Showing papers by "Peidong Yang published in 2022"

The Interactive Dynamics of Nanocatalyst Structure and Microenvironment during Electrochemical CO2 Conversion

Abstract: In the pursuit of a decarbonized society, electrocatalytic CO2 conversion has drawn tremendous research interest in recent years as a promising route to recycling CO2 into more valuable chemicals. To achieve high catalytic activity and selectivity, nanocatalysts of diverse structures and compositions have been designed. However, the dynamic structural transformation of the nanocatalysts taking place under operating conditions makes it difficult to study active site configurations present during the CO2 reduction reaction (CO2RR). In addition, although recognized as consequential to the catalytic performance, the reaction microenvironment generated near the nanocatalyst surface during CO2RR and its impact are still an understudied research area. In this Perspective, we discuss current understandings and difficulties associated with investigating such dynamic aspects of both the surface reaction site and its surrounding reaction environment as a whole. We further highlight the interactive influence of the structural transformation and the microenvironment on the catalytic performance of nanocatalysts. We also present future research directions to control the structural evolution of nanocatalysts and tailor their reaction microenvironment to achieve an ideal catalyst for improved electrochemical CO2RR.

Ferroelectricity in a semiconducting all-inorganic halide perovskite.

Abstract: Ferroelectric semiconductors are rare materials with both spontaneous polarizations and visible light absorptions that are promising for designing functional photoferroelectrics, such as optical switches and ferroelectric photovoltaics. The emerging halide perovskites with remarkable semiconducting properties also have the potential of being ferroelectric, yet the evidence of robust ferroelectricity in the typical three-dimensional hybrid halide perovskites has been elusive. Here, we report on the investigation of ferroelectricity in all-inorganic halide perovskites, CsGeX3, with bandgaps of 1.6 to 3.3 eV. Their ferroelectricity originates from the lone pair stereochemical activity in Ge (II) that promotes the ion displacement. This gives rise to their spontaneous polarizations of ~10 to 20 μC/cm2, evidenced by both ab initio calculations and key experiments including atomic-level ionic displacement vector mapping and ferroelectric hysteresis loop measurement. Furthermore, characteristic ferroelectric domain patterns on the well-defined CsGeBr3 nanoplates are imaged with both piezo-response force microscopy and nonlinear optical microscopic method.

Photoelectrochemical CO2 Reduction toward Multicarbon Products with Silicon Nanowire Photocathodes Interfaced with Copper Nanoparticles.

Abstract: The development of photoelectrochemical systems for converting CO2 into chemical feedstocks offers an attractive strategy for clean energy storage by directly utilizing solar energy, but selectivity and stability for these systems have thus been limited. Here, we interface silicon nanowire (SiNW) photocathodes with a copper nanoparticle (CuNP) ensemble to drive efficient photoelectrochemical CO2 conversion to multicarbon products. This integrated system enables CO2-to-C2H4 conversion with faradaic efficiency approaching 25% and partial current densities above 2.5 mA/cm2 at -0.50 V vs RHE, while the nanowire photocathodes deliver 350 mV of photovoltage under 1 sun illumination. Under 50 h of continual bias and illumination, CuNP/SiNW can sustain stable photoelectrochemical CO2 reduction. These results demonstrate the nanowire/catalyst system as a powerful modular platform to achieve stable photoelectrochemical CO2 reduction and the feasibility to facilitate complex reactions toward multicarbons using generated photocarriers.

Operando Resonant Soft X-ray Scattering Studies of Chemical Environment and Interparticle Dynamics of Cu Nanocatalysts for CO2 Electroreduction.

Abstract: Understanding the chemical environment and interparticle dynamics of nanoparticle electrocatalysts under operating conditions offers valuable insights into tuning their activity and selectivity. This is particularly important to the design of Cu nanocatalysts for CO2 electroreduction due to their dynamic nature under bias. Here, we have developed operando electrochemical resonant soft X-ray scattering (EC-RSoXS) to probe the chemical identity of active sites during the dynamic structural transformation of Cu nanoparticle (NP) ensembles through 1 μm thick electrolyte. Operando scattering-enhanced X-ray absorption spectroscopy (XAS) serves as a powerful technique to investigate the size-dependent catalyst stability under beam exposure while monitoring the potential-dependent surface structural changes. Small NPs (7 nm) in aqueous electrolyte were found to experience a predominant soft X-ray beam-induced oxidation to CuO despite only sub-second X-ray exposure. In comparison, large NPs (18 nm) showed improved resistivity to beam damage, which allowed the reliable observation of surface Cu2O electroreduction to metallic Cu. Small-angle X-ray scattering (SAXS) statistically probes the particle-particle interactions of large ensembles of NPs. This study points out the need for rigorous examination of beam effects for operando X-ray studies on electrocatalysts. The strategy of using EC-RSoXS that combines soft XAS and SAXS can serve as a general approach to simultaneously investigate the chemical environment and interparticle information on nanocatalysts.

Photosynthetic biohybrid coculture for tandem and tunable CO2 and N2 fixation

Abstract: Significance Combining (photo)electrochemical platforms with CO2 -fixing bacteria as “living” biocatalysts has realized the highly selective reduction of CO2 to C2+ products, such as acetate. This approach also enables the downstream conversion of the initial CO2 product to a higher-value one. We report an advance on this concept by coculturing primary CO2-fixing bacteria producing acetate with secondary N2-fixing bacteria that employ the acetate to reduce N2 to NH3 and to generate a bioplastic. The symbiotic coculture can be controlled electrochemically and modularly tuned to generate a desired product stream. We foresee that this platform could be expanded to produce several additional products, including bioplastics, biofuels, and sugars, from only CO2, N2, H2O, and electricity.

Enhancing Biohybrid CO2 to Multicarbon Reduction via Adapted Whole-Cell Catalysts.

Abstract: Catalytic CO2 conversion to renewable fuel is of utmost importance to establish a carbon-neutral society. Bioelectrochemical CO2 reduction, in which a solid cathode interfaces with CO2-reducing bacteria, represents a promising approach for renewable and sustainable fuel production. The rational design of biocatalysts in the biohybrid system is imperative to effectively reduce CO2 into valuable chemicals. Here, we introduce methanol adapted Sporomusa ovata (S. ovata) to enhance the slow metabolic activity of wild-type microorganisms to our semiconductive silicon nanowires (Si NWs) array for efficient CO2 reduction. The adapted whole-cell catalysts enable an enhancement of CO2 fixation with a superior faradaic efficiency on the poised Si NWs cathode. The synergy of the high-surface-area cathode and the adapted strain achieves a CO2-reducing current density of 0.88 ± 0.11 mA/cm2, which is 2.4-fold higher than the wild-type strain. This new generation of biohybrids using adapted S. ovata also decreases the charge transfer resistance at the cathodic interface and facilitates the faster charge transfer from the solid electrode to bacteria.

Supramolecular Assembly of Halide Perovskite Building Blocks.

Abstract: The structural diversity and tunable optoelectronic properties of halide perovskites originate from the rich chemistry of the metal halide ionic octahedron [MX6]n- (M = Pb2+, Sb3+, Te4+, Sn4+, Pt4+, etc.; X = Cl-, Br-, and I-). The properties of the extended perovskite solids are dictated by the assembly, connectivity, and interaction of these octahedra within the lattice environment. Hence, the ability to manipulate and control the assembly of the octahedral building blocks is paramount for constructing new perovskite materials. Here, we propose a systematic supramolecular strategy for the assembly of [MX6]n- octahedra into a solid extended network. Interaction of alkali metal-bound crown ethers with the [M(IV)X6]2- octahedron resulted in a structurally and optoelectronically tunable "dumbbell" structural unit in solution. Single crystals with diverse packing geometries and symmetries will form as the solid assembly of this new supramolecular building block. This supramolecular assembly route introduces a new general strategy for designing halide perovskite structures with potentially new optoelectronic properties.

Technologies Enabling Single-Molecule Super-Resolution Imaging of mRNA

Abstract: The transient nature of RNA has rendered it one of the more difficult biological targets for imaging. This difficulty stems both from the physical properties of RNA as well as the temporal constraints associated therewith. These concerns are further complicated by the difficulty in imaging endogenous RNA within a cell that has been transfected with a target sequence. These concerns, combined with traditional concerns associated with super-resolution light microscopy has made the imaging of this critical target difficult. Recent advances have provided researchers the tools to image endogenous RNA in live cells at both the cellular and single-molecule level. Here, we review techniques used for labeling and imaging RNA with special emphases on various labeling methods and a virtual 3D super-resolution imaging technique.

Spelling out the roles of individual nucleoporins in nuclear export of mRNA

Abstract: ABSTRACT The Nuclear Pore Complex (NPC) represents a critical passage through the nuclear envelope for nuclear import and export that impacts nearly every cellular process at some level. Recent technological advances in the form of Auxin Inducible Degron (AID) strategies and Single-Point Edge-Excitation sub-Diffraction (SPEED) microscopy have enabled us to provide new insight into the distinct functions and roles of nuclear basket nucleoporins (Nups) upon nuclear docking and export for mRNAs. In this paper, we provide a review of our recent findings as well as an assessment of new techniques, updated models, and future perspectives in the studies of mRNA’s nuclear export.

An embedded interfacial network stabilizes inorganic CsPbI3 perovskite thin films

Abstract: Abstract The black perovskite phase of CsPbI 3 is promising for optoelectronic applications; however, it is unstable under ambient conditions, transforming within minutes into an optically inactive yellow phase, a fact that has so far prevented its widespread adoption. Here we use coarse photolithography to embed a PbI 2 -based interfacial microstructure into otherwise-unstable CsPbI 3 perovskite thin films and devices. Films fitted with a tessellating microgrid are rendered resistant to moisture-triggered decay and exhibit enhanced long-term stability of the black phase (beyond 2.5 years in a dry environment), due to increasing the phase transition energy barrier and limiting the spread of potential yellow phase formation to structurally isolated domains of the grid. This stabilizing effect is readily achieved at the device level, where unencapsulated CsPbI 3 perovskite photodetectors display ambient-stable operation. These findings provide insights into the nature of phase destabilization in emerging CsPbI 3 perovskite devices and demonstrate an effective stabilization procedure which is entirely orthogonal to existing approaches.

Controlling the Phase Transition in CsPbI3 Nanowires.

Abstract: Cesium lead iodide (CsPbI3) is a promising semiconductor with a suitable band gap for optoelectronic devices. CsPbI3 has a metastable perovskite phase that undergoes a phase transition into an unfavorable nonperovskite phase in an ambient environment. This phase transition changes the optoelectronic properties of CsPbI3 and hinders its potential for device applications. Therefore, it is of central importance to understand the kinetics of such instability and develop strategies to control and stabilize the perovskite phase. Here, we use ultralong CsPbI3 nanowires as a model platform to investigate the phase transition kinetics. Our results depict the role of environmental stressors (moisture and temperature) in controlling the phase transition dynamics of CsPbI3, which can serve as guiding principles for future phase transition studies and the design of related photovoltaics. Furthermore, we demonstrate the controllability of phase propagation on individual nanowires by varying the moisture level and temperature.

Nature of the Electrical Double Layer on Suspended Graphene Electrodes

Abstract: The structure of interfacial water near suspended graphene electrodes in contact with aqueous solutions of Na2SO4, NH4Cl, and (NH4)2SO4 has been studied using confocal Raman spectroscopy, sum frequency vibrational spectroscopy, and Kelvin probe force microscopy. SO42– anions were found to preferentially accumulate near the interface at an open circuit potential (OCP), creating an electrical field that orients water molecules below the interface, as revealed by the increased intensity of the O–H stretching peak of H-bonded water. No such increase is observed with NH4Cl at the OCP. The intensity of the dangling O–H bond stretching peak however remains largely unchanged. The degree of orientation of the water molecules as well as the electrical double layer strength increased further when positive voltages are applied. Negative voltages on the other hand produced only small changes in the intensity of the H-bonded water peaks but affected the intensity and frequency of dangling O–H bond peaks. The TOC figure is an oversimplified representation of the system in this work.

Chloride-Assisted Corrosion of Copper and Protection by Benzotriazole.

Abstract: The structure and composition of copper surfaces in aqueous solutions of benzotriazole (BTAH) and NaCl was investigated by sum frequency vibrational spectroscopy as a function of concentration and bias during cyclic voltammetry experiments. We found that the protection provided by the BTAH films formed at the copper surface is effective for negative bias voltages below the open circuit potential (OCP) but not at positive voltages where Cl- displaces BTAH. By measuring the Gibbs adsorption energy of BTAH and Cl-, we found that a particularly stable Cl- structure is formed around the OCP, suggesting that electronegative additives that move the OCP to higher negative values can improve BTAH protection, which we confirmed by the addition of a negatively charged sodium dodecyl sulfate surfactant.

Unraveling docking and initiation of mRNA export through the nuclear pore complex

Abstract: The nuclear export of mRNA through the nuclear pore complex (NPC) is a process required for the healthy functioning of human cells, making it a critical area of research. However, the geometries of mRNA and the NPC are well below the diffraction limit of light microscopy, thereby presenting significant challenges in evaluating the discrete interactions and dynamics involved in mRNA nuclear export through the native NPC. Recent advances in biotechnology and single‐molecule super‐resolution light microscopy have enabled researchers to gain granular insight into the specific contributions made by discrete nucleoporins in the nuclear basket of the NPC to the export of mRNA. Specifically, by expanding upon the docking step facilitated by the protein TPR in the nuclear basket as well as identifying NUP153 as being the primary nuclear basket protein initiating export through the central channel of the NPC.

Speed Microscopy: High-Speed Single Molecule Tracking and Mapping of Nucleocytoplasmic Transport.

Abstract: The nuclear pore complex (NPC) functions as a gateway through which molecules translocate into and out of the nucleus. Understanding the transport dynamics of these transiting molecules and how they interact with the NPC has great potentials in the discovery of clinical targets. Single-molecule microscopy techniques are powerful tools to provide sub–diffraction limit information about the dynamic and structural details of nucleocytoplasmic transport. Here we detail single-point edge-excitation subdiffraction (SPEED) microscopy, a high-speed superresolution microscopy technique designed to track and map proteins and RNAs as they cross native NPCs.

Selective Degradation and Quantification of Nucleoporins in the Nuclear Pore by Auxin‐Inducible Degrons and Single‐Molecule Microscopy

Abstract: There is a significant current question regarding the viable copy numbers of nucleoporins required for the function of the nuclear pore complex (NPC) in eukaryotic cells. The NPC consists of approximately 30 different nucleoporins in an eight‐fold symmetry, meaning that there are multiple duplicates of each nucleoporin present within the nuclear pore. We recently developed a method that combines auxin‐inducible degrons and single‐molecule super‐resolution microscopy to evaluate the copy number of nuclear basket nucleoporins required for the successful function of the NPC. Here, we describe the theory behind this auxin‐inducible degron and single‐molecule super‐resolution microscopy method, and we detail a step‐by‐step process to selectively degrade nucleoporins either completely or in a stepwise manner. © 2022 Wiley Periodicals LLC.