Low-temperature Water-gas Shift Reaction Enhanced by Oxygen Vacancies in Pt-loaded Porous Single-crystalline Oxide Monoliths.

Water-gas shift (WGS) reaction at low temperature plays an important role in hydrogen production from fossil fuels and hydrogen purification for proton-exchange membrane fuel cells. However, the activation of H2 O is a critical reaction step that greatly limits the overall performance during WGS reaction. Here we fabricate porous single-crystalline (PSC) MoO3 monoliths at 1 cm scale and deposit atomic-layered Pt clusters at the lattice surface to create the interfacial system toward the low-temperature WGS reaction. The single-crystalline nature stabilizes the oxygen vacancies (VO ) at lattice and facilitates the effective activation of H2 O at the interface. We show the highest Pt-normalized activity of 0.86 molCO molPt -1 s-1 for the ultra-low temperature WGS reaction at 120 °C. The single-crystalline features with enhanced fluxion in porous architectures lead to outstanding performance without visible degradation even after continuous operation for 100 hours.

Superhydrophilic Modified Elastomeric RGO Aerogel Based Hydrated Salt Phase Change Materials for Effective Solar Thermal Conversion and Storage.

As a typical phase-change material (PCM) with high heat storage capacity and wide distribution, hydrated salts play broad and critical roles in solar energy utilization in recent years. However, the leakage and supercooling problems of hydrated salts have been a constraint to their further practical applications. In the current work, the super-hydrophilic reduced graphene oxide (RGO) aerogels modified by konjac glucomannan (KGM) as supporting structural materials are prepared by the hydrothermal reaction-freeze-drying, which can effectively absorb and convert visible sunlight energy into thermal energy. In addition, the super-hydrophilic aerogels compounded with PCMs can ameliorate the shortcoming of leakage and suppress the supercooling temperature as low about 0.2-1.5 °C in the freezing process. Under 1 sun irradiation, the prepared sodium acetate trihydrate/KGM-modified graphene oxide aerogel (SAT/KRGO) composite PCM achieves a high photothermal conversion efficiency (86.3%) due to its good light absorption property. The number of cycles has no apparent effect on the supercooling of the composite materials, suggesting their stable thermal cycles and thermal storage.

Metallic porous nitride single crystals at two-centimeter scale delivering enhanced pseudocapacitance.

Pseudocapacitors that originate from chemisorption contain redox active sites mainly composed of transition metal ions with unsaturated coordination in lattice on the electrode surface. The capacitance is generally dictated by the synergy of the porous microstructure, electronic conduction and active sites in the porous electrode. Here we grow metallic porous nitride single crystals at 2-cm scale to enhance pseudocapacitance through the combination of large surface area with porous microstructure, high conductivity with metallic states and ordered active sites with unsaturated coordination at twisted surfaces. We show the enhanced gravimetric and areal pseudocapacitance and excellent cycling stability both in acidic and alkaline electrolyte with porous MoN, Ta5N6 and TiN single crystals. The long-range ordering of active metal-nitrogen sites account for the fast redox reactions in chemisorption while the high conductivity together with porous microstructure facilitate the charge transfer and species diffusion in electrodes.

Porous single-crystalline titanium dioxide at 2 cm scale delivering enhanced photoelectrochemical performance.

Porous single-crystalline (P-SC) titanium dioxide in large size would significantly enhance their photoelectrochemical functionalities owing to the structural coherence and large surface area. Here we show the growth of P-SC anatase titanium dioxide on an 2 cm scale through a conceptually different lattice reconstruction strategy by direct removal of K/P from KTiOPO4 lattice leaving the open Ti-O skeleton simultaneously recrystallizing into titanium dioxide. The (101) facet dominates the growth of titanium dioxide while the relative titanium densities on different parent crystal facets control the microstructures. Crystal growth in reducing atmospheres produces P-SC TinO2n-1 (n = 7~38) in magneli phases with enhanced visible-infrared light absorption and conductivity. The P-SC TinO2n-1 shows enhanced exciton lifetime and charge mobility. The P-SC TinO2n-1 boosts photoelectrochemical oxidation of benzene to phenol with P-SC Ti9O17 showing 60.1% benzene conversion and 99.6% phenol selectivity at room temperature which is the highest so far to the best of our knowledge.

Metallic Porous Iron Nitride and Tantalum Nitride Single Crystals with Enhanced Electrocatalysis Performance.

Altering a material's catalytic properties would require identifying structural features that deliver electrochemically active surfaces. Single-crystalline porous materials, combining the advantages of long-range ordering of bulk crystals and large surface areas of porous materials, would create sufficient active surfaces by stabilizing 2D active moieties confined in lattice and may provide an alternative way to create high-energy surfaces for electrocatalysis that are kinetically trapped. Here, a radical concept of building active metal-nitrogen moieties with unsaturated nitrogen coordination on a porous surface by directly growing metallic porous metal nitride (Fe3 N and Ta5 N6 ) single crystals at unprecedented 2 cm scale is reported. These porous single crystals demonstrate exceptionally high conductivity of 0.1-1.0 × 105 S cm-1 , while the atomic surface layers of the porous crystals are confirmed to be an Fe termination layer for Fe3 N and a Ta termination layer for Ta5 N6 . The unsaturated metal-nitrogen moieties (Fe6 -N and Ta5 -N3 ) with unique electronic structures demonstrate enhanced electrocatalysis performance and durability.

Nanobubbles: An Effective Way to Study Gas-Generating Catalysis on a Single Nanoparticle.

Gas-generating catalysis is important to many energy-related research fields, such as photocatalytic water splitting, water electrolysis, etc. The technique of single-nanoparticle catalysis is an effective way to search for highly active nanocatalysts and elucidate the reaction mechanism. However, gas-generating catalysis remains difficult to investigate at the single-nanoparticle level because product gases, such as H2 and O2, are difficult to detect on an individual nanoparticle. Here, we successfully find that nanobubbles can be used to study the gas-generating catalysis, i.e., H2 generation from formic acid dehydrogenation on a single Pd-Ag nanoplate, with a high time resolution (50 ms) via dark-field microscopy. The research reveals that the nanobubble evolution process includes nucleation time and lifetime. The nucleation rate of nanobubbles is proportional to the catalytic activity of a single nanocatalyst. The relationship between the catalytic activity and the nucleation rate is quantitatively described by a mathematical model, which shows that an onset reaction rate (ronset) exists for the generation of nanobubbles on a single Pd-Ag nanoplate. The research also reveals that a Pd-Ag nanoplate with larger size usually has a higher activity. However, some large-sized ones still have low activities, indicating the size of the Pd-Ag nanoplate is not the only key factor for the activity. Notablely, further research shows that Pd content is the key factor for the activity of single Pd-Ag nanoplates with similar size. The methodology and knowledge acquired from this research are also applicable to other important gas-generating catalysis reactions at the single-nanoparticle level.

Space debris detection in optical image sequences.

We present a high-accuracy, low false-alarm rate, and low computational-cost methodology for removing stars and noise and detecting space debris with low signal-to-noise ratio (SNR) in optical image sequences. First, time-index filtering and bright star intensity enhancement are implemented to remove stars and noise effectively. Then, a multistage quasi-hypothesis-testing method is proposed to detect the pieces of space debris with continuous and discontinuous trajectories. For this purpose, a time-index image is defined and generated. Experimental results show that the proposed method can detect space debris effectively without any false alarms. When the SNR is higher than or equal to 1.5, the detection probability can reach 100%, and when the SNR is as low as 1.3, 1.2, and 1, it can still achieve 99%, 97%, and 85% detection probabilities, respectively. Additionally, two large sets of image sequences are tested to show that the proposed method performs stably and effectively.

Massively Screening the Temporal Spectra of Single Nanoparticles to Uncover the Mechanism of Nanosynthesis.

Nanosynthesis is the basis of nanotechnology and its applications. It is necessary to understand the growth mechanism of nanoparticles and the functions of growth factors. An effective way to study the synthesis is at the single nanoparticle level. This study reports a single nanoparticle spectrometer, which is based on a commercial dark-field microscopy and a group of narrowband filters. This spectrometer has many advantages, such as high light transparency (35%-75%), low cost (<$1500), massive screening (≈200 nanoplates at a time), and a high time resolution (<5 s). By using this spectrometer, the galvanic replacement reaction (GRR) is studied on single Ag nanoplates in situ and in real time. The research reveals that GRR on single Ag nanoplates has three different types according to the change of peak wavelength during reaction. Such diverse reaction types can be attributed to the different relative reaction rates of GRR on the faces and edges of Ag nanoplate with different facets. Further research shows that the relative reaction rates of different facets vary a lot under different concentrations of tri-sodium citrate. This research successfully demonstrates that the new single nanoparticle spectrometer can study the growth of single nanoparticles and the effect of growth factors.

"Hot spots" growth on single nanowire controlled by electric charge.

"Hot spots" - a kind of highly active site, which are usually composed of some unique units, such as defects, interfaces, catalyst particles or special structures - can determine the performance of nanomaterials. In this paper, we study a model system, i.e. "hot spots" on a single Ag nanowire in the galvanic replacement reaction (GRR), by dark-field microscopy. The research reveals that electric charge can be released by the formation reaction of AgCl, and consequently the electrochemical potential on Ag nanowire drops. The electric charge could induce the reduction of Ag(+) to form the "hot spots" on the nanowire during the GRR. The appearance probability of "hot spots" is almost even along the Ag nanowire, while it is slightly lower near the two ends. The spatial distance between adjacent "hot spots" is also controlled by the charge, and obeys a model based on Boltzmann distribution. In addition, the distance distribution here has an advantage in electron transfer and energy saving. Therefore, it's necessary to consider the functions of electric charge during the synthesis or application of nanomaterials.