Abstract
While inheriting the exceptional merits of single atom catalysts, diatomic site catalysts (DASCs) utilize two adjacent atomic metal species for their complementary functionalities and ...synergistic actions. Herein, a DASC consisting of nickel-iron hetero-diatomic pairs anchored on nitrogen-doped graphene is synthesized. It exhibits extraordinary electrocatalytic activities and stability for both CO
2
reduction reaction (CO
2
RR) and oxygen evolution reaction (OER). Furthermore, the rechargeable Zn-CO
2
battery equipped with such bifunctional catalyst shows high Faradaic efficiency and outstanding rechargeability. The in-depth experimental and theoretical analyses reveal the orbital coupling between the catalytic iron center and the adjacent nickel atom, which leads to alteration in orbital energy level, unique electronic states, higher oxidation state of iron, and weakened binding strength to the reaction intermediates, thus boosted CO
2
RR and OER performance. This work provides critical insights to rational design, working mechanism, and application of hetero-DASCs.
Water electrolysis offers a promising energy conversion and storage technology for mitigating the global energy and environmental crisis, but there still lack highly efficient and pH-universal ...electrocatalysts to boost the sluggish kinetics for both cathodic hydrogen evolution reaction (HER) and anodic oxygen evolution reaction (OER). Herein, we report uniformly dispersed iridium nanoclusters embedded on nitrogen and sulfur co-doped graphene as an efficient and robust electrocatalyst for both HER and OER at all pH conditions, reaching a current density of 10 mA cm
with only 300, 190 and 220 mV overpotential for overall water splitting in neutral, acidic and alkaline electrolyte, respectively. Based on probing experiments, operando X-ray absorption spectroscopy and theoretical calculations, we attribute the high catalytic activities to the optimum bindings to hydrogen (for HER) and oxygenated intermediate species (for OER) derived from the tunable and favorable electronic state of the iridium sites coordinated with both nitrogen and sulfur.
NiFe‐based layered double hydroxides (LDHs) are among the most efficient oxygen evolution reaction (OER) catalysts in alkaline medium, but their long‐term OER stabilities are questionable. In this ...work, it is demonstrated that the layered structure makes bulk NiFe LDH intrinsically not stable in OER and the deactivation mechanism of NiFe LDH in OER is further revealed. Both operando electrochemical and structural characterizations show that the interlayer basal plane in bulk NiFe LDH contributes to the OER activity, and the slow diffusion of proton acceptors (e.g., OH−) within the NiFe LDH interlayers during OER causes dissolution of NiFe LDH and therefore decrease in OER activity with time. To improve diffusion of proton acceptors, it is proposed to delaminate NiFe LDH into atomically thin nanosheets, which is able to effectively improve OER stability of NiFe LDH especially at industrial operating conditions such as elevated operating temperatures (e.g., at 80 °C) and large current densities (e.g., at 500 mA cm−2).
The interlayer basal plane in bulk NiFe layered double hydroxide (LDH) contributes to the oxygen evolution reaction (OER) activity. Restricted diffusion of proton acceptors within the interlayers of bulk NiFe LDH causes catalyst dissolution. Exfoliating multilayered NiFe LDH into single‐layered nanosheets greatly improves the catalytic stability of NiFe LDH in alkaline OER.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Two‐electron oxygen photoreduction to hydrogen peroxide (H2O2) is seriously inhibited by its sluggish charge kinetics. Herein, a polarization engineering strategy is demonstrated by grafting ...(thio)urea functional groups onto covalent triazine frameworks (CTFs), giving rise to significantly promoted charge separation/transport and obviously enhanced proton transfer. The thiourea‐functionalized CTF (Bpt‐CTF) presents a substantial improvement in the photocatalytic H2O2 production rate to 3268.1 µmol h−1 g−1 with no sacrificial agents or cocatalysts that is over an order of magnitude higher than unfunctionalized CTF (Dc‐CTF), and a remarkable quantum efficiency of 8.6% at 400 nm. Mechanistic studies reveal the photocatalytic performance is attributed to the prominently enhanced two‐electron oxygen reduction reaction by forming endoperoxide at the triazine unit and highly concentrated holes at the thiourea site. The generated O2 from water oxidation is subsequently consumed by the oxygen reduction reaction (ORR), thereby boosting overall reaction kinetics. The findings suggest a powerful functional‐groups‐mediated polarization engineering method for the development of highly efficient metal‐free polymer‐based photocatalysts.
(Thio)urea‐functionalized covalent triazine frameworks (CTFs) are rationally designed, showing an outstanding photocatalytic activity toward production of H2O2 in water (3268.1 μmol h−1 g−1 with a quantum yield of 8.6% at 400 nm for the thiourea‐functionalized CTF) via reducing molecular oxygen (O2). This is much higher than most of the reported metal‐free polymer‐based photocatalysts in nonsacrificial systems.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Designing effective electrocatalysts for the carbon dioxide reduction reaction (CO2RR) is an appealing approach to tackling the challenges posed by rising CO2 levels and realizing a closed carbon ...cycle. However, fundamental understanding of the complicated CO2RR mechanism in CO2 electrocatalysis is still lacking because model systems are limited. We have designed a model nickel single‐atom catalyst (Ni SAC) with a uniform structure and well‐defined Ni‐N4 moiety on a conductive carbon support with which to explore the electrochemical CO2RR. Operando X‐ray absorption near‐edge structure spectroscopy, Raman spectroscopy, and near‐ambient X‐ray photoelectron spectroscopy, revealed that Ni+ in the Ni SAC was highly active for CO2 activation, and functioned as an authentic catalytically active site for the CO2RR. Furthermore, through combination with a kinetics study, the rate‐determining step of the CO2RR was determined to be *CO2−+H+→*COOH. This study tackles the four challenges faced by the CO2RR; namely, activity, selectivity, stability, and dynamics.
Ni‐che reaction: In situ reduction of nickel(II) 2,9,16,23‐tetra(amino)phthalocyanine, anchored on the surface of carbon nanotubes, yields nickel single atoms. Advanced spectroscopy of the single‐atom catalyst reveals that Ni+ is a highly active catalytic site for CO2 activation and reduction.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
The development of lithium (Li) metal anodes Li metal batteries faces huge challenges such as uncontrolled Li dendrite growth and large volume change during Li plating/stripping, resulting in severe ...capacity decay and high safety hazards. A 3D porous copper (Cu) current collector as a host for Li deposition can effectively settle these problems. However, constructing a uniform and compact 3D porous Cu structure is still an enormous challenge. Herein, an electrochemical etching method for Cu–Zinc (Zn) alloy is reported to precisely engrave a 3D Cu structure with uniform, smooth, and compact porous network. Such a continuous structure endows 3D Cu excellent mechanical properties and high electrical conductivity. The uniform and smooth pores with a large internal surface area ensures well dispersed current density for homogeneous Li metal deposition and accommodation. A smooth and stable solid electrolyte interphase is formed and meanwhile Li dendrites and dead Li are effectively suppressed. The Li metal anode conceived 3D Cu current collector can stably cycle for 400 h under an Li plating/stripping capacity of 1 mA h cm−2 and a current density of 1 mA cm−2. The Li@3D Cu||LiFePO4 full cells present excellent cycling and rate performances. The electrochemical dealloying is a robust method to construct 3D Cu current collectors for dendrite‐free Li metal anodes.
The electrochemical etching method is presented to prepare 3D Cu with a uniform and compact porous network. As current collector of Li metal anode, the 3D Cu with large internal surface area and enhanced mechanical properties can effectively accommodate Li metal and suppress Li dendrite growth to achieve a high performance in a Li–metal battery.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Solid composite electrolytes (SCEs) that combine the advantages of solid polymer electrolytes (SPEs) and inorganic ceramic electrolytes (ICEs) present acceptable ionic conductivity, high mechanical ...strength, and favorable interfacial contact with electrodes, which greatly improve the electrochemical performance of all‐solid‐state batteries compared to single SPEs and ICEs. However, there are many challenges to overcome before the practical application of SCEs, including the low ionic conductivity less than 10−3 S cm−1 at ambient temperature, poor interfacial stability, and high interfacial resistance, which greatly restrict the room temperature performance. Herein, the advances of SCEs applied in all‐solid‐state lithium batteries are presented, including the Li ion migration mechanism of SCEs, the strategies to enhance the ionic conductivity of SCEs by various morphologies of ICEs, and construction methods of the low resistance and stable interfaces of SCEs with both cathode and anode. Finally, some typical applications of SCEs in lithium batteries are summarized and future development directions are prospected. This work presents how it is quite significant to further enhance the ionic conductivity of SCEs by developing the novel SPEs with the special morphology of ICEs for advanced all‐solid‐state lithium batteries.
Herein, the advantages and ionic transport mechanisms of solid composite electrolyte (SCE) as well as the relationship between morphology of ceramic fillers and ionic conductivity of SCE are reviewed. Recent progress and strategies to settle interfacial issues for high‐performance all‐solid‐state lithium metal batteries with SCE are also concluded and future research directions of SCEs are proposed.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Abstract
Controllable and on‐demand delivery of supramolecular systems have received considerable attention in modern agricultural management, especially for managing intractable plant diseases. ...Here, an intelligent photoresponsive pesticide delivery system is reported based on
β
‐cyclodextrin (
β
‐CD) and azobenzene, which overcomes the resistance of phytopathogens caused by the irrational use of conventional pesticides. Antibacterial bioassays illustrated that designed azobenzene derivative
3a
possesses the most efficient bioactivity with EC
50
values of 0.52–25.31 µg mL
−1
toward three typical phytopathogens. Moreover, the assembly of the supramolecular binary complex
3a
@
β
‐CD is successfully elucidated and displays exceptional inhibitory activity on biofilm formation. Of note, this supramolecular binary complex significantly improves the water solubility, foliar surface wettability, and shows marked light‐responsive properties. In vivo anti‐
Xoo
assays reveal that
3a
@
β
‐CD has excellent control efficiency (protective activity: 51.22%, curative activity: 48.37%) against rice bacterial blight pathogens, and their control efficiency can be elevated to values of 55.84% (protective activity) and 52.05% (curative activity) by UV–vis exposure. In addition, the
3a
@
β
‐CD are non‐toxic toward various non‐target organisms. This study therefore offers new insights into the potential of host‐guest complexes as a feasible pesticide discovery strategy characterized by a safe, biocompatible, light‐responsive release, and antibiofilm properties for overcoming intractable plant bacterial diseases.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
The lithium–sulfur (Li–S) battery is a next generation high energy density battery, but its practical application is hindered by the poor cycling stability derived from the severe shuttling of ...lithium polysulfides (LiPSs). Catalysis is a promising way to solve this problem, but the rational design of relevant catalysts is still hard to achieve. This paper reports the WS2–WO3 heterostructures prepared by in situ sulfurization of WO3, and by controlling the sulfurization degree, the structure is controlled, which balances the trapping ability (by WO3) and catalytic activity (by WS2) toward LiPSs. As a result, the WS2–WO3 heterostructures effectively accelerate LiPS conversion and improve sulfur utilization. The Li–S battery with 5 wt% WS2–WO3 heterostructures as additives in the cathode shows an excellent rate performance and good cycling stability, revealing a 0.06% capacity decay each cycle over 500 cycles at 0.5 C. By building an interlayer with such heterostructure‐added graphenes, the battery with a high sulfur loading of 5 mg cm−2 still shows a high capacity retention of 86.1% after 300 cycles at 0.5 C. This work provides a rational way to prepare the metal oxide–sulfide heterostructures with an optimized structure to enhance the performance of Li–S batteries.
A WS2–WO3 heterostructure catalyst is prepared through a controllable in situ sulfurization of WO3. The well‐balanced composition of this heterostructure optimizes the trapping ability for lithium polysulfides and enhances catalytic conversion, effectively suppressing the polysulfide shuttling and leading to the long cycling stability of Li–S batteries.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Pin1 is the only known peptidyl-prolyl cis-trans isomerase (PPIase) that specifically recognizes and isomerizes the phosphorylated Serine/Threonine-Proline (pSer/Thr-Pro) motif. The Pin1-mediated ...structural transformation posttranslationally regulates the biofunctions of multiple proteins. Pin1 is involved in many cellular processes, the aberrance of which lead to both degenerative and neoplastic diseases. Pin1 is highly expressed in the majority of cancers and its deficiency significantly suppresses cancer progression. According to the ground-breaking summaries by Hanahan D and Weinberg RA, the hallmarks of cancer comprise ten biological capabilities. Multiple researches illuminated that Pin1 contributes to these aberrant behaviors of cancer via promoting various cancer-driving pathways. This review summarized the detailed mechanisms of Pin1 in different cancer capabilities and certain Pin1-targeted small-molecule compounds that exhibit anticancer activities, expecting to facilitate anticancer therapies by targeting Pin1.
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