Fluorescence spectroscopy with strong emitters is a remarkable tool with ultra-high sensitivity for detection and imaging down to the single-molecule level. Plasmon-enhanced fluorescence (PEF) not ...only offers enhanced emissions and decreased lifetimes, but also allows an expansion of the field of fluorescence by incorporating weak quantum emitters, avoiding photobleaching and providing the opportunity of imaging with resolutions significantly better than the diffraction limit. It also opens the window to a new class of photostable probes by combining metal nanostructures and quantum emitters. In particular, the shell-isolated nanostructure-enhanced fluorescence, an innovative new mode for plasmon-enhanced surface analysis, is included. These new developments are based on the coupling of the fluorophores in their excited states with localized surface plasmons in nanoparticles, where local field enhancement leads to improved brightness of molecular emission and higher detection sensitivity. Here, we review the recent progress in PEF with an emphasis on the mechanism of plasmon enhancement, substrate preparation, and some advanced applications, including an outlook on PEF with high time- and spatially resolved properties.
Fluorescence spectroscopy with strong emitters is a remarkable tool with ultra-high sensitivity for detection and imaging down to the single-molecule level.
A hundred years on, the energy‐intensive Haber–Bosch process continues to turn the N2 in air into fertilizer, nourishing billions of people while causing pollution and greenhouse gas emissions. The ...urgency of mitigating climate change motivates society to progress toward a more sustainable method for fixing N2 that is based on clean energy. Surface oxygen vacancies (surface Ovac) hold great potential for N2 adsorption and activation, but introducing Ovac on the very surface without affecting bulk properties remains a great challenge. Fine tuning of the surface Ovac by atomic layer deposition is described, forming a thin amorphous TiO2 layer on plasmon‐enhanced rutile TiO2/Au nanorods. Surface Ovac in the outer amorphous TiO2 thin layer promote the adsorption and activation of N2, which facilitates N2 reduction to ammonia by excited electrons from ultraviolet‐light‐driven TiO2 and visible‐light‐driven Au surface plasmons. The findings offer a new approach to N2 photofixation under ambient conditions (that is, room temperature and atmospheric pressure).
Surface oxygen vacancies play a promotional role in the outer amorphous TiO2 (a‐TiO2) thin layer during the adsorption and activation of N2. The process facilitates N2 reduction to ammonia by excited electrons derived from UV‐light‐driven rutile TiO2 nanorod arrays and visible‐light‐driven gold surface plasmons.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Solid/liquid interfaces are ubiquitous in nature and knowledge of their atomic-level structure is essential in elucidating many phenomena in chemistry, physics, materials science and Earth science
. ...In electrochemistry, in particular, the detailed structure of interfacial water, such as the orientation and hydrogen-bonding network in electric double layers under bias potentials, has a significant impact on the electrochemical performances of electrode materials
. To elucidate the structures of electric double layers at electrochemical interfaces, we combine in situ Raman spectroscopy and ab initio molecular dynamics and distinguish two structural transitions of interfacial water at electrified Au single-crystal electrode surfaces. Towards negative potentials, the interfacial water molecules evolve from structurally 'parallel' to 'one-H-down' and then to 'two-H-down'. Concurrently, the number of hydrogen bonds in the interfacial water also undergoes two transitions. Our findings shed light on the fundamental understanding of electric double layers and electrochemical processes at the interfaces.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
Defects have been found to enhance the electrocatalytic performance of NiFe‐LDH for oxygen evolution reaction (OER). Nevertheless, their specific configuration and the role played in regulating the ...surface reconstruction of electrocatalysts remain ambiguous. Herein, cationic vacancy defects are generated via aprotic‐solvent‐solvation‐induced leaking of metal cations from NiFe‐LDH nanosheets. DFT calculation and in situ Raman spectroscopic observation both reveal that the as‐generated cationic vacancy defects tend to exist as VM (M=Ni/Fe); under increasing applied voltage, they tend to assume the configuration VMOH, and eventually transform into VMOH‐H which is the most active yet most difficult to form thermodynamically. Meanwhile, with increasing voltage the surface crystalline Ni(OH)x in the NiFe‐LDH is gradually converted into disordered status; under sufficiently high voltage when oxygen bubbles start to evolve, local NiOOH species become appearing, which is the residual product from the formation of vacancy VMOH‐H. Thus, we demonstrate that the cationic defects evolve along with increasing applied voltage (VM → VMOH → VMOH‐H), and reveal the essential motif for the surface restructuration process of NiFe‐LDH (crystalline Ni(OH)x → disordered Ni(OH)x → NiOOH). Our work provides insight into defect‐induced surface restructuration behaviors of NiFe‐LDH as a typical precatalyst for efficient OER electrocatalysis.
Along with increasing voltage during the OER process, the structural evolution of cationic defects within NiFe‐LDH, where the simple vacancy VM changes to VMOH and then to the most reactive VMOH‐H, and the surface restructuration, where surface crystalline Ni(OH)x is converted to disordered Ni(OH)x and then to the surface local NiOOH species, are voltage‐regulated concurrent events defining the eventual catalytic performance of the precatalyst.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Designing copper (Cu) current collectors is a convenient way to stabilize lithium (Li) metal anodes. However, Cu current collectors and their derived Li/Cu anodes still face several obstacles, ...including lithiophobic and oxidizable Cu surface, cumbersome anode fabrication process, and low Li utilization. Here, a formate‐treatment strategy is presented to reconstruct Cu current collectors with a passivation layer covered Cu(110) surface. This method can easily be generalized to increase the lithiophilicity and oxidation resistibility of Cu current collectors. Using the formate‐treated Cu nanowire network as an anode current collector, the full cell consisting of a LiFePO4 cathode and Li/Cu anode with a low negative/positive capacity ratio delivers an excellent cycling performance with 74.8% capacity retention after 1000 cycles at 1 C. In addition, a concept of an upper current collector is introduced to simplify the manufacturing procedure of Li/Cu anodes. This work provides new insights into the design and construction of high‐performance Li/Cu anodes.
A formate‐treatment method is proposed to reconstruct copper current collectors with a passivation layer covered Cu(110) surface. Benefiting from the enhanced lithiophilicity and inoxidizability, the formate‐treated copper current collectors can guide dendrite‐free lithium deposition at high current densities and remarkably improve the cycling stabilities of lithium metal batteries.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
The exploring of catalysts with high‐efficiency and low‐cost for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the key issues for many renewable energy systems ...including fuel cells, metal–air batteries, and water splitting. Despite several decades pursuing, bifunctional oxygen catalysts with high catalytic performance at low‐cost, especially the one that could be easily scaled up for mass production are still missing and highly desired. Herein, a hybrid catalyst with NiCo alloy nanoparticles decorated on N‐doped carbon nanofibers is synthesized by a facile electrospinning method and postcalcination treatment. The hybrid catalyst NiCo@N‐C 2 exhibits outstanding ORR and OER catalytic performances, which is even surprisingly superior to the commercial Pt/C and RuO2 catalysts, respectively. The synergetic effects between alloy nanoparticles and the N‐doped carbon fiber are considered as the main contributions for the excellent catalytic activities, which include decreasing the intrinsic and charge transfer resistances, increasing CC, graphitic‐N/pyridinic‐N contents in the hybrid catalyst. This work opens up a new way to fabricate high‐efficient, low‐cost oxygen catalysts with high production.
NiCo alloy nanoparticles decorated on N‐doped carbon nanofibers as a highly active and durable oxygen electrocatalyst at low‐cost are synthesized and reported. The hybrid catalyst with suitable amount of NiCo alloy nanoparticles loading (NiCo@N‐C 2) gives the most outstanding oxygen reduction reaction and oxygen evolution reaction electrocatalytic performances, which is even surprisingly superior to the commercial Pt/C and RuO2 catalysts, respectively.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Gene knockout tools are highly desirable for basic and applied plant research.
Here, we leverage the Cas9-derived cytosine base editor to introduce precise C-to-T mutations to disrupt the highly ...conserved intron donor site GT or acceptor site AG, thereby inducing messenger RNA (mRNA) missplicing and gene disruption.
As proof of concept, we successfully obtained Arabidopsis null mutant of MTA gene in the T₂ generation and rice double null mutant of GL1-1 and NAL1 genes in the T₀ generation by this strategy.
Elimination of the original intron donor site or acceptor site could trigger aberrant splicing at a new specific exonic site, but not at the closest GT or AG site, suggesting cryptic rules governing splice site recognition. The strategy presented expands the applications of base editing technologies in plants by providing a new means for gene inactivation without generating DNA double-strand breaks, and it can potentially serve as a useful tool for studying the biology of mRNA splicing.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NMLJ, NUK, OILJ, PNG, SAZU, SBCE, SBMB, UL, UM, UPUK
It is vital to understand the oxygen reduction reaction (ORR) mechanism at the molecular level for the rational design and synthesis of high activity fuel‐cell catalysts. Surface enhanced Raman ...spectroscopy (SERS) is a powerful technique capable of detecting the bond vibrations of surface species in the low wavenumber range, however, using it to probe practical nanocatalysts remains extremely challenging. Herein, shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS) was used to investigate ORR processes on the surface of bimetallic Pt3Co nanocatalyst structures. Direct spectroscopic evidence of *OOH suggests that ORR undergoes an associative mechanism on Pt3Co in both acidic and basic environments. Density functional theory (DFT) calculations show that the weak *O adsorption arise from electronic effect on the Pt3Co surface accounts for enhanced ORR activity. This work shows SHINERS is a promising technique for the real‐time observation of catalytic processes.
SHINERS (shell‐isolated nanoparticle enhanced Raman spectroscopy) was used to reveal in situ the oxygen reduction reaction (ORR) process on Pt3Co nanocatalysts. An associative mechanism was proposed for ORR on nanocatalysts and the weaker *O adsorption lead to the improved activity.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Plasmonic core–shell nanostructures have attracted considerable attention in the scientific community recently due to their highly tunable optical properties. Plasmon‐enhanced spectroscopies are one ...of the main applications of plasmonic nanomaterials. When excited by an incident laser of suitable wavelength, strong and highly localized electromagnetic (EM) fields are generated around plasmonic nanomaterials, which can significantly boost excitation and/or radiation processes that amplify Raman, fluorescence, or nonlinear signals and improve spectroscopic sensitivity. Herein, recent developments in plasmon‐enhanced spectroscopies utilizing core–shell nanostructures are reviewed, including shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS), plasmon‐enhanced fluorescence spectroscopy, and plasmon‐enhanced nonlinear spectroscopy.
The highly localized and strong electromagnetic fields generated by plasmonic nanomaterials, when excited by incident lasers with suitable wavelengths, can greatly boost the excitation and/or radiation processes of various spectroscopies, including Raman, fluorescence, or nonlinear spectroscopies, giving enhanced signals and improved spectral sensitivity.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
The Co‐based electrocatalyst is among the most promising candidates for electrochemical oxidation of 5‐hydroxymethylfurfural (HMF). However, the intrinsic active sites and detailed mechanism of this ...catalyst remains unclear. We combine experimental evidence and a theoretical study to show that electrogenerated Co3+ and Co4+ species act as chemical oxidants but with distinct roles in selective HMF oxidation. It is found that Co3+ is only capable of oxidizing formyl group to produce carboxylate while Co4+ is required for the initial oxidation of hydroxyl group with significantly faster kinetics. As a result, the product distribution shows explicit dependence on the Co oxidation states and selective production of 5‐hydroxymethyl‐2‐furancarboxylic acid (HMFCA) and 2,5‐furandicarboxylic acid (FDCA) are achieved by tuning the applied potential. This work offers essential mechanistic insight on Co‐catalyzed organic oxidation reactions and might guide the design of more efficient electrocatalysts.
A detailed mechanism for cobalt‐catalyzed electrochemical 5‐hydroxymethylfurfural (HMF) oxidation is revealed. A combined experimental and theoretical study shows that a Co3+ species is capable of oxidizing the formyl group to produce carboxylate but remains inert towards oxidation of the hydroxyl group. In contrast, a Co4+ species is required for the initial oxidation of the hydroxyl group in HMF.
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