S,N-GQD sensitization effect on the improvement of ZnO nanopencil photoelectrochemical properties.

ZnO photoanodes in photoelectrochemical (PEC) water splitting for green-hydrogen production are limited due to the large bandgap that is only confined to UV light. One of the strategies for broadening the photo absorption range and improving light harvesting is to modify a one-dimensional (1D) nanostructure to a three-dimensional (3D) ZnO superstructure coupling with a narrow-bandgap material, in this case, a graphene quantum dot photosensitizer. Herein, we studied the effect of sulfur and nitrogen co-doped graphene quantum dot (S,N-GQD) sensitization on the surface of ZnO nanopencil (ZnO NPc) to give a photoanode in the visible light spectrum. In addition, the photo energy harvesting between the 3D-ZnO and 1D-ZnO, as represented by neat ZnO NPc and ZnO nanorods (ZnO NRs), was also compared. Several instruments, including SEM-EDS, FTIR, and XRD revealed the successful loading of S,N-GQDs on the ZnO NPc surfaces through the layer-by-layer assembly technique. The advantages are S,N-GQDs's band gap energy (2.92 eV) decreasing ZnO NPc's band gap value from 3.169 eV to 3.155 eV after being composited with S,N-GQDs and facilitating the generation of electron-hole pairs for PEC activity under visible light irradiation. Furthermore, the electronic properties of ZnO NPc/S,N-GQDs were improved significantly over those of bare ZnO NPc and ZnO NR. The PEC measurements revealed that the ZnO NPc/S,N-GQDs stood out with a maximum current density of 1.82 mA cm-2 at +1.2 V (vs. Ag/AgCl), representing a 153% and 357% improvement over the bare ZnO NPc (1.19 mA cm-2) and the ZnO NR (0.51 mA cm-2), respectively. These results suggest that ZnO NPc/S,N-GQDs could have potential for water splitting applications.

3D-ZnO Superstructure Decorated with Carbon-Based Material for Efficient Photoelectrochemical Water-Splitting under Visible-Light Irradiation.

The depletion of fossil fuels is a worldwide problem that has led to the discovery of alternative energy sources. Solar energy is the focus of numerous studies due to its huge potential power and environmentally friendly nature. Furthermore, one such area of study is the production of hydrogen energy by engaging photocatalysts using the photoelectrochemical (PEC) method. 3-D ZnO superstructures are extensively explored, showing high solar light-harvesting efficiency, more reaction sites, great electron transportation, and low electron-hole recombination. However, further development requires the consideration of several aspects, including the morphological effects of 3D-ZnO on water-splitting performance. This study reviewed various 3D-ZnO superstructures fabricated through different synthesis methods and crystal growth modifiers, as well as their advantages and limitations. Additionally, a recent modification by carbon-based material for enhanced water-splitting efficiency has been discussed. Finally, the review provides some challenging issues and future perspectives on the improvement of vectorial charge carrier migration and separation between ZnO as well as carbon-based material, using rare earth metals, which appears to be exciting for water-splitting.

Recent Progress in Colloidal Quantum Dot Thermoelectrics.

Semiconducting colloidal quantum dots (CQDs) represent an emerging class of thermoelectric materials for use in a wide range of future applications. CQDs combine solution processability at low temperatures with the potential for upscalable manufacturing via printing techniques. Moreover, due to their low dimensionality, CQDs exhibit quantum confinement and a high density of grain boundaries, which can be independently exploited to tune the Seebeck coefficient and thermal conductivity, respectively. This unique combination of attractive attributes makes CQDs very promising for application in emerging thermoelectric generator (TEG) technologies operating near room temperature. Herein, recent progress in CQDs for application in emerging thin-film thermoelectrics is reviewed. First, the fundamental concepts of thermoelectricity in nanostructured materials are outlined, followed by an overview of the popular synthetic methods used to produce CQDs with controllable sizes and shapes. Recent strides in CQD-based thermoelectrics are then discussed with emphasis on their application in thin-film TEGs. Finally, the current challenges and future perspectives for further enhancing the performance of CQD-based thermoelectric materials for future applications are discussed.

Recent advances and rational design strategies of carbon dots towards highly efficient solar evaporation.

Solar evaporation using photothermal materials is an environmentally friendly and feasible solution to overcome the water scarcity issue by utilizing the abundant solar energy source. Some key points for efficient solar-to-thermal energy conversion have been extensively studied. Among them, the advancement of solar absorber materials has emerged as an attractive research topic, owing to their potential to enhance the efficiency of solar to thermal conversion significantly. Recently, carbon dots (CDs) have attracted great interest for their applications in this field. CDs have many desirable properties, such as broad light absorption (200-800 nm), high photothermal conversion efficiency (more than 90%), tunable structure and surface functionalization, easy to produce and abundant raw materials that meet the requirements for this application. In this review, the integration of CDs into solar evaporation systems and recent advances in CD-based solar absorbers will be summarized and discussed. Before that, brief knowledge of carbon-based solar thermal evaporation, including its mechanism and strategies to improve the efficiency, is provided, followed by CDs' synthesis and tunable properties that can be optimized for this application. Finally, the challenges and perspectives of research for CD-based solar evaporation are proposed, for example, optimizing solar absorbers by decorating hydroxyl-rich CDs in 2D or 3D structures.

Functionalized HgTe nanoparticles promote laser-induced solid phase ionization/dissociation for comprehensive glycan sequencing.

Glycoconjugates are ubiquitously present and play a critical role in various biological processes. Due to their low stability and incredibly high degree of structural diversity, the structural characterization of glycan generally requires chemical derivatization and sophisticated instrumentation. Herein, we report a method for complicated glycan characterization in a single assay by employing 2,5-dihydroxybenzoic acid functionalized mercury telluride nanoparticles (HgTe@DHB NPs) as a dual ionization-dissociation element in matrix-assisted laser desorption/ionization mass spectrometry. Using a linear glycan, HgTe@DHB NPs promote laser-induced extensive and intense dissociation of the glycan, superior to HgTe microparticles and other inorganic nanoparticles (TiO2, ZnO, and Mn2O3 NPs). Abundant generation of diagnostic glycosidic (Y-, and B-type ions) and cross-ring cleavage (A-type ions) ions permits unambiguous determination of the composition, sequence, branching, and linkage of labile sialylated glycans. The general utility of this approach was demonstrated by the characterization of labile sialylated glycans and two sets of complicated isomeric glycans. This phenomenon was delineated further by investigating the NP's physico-chemical characteristics, revealing that their nanoscale-dependent thermodynamic properties, including UV absorption, photoelectron release dynamics and thermal energy, were the key to levitate temperature synergistically, thus inducing spontaneous glycan decomposition during the nanoparticle-assisted laser desorption-ionization process. Our results show that this "pseudo-MS/MS" obtained by HgTe@DHB can be beneficial for the analysis of biologically relevant and more complicated carbohydrates, without the need for chemical pre-derivatization and conventional tandem mass spectrometry.

UV-activated multilayer nanomatrix provides one-step tunable carbohydrate structural characterization in MALDI-MS.

The structure-specific fragmentation of gas-phase ions in tandem mass spectrometry among other techniques provides an efficient analytical method for confirming unknown analytes or for elucidating chemical structures. Using concentration-dependent UV-absorbing matrix-functionalized magnetic nanoparticles and matrix-assisted laser desorption-ionization mass spectrometry (MALDI MS), we developed a single-step pseudo-MS/MS approach for tunable ionization and fragmentation to facilitate structure determination. Without chemical derivatization, we have demonstrated that this approach successfully distinguished isomeric sets of di-, tri- and tetrasaccharides. Low concentration of nanomatrix provided an enhanced signal for accurate mass determination of the intact molecular ions of analytes present in the sample. In contrast, high concentration of nanomatrix induced extensive and unique fragmentation, including high-energy facile bond breakage (A- and X-type cross-ring cleavages), which facilitated the linkage and sequence characterization of oligosaccharides without conventional tandem mass spectrometric instrumentation. The practicality of this approach for complex sample analysis was evaluated by an oligosaccharide mixture, wherein molecular ions are unambiguously observed and signature product ions are distinguishable enough for molecular identification and isomer differentiation by this simple tunable approach. By probing the roles of the multilayer nanomatrix components: matrix (energy absorption), silane-coating (energy pooling and dissipation) and core Fe3O4 (fragmentation), a plausible energy transfer mechanism was proposed based on a computational study and photoelectron experiments. The differentiation of tri- and tetra-oligosaccharide shown in this study not only demonstrated the first step toward glycan characterization by nanoparticle-assisted MALDI-MS, but also shed some insight on the nanoparticle-mediated energy transfer dynamics behind our approach.

Sequential one-pot enzymatic synthesis of oligo-N-acetyllactosamine and its multi-sialylated extensions.

A simple and efficient protocol for the preparative-scale synthesis of various lengths of oligo-N-acetyllactosamine (oligo-LacNAc) and its multi-sialylated extensions is described. The strategy utilizes one thermophilic bacterial thymidylyltransferase (RmlA) coupled with corresponding sugar-1-phosphate kinases to generate two uridine diphosphate sugars, UDP-galactose and UDP-N-acetylglucosamine. By incorporating glycosyltransferases, oligo-LacNAcs and their sialylated analogs were synthesized.