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At least 523 records · Page 29

Hot-Hole versus Hot-Electron Transport at Cu/GaN Heterojunction Interfaces

Among all plasmonic metals, copper (Cu) has the greatest potential for realizing optoelectronic and photochemical hot-carrier devices, thanks to its CMOS compatibility and outstanding catalytic properties. Yet, relative to gold (Au) or silver (Ag), Cu has rarely been studied and the fundamental properties of its photoexcited hot carriers are not well understood. Here, we demonstrate that Cu nanoantennas on p-type gallium nitride (p-GaN) enable hot-hole-driven photodetection across the visible spectrum. Importantly, we combine experimental measurements of the internal quantum efficiency (IQE) with ab initio theoretical modeling to clarify the competing roles of hot-carrier energy and mean-free path on the performance of hot-hole devices above and below the interband threshold of the metal. We also examine Cu-based plasmonic photodetectors on corresponding n-type GaN substrates that operate via the collection of hot electrons. By comparing hot hole and hot electron photodetectors that employ the same metal/semiconductor interface (Cu/GaN), we further elucidate the relative advantages and limitations of these complementary plasmonic systems. In particular, we find that harnessing hot holes with p-type semiconductors is a promising strategy for plasmon-driven photodetection across the visible and ultraviolet regimes. Given the technological relevance of Cu and the fundamental insights provided by our combined experimental and theoretical approach, we anticipate that our studies will have a broad impact on the design of hot-carrier optoelectronic devices and plasmon-driven photocatalytic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic Behavior of Bound Interlayer Excitons in Interlayer-Doped Cs 3 Bi 2 Br 9 Vacancy-Ordered Perovskite

Interlayer doping of the vacancy-ordered 2D perovskite Cs 3 Bi 2 Br 9 (CBB) enables the formation of bound interlayer excitons (BIEs), a unique charge-transfer excited state within the layered solid. BIEs previously reported with silver (Ag + ) as an interlayer dopant exhibited bright broadband photoluminescence (PL) with prolonged lifetime at room temperature, offering potential applications in efficient white light emission, photocatalysis, and optoelectronics. However, the dynamic behavior of radiation and excited carriers remains poorly understood due to the limitations of ensemble spectroscopic measurements. Here, we investigate the temperature-dependent dynamics of Ag-doped Cs 3 Bi 2 Br 9 (Ag-CBB) using single-particle time-resolved PL spectroscopy and ultrafast transient absorption imaging. Single-particle PL measurements reveal three distinct emission regimes across temperature: (i) BIE-dominant emission at high temperatures, (ii) a mixture of radiation from BIEs and self-trapped excitons (STEs) at intermediate temperatures, and (iii) STE-dominant emission below 100 K. Rapid transient absorption mapping using Parallel Rapid Imaging with Spectroscopic Mapping (PRISM) reveals subpicosecond STE formation in pristine CBB and long-lived photoinduced absorption by BIEs, consistent with electron–hole separation and suppressed STE transfer. The spatial uniformity of these signals confirms homogeneous Ag doping across single crystals. These findings highlight the role of Ag interlayer dopants in governing the BIE dynamics.

bound interlayer exciton↗

Efficient Measurement of Length Distribution of 1D Nanoparticles in Solution via Optical Polarimetry

The efficient measurement of the length distribution of nanotubes, nanowires, and other one-dimensional (1D) nanoparticles in solution is important to enable their incorporation into materials and devices and to optimize their processing for properties of interest, such as thermal/electrical conductivity or mechanical strength, in suspensions and composites. We report an electric-field (E-field)-assisted optical-polarimetry technique to measure the length distribution of ensembles of high-aspect-ratio particles in dilute suspension. The degree of alignment of polarizable 1D particles suspended in a fluid under Brownian motion explicitly depends on the E-field strength and the particle length. We show that it is possible to extract the length distribution of 1D nanoparticles suspended in an insulating fluid by applying a range of E-fields and using optical polarimetry to measure the corresponding alignment order parameter. Notably, the method is relatively insensitive to the diameter of the 1D particles, which can be poorly known or vary within a sample. The technique is validated with silver nanowires and carbon nanotubes of known lengths, as well as polymer-depletion-length-separated single-wall carbon nanotube samples with length distributions independently measured with analytical ultracentrifugation. Finally, we demonstrate the ability of the optical-polarimetry technique to quantify changes in the length distribution of ultranarrow, sub-nanometer-diameter single-wall carbon nanotubes under different types and durations of ultrasonication. Within its range of applicability (polarizable 1D nanoparticles in the 0.5 to 15 μm length range, constrained by the voltage stability of the media and the suspended particles), the E-field-assisted optical-polarimetry method is a particularly efficient and accurate method to measure the length distribution of nanowires and nanotubes in suspension.

1D nanoparticles↗

Iodine capture with mechanically robust heat-treated Ag-Al-Si-O xerogel sorbents

Silver-loaded heat-treated aluminosilicate xerogels (Ag-HTX) were evaluated as sorbents for iodine [I2(g)] capture. The heat treatment step was performed to help increase the mechanical integrity of the gels. The synthesized xerogels were characterized using powder X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, Brunauer-Emmett-Teller analysis, gravimetric iodine loading, nanoindentation, and dynamic mechanical analysis. The structural and chemical analyses of Ag-HTX showed uniform distribution of Ag throughout the gel network after Ag-exchange. After I2(g) capture, the AgI crystallites were observed in the sorbent verifying chemisorption as the iodine capture mechanism. Iodine loading of this xerogel was 0.43 g g-1 at 150°C over 1 d and 0.52 g g-1 at 22°C over 33 d. The specific surface area of Ag-HTX was 202 m2 g-1 and decreased to 87 m2 g-1 after iodine loading. The hardness of the heat-treated xerogel was 160 times higher than heat-treated aerogel of the same composition. The heat-treatment process increased the modulus value to 40.77 MPa from 6.99 MPa of as-made xerogel, demonstrating the need for this added step in the synthesis process. These results show that Ag-HTX is a promising sorbent for I2(g) capture with good loading capacity and mechanical stability.

xerogels, aerogels, iodine capture, hardness testi↗

Surface-Enhanced Raman Scattering Optophysiology Nanofibers for the Detection of Heavy Metals in Single Breast Cancer Cells

Mercury(II) ions (Hg2+) and silver ions (Ag+) are two of the most hazardous pollutants causing serious damage to human health. Here, we constructed surface enhanced Raman scattering (SERS)-active nanofibers covered with 4-mercaptopyridine (4-Mpy)-modified gold nanoparticles (AuNPs) to detect Hg2+ and Ag+. Experimental evidence suggests that the observed spectral changes originate from the combined effect of (i) the coordination between the nitrogen on 4-Mpy and the metal ions and (ii) the 4-Mpy molecular orientation (from flatter to more perpendicular with respect to the metal surface). The relative intensity of a pair of characteristic Raman peaks (at ~428 and ~708 cm-1) was used to quantify the metal ion concentration, greatly increasing the reproducibility of the measurement compared to signal-on or signal-off detection based on a single SERS peak. The detection limit of this method for Hg2+ is lower than that for the Ag+ (5 nM vs 100 nM), which can be explained by the stronger interaction energy between Hg2+ and N compared to Ag+ and N, as demonstrated by density functional theory (DFT) calculations. The Hg2+ and Ag+ ions can be masked by adding ethylenediaminetetraacetate (EDTA) and Cl-, respectively, to the Hg2+ and Ag+ samples. The good sensitivity, high reproducibility and excellent selectivity of these nanosensors were also demonstrated. Furthermore, detection of Hg2+ in living breast cancer cells at the subcellular level is possible thanks to the nanometric size of the herein described SERS nanosensors, allowing high spatial resolution and minimal cell damage.

Zhao, Xingjuan↗

Cascade Reaction of Ethanol to Butadiene over Multifunctional Silica-Supported Ag and ZrO 2 Catalysts

Although butadiene is currently a by-product of naphtha cracking, interest in producing butadiene from bio-based ethanol has increased because of the lower environmental impact of the ethanol to butadiene reaction. Furthermore, this work explores a multifunctional catalyst system composed of silica-supported Ag and ZrO 2 used for the cascade reaction of ethanol to butadiene at 573 K. The Ag and ZrO 2 components were synthesized on separate support particles enabling characterization of each component without interference from the other. High selectivity to butadiene (65%) at high ethanol conversion (75%) was achieved with an appropriate ratio of Ag and ZrO 2 in the reactor. Silver catalyzed the initial dehydrogenation of ethanol to acetaldehyde while ZrO 2 catalyzed the C-C coupling and subsequent dehydration reactions. The silica-supported ZrO 2 exhibited superior selectivity relative to bulk ZrO 2 in the Ag-promoted ethanol to butadiene reaction. Results from Zr K-edge X-ray absorption spectroscopy and UV-Vis spectroscopy showed that ZrO 2 was highly dispersed on the silica support over a range of loadings. Infrared spectroscopy of adsorbed pyridine, CO, and CO 2 , and kinetics of probe reactions 1-butene double bond isomerization, 2-propanol decomposition, and ethanol hydrogenation of acetone were used to compare the acid-base nature and chemical reactivity of silica-supported ZrO 2 to bulk ZrO 2 .

09 BIOMASS FUELS↗

Dual-Bed Radioiodine Capture from Complex Gas Streams with Zeolites: Regeneration and Reuse of Primary Sorbent Beds for Sustainable Waste Management

Dual-sorbent systems are proposed for radioiodine management with a regenerated primary bed for multiple cycles of use in complex conditions and a secondary bed for disposal with higher waste loadings. Sorbent approaches for the effective capture of gaseous radioiodine (isotopes 129 I and 131 I) produced from a range of nuclear processes have been studied for over half a century. (1−5) Whether or not a sorbent (e.g., molecular sieve) is required to physically screen/trap or chemically bind a radionuclide of interest through chemisorption, the complexity of the gas stream has a large impact on the performance (e.g., loading capacity, selectivity) and active life of a sorbent bed. (3) Silver mordenite (AgZ), the U.S. Department of Energy baseline sorbent for radioiodine capture from nuclear processes, performs well within acidic conditions and at elevated temperatures (6) and can be consolidated into a chemically durable waste form for long-term disposal. (7,8) However, new sorbents are being sought because optimal capture performance of AgZ significantly decreases in dynamic oxidizing environments with competing species, and it is expensive and it contains Ag (a toxic metal). (9) Until a new sorbent is found to replace AgZ, the regeneration and reuse of AgZ is an attractive alternative to a single-use primary sorbent bed. In this regard, a primary sorbent could be designed for enhanced capture in complex gas streams and the ability to be regenerated for reuse. Here, a secondary sorbent could then be tailored for maximum iodine loading in the gas stream and chemical durability within a disposal facility.

chemisorption↗

Compact Peptoid Molecular Brushes for Nanoparticle Stabilization

Controlling the interfaces and interactions of colloidal nanoparticles (NPs) via tethered molecular moieties is crucial for NP applications in engineered nanomaterials, optics, catalysis, and nanomedicine. Despite a broad range of molecular types explored, there is a need for a flexible approach to rationally vary the chemistry and structure of these interfacial molecules for controlling NP stability in diverse environments, while maintaining a small size of the NP molecular shell. Here, we demonstrate that low-molecular-weight, bifunctional comb-shaped, and sequence-defined peptoids can effectively stabilize gold NPs (AuNPs). The generality of this robust functionalization strategy was also demonstrated by coating of silver, platinum, and iron oxide NPs with designed peptoids. Each peptoid (PE) is designed with varied arrangements of a multivalent AuNP-binding domain and a solvation domain consisting of oligo-ethylene glycol (EG) branches. Among designs, a peptoid (PE5) with a diblock structure is demonstrated to provide a superior nanocolloidal stability in diverse aqueous solutions while forming a compact shell (similar to 1.5 nm) on the AuNP surface. We demonstrate by experiments and molecular dynamics simulations that PE5-coated AuNPs (PE5/AuNPs) are stable in select organic solvents owing to the strong PE5 (amine)-Au binding and solubility of the oligo-EG motifs. At the vapor-aqueous interface, we show that PE5/AuNPs remain stable and can self-assemble into ordered 2D lattices. The NP films exhibit strong near-field plasmonic coupling when transferred to solid substrates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Achieving Ultra-High Selectivity to Hydrogen Production from Formic Acid on Pd–Ag Alloys

Palladium-silver based alloy catalysts have a great potential for CO-free hydrogen production from formic acid for fuel cell applications. However, the structural factors affecting the selectivity of formic acid decomposition is still debated. Herein, the decomposition pathways of formic acid on Pd-Ag alloys with different atomic configurations have been investigated to identify the alloy structures yielding high H 2 selectively. Several Pd x Ag 1-x surface alloys with various compositions were generated on a Pd(111) single crystal; their atomic distribution and electronic structure were determined by a combination of infrared reflection absorption spectroscopy (IRAS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). It was established that the Ag atoms with Pd neighbors are electronically altered, and the degree of alteration correlates with the number of nearest Pd. Temperature programmed reaction spectroscopy (TPRS) and DFT demonstrated that the electronically altered Ag domains create a new reaction pathway that selectively dehydrogenates formic acid. In contrast, Pd monomers surrounded by Ag are demonstrated to have a similar reactivity compared to pristine Pd(111), yielding CO and H 2 O in addition to the dehydrogenation products. Furthermore, they bind to the produced CO weaker than pristine Pd, demonstrating an enhancement in resistance to CO poisoning. This work therefore shows that surface Ag domains modified by interaction with subsurface Pd are the key active sites for selective decomposition of formic acid, while surface Pd atoms are detrimental for selectivity. Hence the decomposition pathways can be tailored for CO-free H 2 production on Pd-Ag alloy systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical and Structural Evolution of AgCu Catalysts in Electrochemical CO 2 Reduction

Silver–copper (AgCu) bimetallic catalysts hold great potential for electrochemical carbon dioxide reduction reaction (CO 2 RR), which is a promising way to realize the goal of carbon neutrality. Although a wide variety of AgCu catalysts have been developed so far, it is relatively less explored how these AgCu catalysts evolve during CO 2 RR. The absence of insights into their stability makes the dynamic catalytic sites elusive and hampers the design of AgCu catalysts in a rational manner. Here, in this study, we synthesized intermixed and phase-separated AgCu nanoparticles on carbon paper electrodes and investigated their evolution behavior in CO 2 RR. Our time-sequential electron microscopy and elemental mapping studies show that Cu possesses high mobility in AgCu under CO 2 RR conditions, which can leach out from the catalysts by migrating to the bimetallic catalyst surface, detaching from the catalysts, and agglomerating as new particles. Besides, Ag and Cu manifest a trend to phase-separate into Cu-rich and Ag-rich grains, regardless of the starting catalyst structure. The composition of the Cu-rich and Ag-rich grains diverges during the reaction and eventually approaches thermodynamic values, i.e., Ag 0.88 Cu 0.12 and Ag 0.05 Cu 0.95 . The separation between Ag and Cu has been observed in the bulk and on the surface of the catalysts, highlighting the importance of AgCu phase boundaries for CO 2 RR. In addition, an operando high-energy-resolution X-ray absorption spectroscopy study confirms the metallic state of Cu in AgCu as the catalytically active sites during CO 2 RR. Taken together, this work provides a comprehensive understanding of the chemical and structural evolution behavior of AgCu catalysts in CO 2 RR.

Chen, Peng-Cheng↗

Ferroelectric Polarization in BaTiO 3 Nanocrystals Controls Photoelectrochemical Water Oxidation and Photocatalytic Hydrogen Evolution

Ferroelectric (FE) semiconductors such as BaTiO 3 support a remnant polarization after the application of an electric field that can promote the separation of photogenerated charge carriers. Here, we demonstrate FE-enhanced photocatalytic hydrogen evolution and photoelectrochemical water oxidation with barium titanate nanocrystals for the first time. Nanocrystals of the ferroelectric tetragonal structure type were obtained by a hydrothermal synthesis from TiO 2 and barium hydroxide in 63% yield. BaTiO 3 nanocrystal films on tantalum substrates exhibit water oxidation photocurrents of 0.141 mA cm –2 at 1.23 V RHE under UV light (60 mW cm –2 ) illumination. Electric polarization at 52.8 kV cm –1 normal to the film plane increases the photocurrent by a factor of 2 or decreases it by a factor of 3.5, depending on the field polarity. It also shifts the onset potential by –0.15 or +0.09 V and it modifies the surface photovoltage signal. Lastly, exposure to an electric field increases the H 2 evolution rate of Pt/BaTiO 3 by a factor of ~1.5, and it raises the selectivity of photodeposition of silver onto the (001) facets of the nanocrystal. All FE enhancements can be removed by heating samples above the Curie temperature of BaTiO 3 . Furthermore, these findings can be explained by FE dipole-induced changes to the potential drop across the space charge layer of the material. The ability to use the ferroelectric effect to enhance hydrogen evolution and water oxidation is of potential interest for the development of improved solar energy for fuel conversion systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synergistic Effects of the Electric Field Induced by Imidazolium Rotation and Hydrogen Bonding in Electrocatalysis of CO 2

The roles of the ionic liquid, 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF₄]), and water in controlling the mechanism, energetics, and electrocatalytic activity of CO₂ reduction to CO on silver in non-aqueous electrolytes were investigated. The first electron transfer occurs to CO₂ at reduced overpotentials when it is trapped between the planes of [EMIM]⁺ ring and electrode surface due to cation re-orientation as determined from voltammetry, in-situ surface-enhanced Raman spectroscopy, and density functional theory calculations. Within this interface, water up to 0.5 M does not induce significant faradaic activity, opposing the notion of it as a free proton source. Instead, water acts as a hydrogen bond donor and the proton is sourced from [EMIM]⁺. Furthermore, this study demonstrates that alcohols with varying acidity tune the hydrogen bonding network in the interfacial microenvironment to lower the energetics required for CO₂ reduction. Here, the hydrogen bonding suppresses the formation of inactive carboxylate species, thus preserving the catalytic activity of [EMIM]⁺. The ability to tune the hydrogen bonding network opens new avenues for advancing IL-mediated electrocatalytic reactions in non-aqueous electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Systematic Bandgap Engineering of a 2D Organic–Inorganic Chalcogenide Semiconductor via Ligand Modification

Hybrid organic–inorganic semiconductors present new opportunities for optoelectronic materials design not available in all-organic or all-inorganic materials. One example is silver phenylselenide (AgSePh) – or “mithrene” – a blue-emitting 2D organic–inorganic semiconductor exhibiting strong optical and electronic anisotropy. Here, we show that the bandgap of mithrene can be systematically tuned by introducing electron-donating and electron-withdrawing groups to the phenyl ligands. We synthesized nine mithrene variants, eight of which formed 2D van der Waals crystals analogous to those of AgSePh. Density functional theory calculations reveal that these 2D mithrene variants are direct-gap or nearly direct gap semiconductors. Furthermore, we identify correlations between the optical gap and three experimental observables – the Hammett constant, 77 Se chemical shift, and selenium partial charge – offering predictive power for bandgap tuning. These findings highlight new opportunities for applying the tools of chemical synthesis to semiconductor materials design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interfacial Cation Arrangement Controls Electrocatalytic Kinetics in CO 2 Reduction

The identity of electrolyte cations is known to strongly influence electrocatalytic activity, but the relationship between their interfacial arrangement and observed performance remains poorly understood. Organic cations, with their molecular tunability, provide a powerful platform for systematically probing these effects. Here, we leverage phosphonium-based geminal dications to control interfacial cation arrangement and identify the variables that most strongly influence catalytic rates. As a case study, we examine CO 2 reduction to CO over polycrystalline silver electrodes in dry aprotic acetonitrile. Through a combination of rotating disk electrode measurements, electrochemical impedance spectroscopy, and molecular dynamics simulations, we decouple the effects of cation–electrode distance and interfacial cation density on catalytic rates. We find that smaller, more densely packed cations induce stronger interfacial electric fields, which lower the activation barrier for CO 2 adsorption and increase reaction rates. Using geminal phosphonium dications [C n (P mmm ) 2 ][ClO 4 ] 2 , we demonstrate that both the vertical and lateral positioning of organic cations within the electrical double layer independently affect reactivity. These results demonstrate that electrolyte cation identity primarily influences catalytic kinetics by determining how efficiently charge can be arranged at electrochemical interfaces. Altogether, our findings support an electrostatic view of cation effects in catalysis and provide design principles for next-generation electrolytes.

Cations↗

Aerosol jet printing of piezoelectric surface acoustic wave thermometer

Abstract Surface acoustic wave (SAW) devices are a subclass of micro-electromechanical systems (MEMS) that generate an acoustic emission when electrically stimulated. These transducers also work as detectors, converting surface strain into readable electrical signals. Physical properties of the generated SAW are material dependent and influenced by external factors like temperature. By monitoring temperature-dependent scattering parameters a SAW device can function as a thermometer to elucidate substrate temperature. Traditional fabrication of SAW sensors requires labor- and cost- intensive subtractive processes that produce large volumes of hazardous waste. This study utilizes an innovative aerosol jet printer to directly write consistent, high-resolution, silver comb electrodes onto a Y-cut LiNbO 3 substrate. The printed, two-port, 20 MHz SAW sensor exhibited excellent linearity and repeatability while being verified as a thermometer from 25 to 200 ∘ C. Sensitivities of the printed SAW thermometer are $$-96.9\times 1{0{}^{-6}}^{\circ }$$ − 96.9 × 1 0 − 6 ∘ C −1 and $$-92.0\times 1{0{}^{-6}}^{\circ }$$ − 92.0 × 1 0 − 6 ∘ C −1 when operating in pulse-echo mode and pulse-receiver mode, respectively. These results highlight a repeatable path to the additive fabrication of compact high-frequency SAW thermometers.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Aerosol jet printing of surface acoustic wave microfluidic devices

Abstract The addition of surface acoustic wave (SAW) technologies to microfluidics has greatly advanced lab-on-a-chip applications due to their unique and powerful attributes, including high-precision manipulation, versatility, integrability, biocompatibility, contactless nature, and rapid actuation. However, the development of SAW microfluidic devices is limited by complex and time-consuming micro/nanofabrication techniques and access to cleanroom facilities for multistep photolithography and vacuum-based processing. To simplify the fabrication of SAW microfluidic devices with customizable dimensions and functions, we utilized the additive manufacturing technique of aerosol jet printing. We successfully fabricated customized SAW microfluidic devices of varying materials, including silver nanowires, graphene, and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS). To characterize and compare the acoustic actuation performance of these aerosol jet printed SAW microfluidic devices with their cleanroom-fabricated counterparts, the wave displacements and resonant frequencies of the different fabricated devices were directly measured through scanning laser Doppler vibrometry. Finally, to exhibit the capability of the aerosol jet printed devices for lab-on-a-chip applications, we successfully conducted acoustic streaming and particle concentration experiments. Overall, we demonstrated a novel solution-based, direct-write, single-step, cleanroom-free additive manufacturing technique to rapidly develop SAW microfluidic devices that shows viability for applications in the fields of biology, chemistry, engineering, and medicine.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

The impact of nitrogen oxides on electrochemical carbon dioxide reduction

The electroreduction of carbon dioxide offers a promising avenue to produce valuable fuels and chemicals using greenhouse gas carbon dioxide as the carbon feedstock. Because industrial carbon dioxide point sources often contain numerous contaminants, such as nitrogen oxides, understanding the potential impact of contaminants on carbon dioxide electrolysis is crucial for practical applications. Herein, we investigate the impact of various nitrogen oxides, including nitric oxide, nitrogen dioxide, and nitrous oxide, on carbon dioxide electroreduction on three model electrocatalysts (i.e., copper, silver, and tin). We demonstrate that the presence of nitrogen oxides (up to 0.83%) in the carbon dioxide feed leads to a considerable Faradaic efficiency loss in carbon dioxide electroreduction, which is caused by the preferential electroreduction of nitrogen oxides over carbon dioxide. The primary products of nitrogen oxides electroreduction include nitrous oxide, nitrogen, hydroxylamine, and ammonia. Despite the loss in Faradaic efficiency, the electrocatalysts exhibit similar carbon dioxide reduction performances once a pure carbon dioxide feed is restored, indicating a negligible long-term impact of nitrogen oxides on the catalytic properties of the model catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metallic surface doping of metal halide perovskites

Abstract Intentional doping is the core of semiconductor technologies to tune electrical and optical properties of semiconductors for electronic devices, however, it has shown to be a grand challenge for halide perovskites. Here, we show that some metal ions, such as silver, strontium, cerium ions, which exist in the precursors of halide perovskites as impurities, can n-dope the surface of perovskites from being intrinsic to metallic. The low solubility of these ions in halide perovskite crystals excludes the metal impurities to perovskite surfaces, leaving the interior of perovskite crystals intrinsic. Computation shows these metal ions introduce many electronic states close to the conduction band minimum of perovskites and induce n-doping, which is in striking contrast to passivating ions such as potassium and rubidium ion. The discovery of metallic surface doping of perovskites enables new device and material designs that combine the intrinsic interior and heavily doped surface of perovskites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗