electron trapping, while the urea treatment generates a N 2p acceptor level for hole trapping. After annealing in N2, the sufficient N atoms generate abundant oxygen vacancies for trapping electrons, resulting in further improved charge separation efficiency. The N-doped TiO2 exhibits the highest H2 evolution rate, reaching 2867[Formula: see text][Formula: see text]mol[Formula: see text]g[Formula: see text][Formula: see text]h[Formula: see text], which is six times higher than that of pristine TiO2 hollow nanospheres. The introduction of oxygen vacancies by interstitial N provides a promising way to improve the photocatalysis activity of photocatalysts.

Visible‐Light‐Induced Photocatalytic Hydrogen Evolution Performance of Graphdiyne‐Alkyne Phosphating Mo–Metal‐Organic Frameworks Heterojunction

Herein, the application of graphdiyne (GDY) in photocatalytic splitting of water and hydrogen evolution is explored. In this article, GDY is prepared by ball milling using calcium carbide as raw material, and it is compounded with phosphating Mo–metal‐organic frameworks (MOFs), to explore the photocatalytic hydrogen evolution performance and hydrogen evolution mechanism of composite catalysts. In the results, it is shown that the P–Mo–MOFs (PMF)/G‐25 composite photocatalyst has the best hydrogen evolution activity, and the hydrogen evolution rate is highest at pH = 9, reaching 1668.5 μmol g−1 h−1. Through the four‐cycle hydrogen evolution cycle stability test, the PMF/G‐25 composites still has good hydrogen evolution stability. It is shown that the combination of phosphating Mo–MOFs and GDY can enhance the hydrogen evolution activity and has excellent hydrogen evolution performance. In the Mott–Schottky test, it is found that PMF and GDY are n‐type semiconductors. The conduction and valence values are −0.56 and 1.10 eV for GDY, and −0.68 and 0.97 eV for PMF, respectively. The mechanism of photocatalytic hydrogen evolution is analyzed, and it is speculated that S‐Scheme heterojunction is formed between PMF and GDY to further promote photocatalytic hydrogen evolution.

Combining Molecular, Macroevolutionary, and Macroecological Perspectives on the Generation of Diversity.

Charles Darwin presented a unified process of diversification driven by the gradual accumulation of heritable variation. The growth in DNA databases and the increase in genomic sequencing, combined with advances in molecular phylogenetic analyses, gives us an opportunity to realize Darwin's vision, connecting the generation of variation to the diversification of lineages. The rate of molecular evolution is correlated with the rate of diversification across animals and plants, but the relationship between genome change and speciation is complex: Mutation rates evolve in response to life history and niche; substitution rates are influenced by mutation, selection, and population size; rates of acquisition of reproductive isolation vary between populations; and traits, niches, and distribution can influence diversification rates. The connection between mutation rate and diversification rate is one part of the complex and varied story of speciation, which has theoretical importance for understanding the generation of biodiversity and also practical impacts on the use of DNA to understand the dynamics of speciation over macroevolutionary timescales.

The macroevolution of sexual size dimorphism in birds

Abstract There is considerable variation of sexual size dimorphism (SSD) in body mass among animal groups, yet the drivers of interspecific variation in SSD are still poorly understood. Possible mechanisms have been suggested, including sexual selection, selection for fecundity in females, niche divergence between sexes, and allometry, yet their relative importance is still poorly understood. Here, we tested predictions of these four hypotheses in different avian groups using a large-scale dataset on SSD of body mass for 4761 species. Specifically, we estimated the probability of transition between male- and female-biased SSD, tested for differences in evolutionary rates of body mass evolution for males and females, and assessed the potential ecological and spatial correlates of SSD. Our results were consistent with the sexual selection, fecundity, and niche divergence hypotheses, but their support varied considerably among avian orders. In addition, we found little evidence that the direction of SSD affected the evolution of male or female body mass, and no relationship was detected between SSD and environmental predictors (i.e. temperature and precipitation seasonality, productivity, species richness, and absolute latitude). These results suggest that avian evolution of SSD is likely to be multifactorial, with sexual selection, fecundity, and niche divergence playing important roles in different avian orders.

Metal-free thiophene-based covalent organic frameworks achieve efficient photocatalytic hydrogen evolution by accelerating interfacial charge transfer

Photocatalysis is widely recognized as an efficient and environmentally friendly pathway for the conversion of solar energy into chemical energy. In recent years, designing efficient hydrogen evolution to obtain green clean energy has been one of the major challenges faced by researchers. Covalent organic frameworks (COFs) are considered as new and effective photocatalyst due to the inherent porosity, high crystallinity and structural adjustability. In this study, two metal-free thiophene-based covalent organic frameworks (JLNU-308 and JLNU-309) were constructed by solvothermal method through effective modulation sites. Because JLNU-COFs has a narrow band gap and good absorption capacity in the spectral range, the interfacial charge transfer speed is accelerated to solve the problem of low charge separation efficiency. Remarkably, JLNU-309 displays an impressive hydrogen evolution rate of 2868.57 μmol g−1 h−1 under visible light irradiation (λ > 420 nm). The superior hydrogen evolution reaction (HER) activity is due to the triazine units, which have high visible light absorption capacity, one-dimensional nanochannels of two-dimensional COFs and synergy with charge mobility. The photoelectrochemical measurements and calculation of density functional theory (DFT) supports the accuracy of the experiment. This work opens an avenue for constructing functional covalent organic frameworks for environmentally relevant critical applications. In addition, the simple synthesis process, excellent activity and high chemical stability indicate that JLNU-COFs are promising photocatalytic hydrogen production materials.

A triazine-based covalent organic framework decorated with cadmium sulfide for efficient photocatalytic hydrogen evolution from water

Construction of inorganic/organic heterostructures has been proven to be a very promising strategy to design highly efficient photocatalysts for solar driven hydrogen evolution from water. Herein, we report the preparation of a direct Z-scheme heterojunction photocatalyst by in situ growth of cadmium sulfide on a triazine-based covalent organic framework (COF). The triazine based-COF was synthesized by condensation reaction of precursors 1,3,5-tris-(4-formyl-phenyl) triazine (TFPT) and 2,5-bis-(3-hydroxypropoxy) terephthalohydrazide (DHTH), termed as TFPT-DHTH-COF. Widely distributed nitrogen atoms throughout TFPT-DHTH-COF skeletons serve as anchoring sites for strong interfacial interactions with CdS. The CdS/TFPT-DHTH-COF composite showed a hydrogen evolution rate of 15.75 mmol h−1 g−1, which is about 75 times higher than that of TFPT-DHTH-COF (0.21 mmol h−1 g−1) and 3.4 times higher than that of CdS (4.57 mmol h−1 g−1). With the properly staggered band alignment and strong interfacial interaction between TFPT-DHTH-COF and CdS, a Z-scheme charge transfer pathway is achieved. The mechanism has been systematically analyzed by steady state and time-resolved photoluminescence measurements as well as in situ irradiated X-ray photoelectron spectroscopy.

Excellent Charge Separation of NCQDs/ZnS Nanocomposites for the Promotion of Photocatalytic H2 Evolution.

Carbon Quantum dots (CQDs) are widely studied because of their good optical and electronic characteristics and because they can easily generate photocarriers. Nitrogen-doped CQDs (NCQDs) may exhibit improved hydrophilic, optical, and electron-transfer properties, which are conducive to photocatalytic hydrogen evolution. In this paper, NCQD-modified ZnS catalysts were successfully prepared. Under the irradiation of the full spectrum, the H2 evolution rate of the optimal catalyst 0.25 wt % NCQDs/ZnS achieves 5.70 mmol g-1 h-1, which is 11.88, 43.84, and 5.14 times the values of ZnS (0.48 mmol g-1 h-1), NCQDs (0.13 mmol g-1 h-1), and CQDs/ZnS (1.11 mmol g-1 h-1), respectively. Furthermore, it shows good stability, indicating that the modification of NCQDs prevents the photocorrosion and oxidation of ZnS. The enhanced performance is due to NCQD loading, which promotes the separation of photogenerated carriers, optimizes the structures, and increases the specific surface area. This work highlights the fact that NCQD-modified ZnS may afford a new strategy to synthesize ZnS-based photocatalysts with enhanced H2 production performance.

Multiobjective‐Optimization MoS2/Cd‐ZnIn2S4/CdS Composites Prepared by In Situ Structure‐Tailored Technique for High‐Efficiency Hydrogen Generation

Photocatalytic water splitting into hydrogen production provides a new avenue to produce clean chemical fuels. However, developing high‐efficiency photocatalytic materials still remains a challenge till now. Herein, multiobjective‐optimization MoS2/Cd‐ZnIn2S4/CdS (MS/CZIS/CS) composites are successfully constructed by an in situ structure‐tailored technique. Benefiting from the synergistic feature integrating sulfur vacancy, II‐type CZIS/CS heterojunction and Schottky‐type MS/CS heterojunction, such composites not only effectively steer photogenerated carrier transfer but also markedly expedite surface reaction kinetics for hydrogen reduction reaction. As a result, an optimal hydrogen evolution rate of 11.49 mmol g−1 h−1 is achieved over the MS/CZIS/CS catalysts, which is approximately 4.79 times higher than that of pristine ZIS (2.40 mmol g−1 h−1). This work provides some new inspirations for the steering of carrier transfer and the design of multiobjective‐optimization photocatalysts with high efficiency.

Dual Function of Naphthalenediimide Supramolecular Photocatalyst with Giant Internal Electric Field for Efficient Hydrogen and Oxygen Evolution.

Organic supramolecular photocatalysts have garnered widespread attention due to their adjustable structure and exceptional photocatalytic activity. Herein, a novel bis-dicarboxyphenyl-substituent naphthalenediimide self-assembly supramolecular photocatalyst (SA-NDI-BCOOH) with efficient dual-functional photocatalytic performance is successfully constructed. The large molecular dipole moment and short-range ordered stacking structure of SA-NDI-BCOOH synergistically create a giant internal electric field (IEF), resulting in a remarkable 6.7-fold increase in its charge separation efficiency. Additionally, the tetracarboxylic structure of SA-NDI-BCOOH greatly enhances its hydrophilicity. Thus, SA-NDI-BCOOH demonstrates efficient dual-functional activity for photocatalytic hydrogen and oxygen evolution, with rates of 372.8 and 3.8µmol h-1 , respectively. Meanwhile, a notable apparent quantum efficiency of 10.86% at 400nm for hydrogen evolution is achieved, prominently surpassing many reported supramolecular photocatalysts. More importantly, with the help of dual co-catalysts, it exhibits photocatalytic overall water splitting activity with H2 and O2 evolution rates of 3.2 and 1.6µmol h-1 . Briefly, this work sheds light on enhancing the IEF by controlling the molecular polarity and stacking structure to dramatically improve the photocatalytic performance of supramolecular materials.

Thermoplasmonic TiN boosts photocatalysis in covalent-organic frameworks

Covalent-organic frameworks (COFs) hold promise for photocatalysis, but their efficiency is hindered by strong excitonic effects that limit charge separation and transfer. Here, we demonstrate a novel strategy to overcome this challenge by integrating thermoplasmonic TiN nanoparticles with a β-ketoenamine-linked COFs (TFP-BD). The enhanced local electromagnetic field generated by TiN promotes the separation of electron-hole pairs in TFP-BD. This enhancement is evidenced by a doubled carrier lifetime (∼0.99 ns) and photocurrent density (1.67 μA cm⁻²) in the 3% TiN@TFP-BD composite compared to pristine TFP-BD. Additionally, thermoplasmonic heating in 3% TiN@TFP-BD (69.2 °C) surpasses that of TFP-BD (62.15 °C), accelerating mass transport during the photocatalytic process. This synergistic effect leads to a remarkable hydrogen evolution rate (HER) of 37.59 mmol g⁻¹ h⁻¹, an 8.5-fold improvement over the pristine COFs. Our work highlights the potential of thermoplasmonic enhancement for solar fuel production and establishes a new approach to mitigate excitonic limitations in COF-based photocatalysts.

A new sphenodontian (Diapsida: Lepidosauria) from the Upper Triassic (Norian) of Germany and its implications for the mode of sphenodontian evolution

The Arnstadt Formation of Saxony-Anhalt, Germany has yielded some of Germany’s most substantial finds of Late Triassic tetrapods, including the sauropodomorph Plateosaurus and the stem-turtle Proganochelys quenstedti. Here, we describe an almost complete skull of a new sphenodontian taxon from this formation (Norian, 227–208 Ma), making it the oldest known articulated sphenodontian skull from Europe and one of the oldest in the world. The material is represented by the dermal skull roof and by the complete maxilla and temporal region, as well as parts of the palate, braincase, and lower jaw. A phylogenetic assessment recovers it as a basal sphenodontian closely related to Planocephalosaurus robinsonae and to Eusphenodontia, making it the earliest-diverging sphenodontian known with an articulated skull. Its cranial anatomy is generally similar to the well-known Diphydontosaurus avonis from the Rhaetian of England, showing that this successful phenotype was already established in the clade around 10 myr earlier than assumed. An analysis of evolutionary change rates recovers high rates of evolution in basal sphenodontians, with decreasing rates throughout the evolution of the group. However, contrary to previous studies, reversals in this trend were identified, indicating additional peaks of evolutionary change. These results improve our understanding of the early sphenodontian diversity in Europe, providing critical information on evolutionary trends throughout the history of the clade and sparking renewed interest in its evolution.

Oxygen vacancies-tuned BiOBr nanosheets for accelerating CO2 and Cr(VI) photoreduction

Unsatisfactory charge separation ability and insufficient active sites are the main factors leading to low efficiency for photocatalytic CO2 conversion and Cr(VI) reduction. Constructing surface defects to accelerate charge separation is an effective strategy for promoting photocatalytic process. Herein, the oxygen vacancies modulated BiOBr nanosheets were constructed by NaBH4 solution treatment. Density functional theory calculation results found that the formed oxygen vacancies would increase the electron density around Bi atoms near the oxygen vacancies, and inhibiting recombination of the photoinduced carriers. Besides, abundant oxygen vacancies can effectively enhance the adsorption of CO2 molecules. Therefore, the BiOBr with rich oxygen vacancies (BiOBr-ROV) shows higher evolution rates for CO (15.66 μmol g−1) and CH4 (0.22 μmol g−1) under irradiation of 300 W Xe lamp for 4 h compared with pristine BiOBr nanosheets (BiOBr) and BiOBr with deficient oxygen vacancies (BiOBr-DOV). The intermediate products in the CO2 reduction process have been detected by in-situ Fourier-transform infrared spectroscopy. Besides, the photodegradation activity of Cr(VI) over BiOBr-ROV is 98.65% under 80 min of irradiation, which is higher than that of BiOBr (78.01%) and BiOBr-DOV (53.67%). The work provides a new possibility to construct photocatalysts with high-performance for solar energy conversion.

Robust Er2O3/UiO-66-NH2 core–shell nanohybrid for efficient CO2 photoreduction via fast interfacial charge-transfer

Interfacial charge transfer in nanocomposites is one of the leading factors to CO2 photoreduction activity and selectivity; however, the modulation of interfacial contact still remains a compelling challenge. Here we present an in-situ assembly strategy to synthesize core–shell structured Er-UiO-66-NH2 heterojunction photocatalysts, achieving a stable CO evolution rate of 106.2 μmol·g−1·h−1 and a selectivity over 92 %. Our findings demonstrate that the coupled intermediate layer formed by solvothermal transformation creates a charge-transfer channel between Er2O3 and UiO-66-NH2, contributing to the effective spatial separation of photogenerated carriers. The well-defined gradient of band structures and interfacial built-in electric field at p-n heterojunctions direct photoelectrons migration, and facilitates the fast access to active Zr-oxo sites for efficient CO2 reduction. In-situ DRIFTS unravels that the superior catalytic activities can be attributed to the strong adsorption and activation capabilities for CO2 conversion to COOH* and CO* species. This work highlights an interfacial assembling strategy to design heterojunction photocatalysts for efficient solar fuel production.

Rational design of covalent organic frameworks/NaTaO3 S-scheme heterostructure for enhanced photocatalytic hydrogen evolution

As a typical perovskite material, NaTaO3 has been regarded as a potential catalyst for photocatalytic hydrogen evolution (PHE) process, due to its excellent photoelectric property and superior chemical stability. However, the photocatalytic activity of pure NaTaO3 was largely restricted by its poor visible-light absorption ability and rapid recombination of photogenerated charge carriers. Therefore, a covalently bonded TpBpy covalent organic framework (COF)/NaTaO3 (TpBpy/NaTaO3) heterostructure was designed and synthesized by the post modification strategy with (3-aminopropyl) triethoxysilane (APTES) and the in situ solvothermal process. Benefiting from the enhanced built-in electric field by the interfacial covalent bonds and the formation of S-scheme heterostructure between TpBpy and NaTaO3, which were proved by the Ar+-cluster depth profile and X-ray photoelectron spectroscopy (XPS), as well as density functional theory (DFT) calculation results, both the charge transfer efficiency and the PHE performance of the TpBpy/NaTaO3 composites were significantly improved. Additionally, the composites exhibited an excellent absorption performance in the visible region, which was also beneficial for the photocatalytic process. As expected, the optimal TpBpy/20%NaTaO3 composite achieved a remarkable hydrogen evolution rate of 17.3 mmol·g−1·h−1 (10 mg of catalyst) under simulated sunlight irradiation, which was about 173 and 2.4 times higher than that of pure NaTaO3 and TpBpy, respectively. This work provided a novel strategy for constructing highly effective and stable semiconductor/COFs heterostructures with strong interfacial interaction for photocatalytic hydrogen evolution.