With the serious impact of fossil fuels on the environment and the rapid development of the global economy, the development of clean and usable energy storage devices has become one of the most ...important themes of sustainable development in the world today. Supercapacitors are a new type of green energy storage device, with high power density, long cycle life, wide temperature range, and both economic and environmental advantages. In many industries, they have enormous application prospects. Electrode materials are an important factor affecting the performance of supercapacitors. MnO2‐based materials are widely investigated for supercapacitors because of their high theoretical capacitance, good chemical stability, low cost, and environmental friendliness. To achieve high specific capacitance and high rate capability, the current best solution is to use MnO2 and carbon composite materials. Herein, MnO2–carbon composite as supercapacitor electrode materials is reviewed including the synthesis method and research status in recent years. Finally, the challenges and future development directions of an MnO2–carbon based supercapacitor are summarized.
In this paper, the mechanism of MnO2‐based supercapacitors is summarized, and the synthesis method and research status of MnO2‐carbon based supercapacitor electrode materials in recent years are reviewed. Finally, the challenges and future development directions of MnO2‐carbon based supercapacitors are discussed.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Charge kinetics is highly critical in determining the quantum efficiency of solar-to-chemical conversion in photocatalysis, and this includes, but is not limited to, the separation of photoexcited ...electron-hole pairs, utilization of plasmonic hot carriers and delivery of photo-induced charges to reaction sites, as well as activation of reactants by energized charges. In this review, we highlight the recent progress on probing and steering charge kinetics toward designing highly efficient photocatalysts and elucidate the fundamentals behind the combinative use of controlled synthesis, characterization techniques (with a focus on spectroscopic characterizations) and theoretical simulations in photocatalysis studies. We first introduce the principles of various processes associated with charge kinetics that account for or may affect photocatalysis, from which a set of parameters that are critical to photocatalyst design can be summarized. We then outline the design rules for photocatalyst structures and their corresponding synthetic approaches. The implementation of characterization techniques and theoretical simulations in different steps of photocatalysis, together with the associated fundamentals and working mechanisms, are also presented. Finally, we discuss the challenges and opportunities for photocatalysis research at this unique intersection as well as the potential impact on other research fields.
This review outlines the recent progress on probing and steering charge kinetics toward designing highly efficient photocatalysts.
Defect engineering is a versatile approach to modulate band and electronic structures as well as materials performance. Herein, metal–organic frameworks (MOFs) featuring controlled structural ...defects, namely UiO‐66‐NH2‐X (X represents the molar equivalents of the modulator, acetic acid, with respect to the linker in synthesis), were synthesized to systematically investigate the effect of structural defects on photocatalytic properties. Remarkably, structural defects in MOFs are able to switch on the photocatalysis. The photocatalytic H2 production rate presents a volcano‐type trend with increasing structural defects, where Pt@UiO‐66‐NH2‐100 exhibits the highest activity. Ultrafast transient absorption spectroscopy unveils that UiO‐66‐NH2‐100 with moderate structural defects possesses the fastest relaxation kinetics and the highest charge separation efficiency, while excessive defects retard the relaxation and reduce charge separation efficiency.
Volcano‐type trend: A series of metal–organic frameworks (MOFs) decorated with Pt nanoparticles, Pt@UiO‐66‐NH2‐X, were fabricated with increasing levels of structural defects in the MOF to investigate how defect levels affect photocatalysis. The catalysts exhibit an impressive volcano‐type trend in H2 production, maximizing at a moderate defect level.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Higher‐order cycloadditions, particularly 8+2 cycloadditions, are a straightforward and efficient strategy for constructing significant medium‐sized architectures. Typically, configuration‐restrained ...conjugated systems are utilized as 8π‐components for higher‐order concerted cycloadditions. However, for this reason, 10‐membered monocyclic skeletons have never been constructed via catalytic asymmetric 8+2 cycloaddition with high peri‐ and stereoselectivity. Here, we accomplished an enantioselective 8+2 dipolar cycloaddition via the merger of visible‐light activation and asymmetric palladium catalysis. This protocol provides a new route to 10‐membered monocyclic architectures bearing chiral quaternary stereocenters with high chemo‐, peri‐, and enantioselectivity. The success of this strategy relied on the facile in situ generation of Pd‐containing 1,8‐dipoles and their enantioselective trapping by ketene dipolarophiles, which were formed in situ via a photo‐Wolff rearrangement.
With the help of visible‐light irradiation and a chiral palladium catalyst, enantioselective 8+2 cycloaddition of vinyl carbomates and α‐diazoketones has been accomplished with high peri‐, chemo‐ and stereoselectivity. This protocol provides an unprecedented and straightforward route to 10‐membered monocyclic products bearing chiral quaternary stereocenters under extremely mild conditions (i.e., room temperature and 6 W blue LEDs).
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Catalytic asymmetric cycloadditions of ambident Pd‐containing dipolar species with nucleophilic dipolarophiles, namely, inverse‐electron‐demand cycloadditions, are challenging and underdeveloped. ...Possibly, the inherent linear selectivity of Pd‐catalyzed intermolecular allylations and the lack of efficient chiral ligands are responsible for this limitation. Herein, two cycloadditions of such intermediates with deconjugated butenolides and azlactones were accomplished by using a novel chiral hybrid P,S‐ligand and hydrogen bonding. By doing so, highly functionalized, optically active dihydroquinol‐2‐ones were produced with generally high reaction efficiencies and selectivities. Preliminary DFT calculations were performed to explain the high enantio‐ and diastereoselectivities.
By popular demand: With the help of chiral P,S‐ligands and hydrogen‐bonding interactions, inverse‐electron‐demand asymmetric 4+2 cycloadditions were accomplished for the first time. A variety of optically active, highly functionalized hydroquinolin‐2‐ones were produced in good yields with excellent stereocontrol from readily available starting materials.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
It is highly desirable to convert CO2 to valuable fuels or chemicals by means of solar energy, which requires CO2 enrichment around photocatalysts from the atmosphere. Here we demonstrate that a ...porphyrin-involved metal–organic framework (MOF), PCN-222, can selectively capture and further photoreduce CO2 with high efficiency under visible-light irradiation. Mechanistic information gleaned from ultrafast transient absorption spectroscopy (combined with time-resolved photoluminescence spectroscopy) has elucidated the relationship between the photocatalytic activity and the electron–hole separation efficiency. The presence of a deep electron trap state in PCN-222 effectively inhibits the detrimental, radiative electron–hole recombination. As a direct result, PCN-222 significantly enhances photocatalytic conversion of CO2 into formate anion compared to the corresponding porphyrin ligand itself. This work provides important insights into the design of MOF-based materials for CO2 capture and photoreduction.
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IJS, KILJ, NUK, PNG, UL, UM
Excitonic effects mediated by Coulomb interactions between photogenerated electrons and holes play crucial roles in photoinduced processes of semiconductors. In terms of photocatalysis, however, ...efforts have seldom been devoted to the relevant aspects. For the catalysts with giant excitonic effects, the coexisting, competitive exciton generation serves as a key obstacle to the yield of free charge carriers, and hence, transformation of excitons into free carriers would be beneficial for optimizing the charge-carrier-involved photocatalytic processes. Herein, by taking bismuth oxybromide (BiOBr) as a prototypical model system, we demonstrate that excitons can be effectively dissociated into charge carriers with the incorporation of oxygen vacancy, leading to excellent performances in charge-carrier-involved photocatalytic reactions such as superoxide generation and selective organic syntheses under visible-light illumination. This work not only establishes an in-depth understanding of defective structures in photocatalysts but also paves the way for excitonic regulation via defect engineering.
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IJS, KILJ, NUK, PNG, UL, UM
Tea is the world＇s oldest and most popular caffeine-containing beverage with immense economic, medicinal, and cultural importance. Here, we present the first high-quality nucleotide sequence of the ...repeat-rich （80.9%）, 3.02-Gb genome of the cultivated tea tree Camellia sinensis. We show that an extraordinarily large genome size of tea tree is resulted from the slow, steady, and long-term amplification of a few LTR retrotransposon families. In addition to a recent whole-genome duplication event, lineage-specific expansions of genes associated with flavonoid metabolic biosynthesis were discovered, which enhance catechin production, terpene enzyme activation, and stress tolerance, important features for tea flavor and adaptation. We demonstrate an independent and rapid evolution of the tea caffeine synthesis pathway relative to cacao and coffee. A comparative study among 25 Camellia species revealed that higher expression levels of most flavonoid- and caffeinebut not theanine-related genes contribute to the increased production of catechins and caffeine and thus enhance tea-processing suitability and tea quality. These novel findings pave the way for further metabolomic and functional genomic refinement of characteristic biosynthesis pathways and will help develop a more diversified set of tea flavors that would eventually satisfy and attract more tea drinkers worldwide.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
The ubiquity of microplastics in aquatic and terrestrial environments and related ecological impacts have gained global attention. Microplastics have been detected in table salt, drinking water, and ...air, posing inevitable human exposure risk. However, rigorous analytical methods for detection and characterization of microplastics remain scarce. Knowledge about the potential adverse effects on human health via dietary and respiratory exposures is also limited. To address these issues, we reviewed 46 publications concerning abundances, potential sources, and analytical methods of microplastics in table salt, drinking water, and air. We also summarized probable translocation and accumulation pathways of microplastics within human body. Human body burdens of microplastics through table salt, drinking water, and inhalation were estimated to be (0–7.3)×104, (0–4.7)×103, and (0–3.0)×107 items per person per year, respectively. The intake of microplastics via inhalation, especially via indoor air, was much higher than those via other exposure routes. Moreover, microplastics in the air impose threats to both respiratory and digestive systems through breathing and ingestion. Given the lifetime inevitable exposure to microplastics, we urgently call for a better understanding of the potential hazards of microplastics to human health.
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IJS, KILJ, NUK, PNG, UL, UM
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