Hao Shan

In Situ Environmental TEM in Imaging Gas and Liquid Phase Chemical Reactions for Materials Research

Gas and liquid phase chemical reactions cover a broad range of research areas in materials science and engineering, including the synthesis of nanomaterials and application of nanomaterials, for example, in the areas of sensing, energy storage and conversion, catalysis, and bio-related applications. Environmental transmission electron microscopy (ETEM) provides a unique opportunity for monitoring gas and liquid phase reactions because it enables the observation of those reactions at the ultra-high spatial resolution, which is not achievable through other techniques. Here, the fundamental science and technology developments of gas and liquid phase TEM that facilitate the mechanistic study of the gas and liquid phase chemical reactions are discussed. Combined with other characterization tools integrated in TEM, unprecedented material behaviors and reaction mechanisms are observed through the use of the in situ gas and liquid phase TEM. These observations and also the recent applications in this emerging area are described. The current challenges in the imaging process are also discussed, including the imaging speed, imaging resolution, and data management.

Tuning Surface Structure and Strain in Pd–Pt Core–Shell Nanocrystals for Enhanced Electrocatalytic Oxygen Reduction

Icosahedral, octahedral, and cubic Pd@Pt core-shell nanocrystals with two atomic Pt layers are epitaxially generated under thermodynamic control. Such icosahedra exhibit remarkably enhanced catalytic properties for oxygen reduction reaction compared to the octahedra and cubes as well as commercial Pt/C, which can be attributed to ligand and geometry effects, especially twin-induced strain effect that is revealed by geometrical phase analysis.

Platinum‐Based Nanowires as Active Catalysts toward Oxygen Reduction Reaction: In Situ Observation of Surface‐Diffusion‐Assisted, Solid‐State Oriented Attachment

Facile fabrication of advanced catalysts toward oxygen reduction reaction with improving activity and stability is significant for proton-exchange membrane fuel cells. Based on a generic solid-state reaction, this study reports a modified hydrogen-assisted, gas-phase synthesis for facile, scalable production of surfactant-free, thin, platinum-based nanowire-network electrocatalysts. The free-standing platinum and platinum-nickel alloy nanowires show improvements of up to 5.1 times and 10.9 times for mass activity with a minimum 2.6% loss after an accelerated durability test for 10k cycles; 8.5 times and 13.8 times for specific activity, respectively, compared to commercial Pt/C catalyst. In addition, combined with a wet impregnation method, different substrate-materials-supported platinum-based nanowires are obtained, which paves the way to practical application as a next-generation supported catalyst to replace Pt/C. The growth stages and formation mechanism are investigated by an in situ transmission electron microscopy study. It reveals that the free-standing platinum nanowires form in the solid state via metal-surface-diffusion-assisted oriented attachment of individual nanoparticles, and the interaction with gas molecules plays a critical role, which may represent a gas-molecular-adsorbate-modified growth in catalyst preparation.

Bioinspired infrared detection using thermoresponsive hydrogel nanoparticles

Abstract The development of high performance uncooled infrared (IR) detection and imaging systems will greatly expand the application of IR technology in broad areas such as transportation, environmental monitoring, and medical care. Inspired by the superior IR detection capability of beetle Melanophila acuminata, we explored the potential use of hydrogel nanoparticles (NPs) in uncooled IR detection system. In the system, the absorption of the incoming IR radiation by the temperature-sensitive hydrogel NPs, together with water, induces the volume change of the hydrogel NPs, similar to the volume change of the biofluid inside the sensillae receptors in M. acuminata caused by the IR radiation. This volume change results in the change of optical readout (transmittance in this study) in visible range and provides the sensitive detection of the IR radiation. In this work, poly(N-isopropylacrylamide-co-acrylic acid) (poly(NIPAM-co-AAc)) copolymer NPs with different sizes were synthesized and their IR sensing performances were studied in detail. The correlation between the NP size and concentration and the IR sensing property was also discussed in the paper. This work helps enhance the understanding of the response of hydrogel NPs under IR radiation, and offers a potential material system for uncooled IR detection that is inspired by M. acuminata. The direct use of transmittance of the NP solution as the readout for IR detection also provides a simple and sensitive IR detection approach for low cost and portable industrial applications.

Enhancing the Photocatalytic Hydrogen Evolution Performance of a Metal/Semiconductor Catalyst through Modulation of the Schottky Barrier Height by Controlling the Orientation of the Interface

Construction of a metal-semiconductor heterojunction is a promising method to improve heterogeneous photocatalysis for various reactions. Although the structure and photocatalytic performance of such a catalyst system have been extensively studied, few reports have demonstrated the effect of interface orientation at the metal-semiconductor junction on junction-barrier bending and the electronic transport properties. Here, we construct a Pt/PbS heterojunction, in which Pt nanoparticles are used as highly active catalysts and PbS nanocrystals (NCs) with well-controlled shapes are used as light-harvesting supports. Experimental results show that the photoelectrocatalytic activities of the Pt/PbS catalyst are strongly dependent on the contacting facets of PbS at the junction. Pt/octahedral PbS NCs with exposed PbS(111) facets show the highest photoinduced enhancement of hydrogen evolution reaction activity, which is ∼14.38 times higher than that of the ones with only PbS(100) facets (Pt/cubic PbS NCs). This enhancement can further be rationalized by the different energy barriers of the Pt/PbS Schottky junction due to the specific band structure and electron affinity, which is also confirmed by the calculations based on density functional theory. Therefore, controlling the contacting interfaces of a metal/semiconductor material may offer an effective approach to form the desired heterojunction for optimization of the catalytic performance.

Ag3PO4 electrocatalyst for oxygen reduction reaction: enhancement from positive charge

We have demonstrated Ag3PO4 as an active non-Pt electrocatalyst with enhanced activity compared with Ag for oxygen reduction reaction (ORR). Density functional theory reveals that better ORR performance of Ag atoms on Ag3PO4 surface than that on pure silver surface originates from more appropriate oxygen adsorption on positively charged Ag atoms. Further study of the surface geometry of Ag3PO4 including tetrahedron, rhombic dodecahedron and cube indicates that the highest density of Ag and appropriate oxygen adsorption on {110} surface of rhombic dodecahedral Ag3PO4 lead to the highest ORR activity, which is about 12 times that of Pt catalysts from a commercial perspective. It may be applicable for developing low-cost and highly active non-Pt catalytic materials from a broader range of material systems.

Controllable assembly of Pd nanosheets: a solution for 2D materials storage

Two-dimensional (2D) materials have attracted wide attention in photonic, electric, catalysis, and energy fields. Compared to the gas phase synthesis, the liquid phase route enables mass production of 2D materials with relatively low costs. However, these free-standing 2D materials obtained via the wet chemical route have a strong tendency to stack on each other; moreover, their 2D structure and the relevant functions degrade over time. Thus, we developed a strategy to achieve the reversibility of assembly/disassembly in Pd nanosheets (NSs) by utilizing anionic/cationic surfactants. Based on this methodology, the 2D structure of free-standing Pd NSs can be preserved with excellent performances for long-term use. Our results showed that free-standing Pd NSs were extremely unstable and decomposed into nanoparticles in 9 days. However, the assembled Pd NSs stacks maintained their 2D structure and preserved the methanol oxidation reaction (MOR) properties after disassembling.