Ag Catalysts Research Articles

Ag(I)-Catalyzed Oxidative Cyclization of 1,4-Diynamide-3-ols with N-Oxide for Divergent Synthesis of 2-Substituted Furan-4-carboxamide Derivatives.

This work reports Ag(I)-catalyzed oxidative cyclizations of 1,4-diynamide-3-ols with 8-methylquinoline oxide to form 2-substituted furan-4-carboxamides. The reaction chemoselectivity is distinct from that reported in previous work by Hashmi. We performed density functional theory calculations to elucidate our proposed mechanism after evaluation of the energy profiles of two possible pathways. In this Ag(I) catalysis, the calculations suggest that the amide and alkyne groups of the 3,3-dicarbonyl-2-alkyne intermediates tend to chelate with the Ag(I) catalyst, further inducing a formyl attack at the Ag(I)-π-alkyne moiety to deliver the observed products.

Effect of the cryogenic treatment on the electrocatalytic performance of the active self-supporting nanoporous Pd–Ag catalyst with high-index facets’ preferred orientation

Effect of the cryogenic treatment on the electrocatalytic performance of the active self-supporting nanoporous Pd–Ag catalyst with high-index facets’ preferred orientation

Polyelectrolyte Additive-Modulated Interfacial Microenvironment Boosting CO2 Electrolysis in Acid.

Acidic CO2 electrolysis offers a promising strategy to achieve high carbon utilization and high energy efficiency. However, challenges remain in suppressing the competitive hydrogen evolution reaction (HER) and improving product selectivity. High concentrations of potassium ions (K+) can suppress HER and accelerate CO2 reduction, but they still inevitably suffer from salt precipitation problems. In this study, we demonstrate that the sulfonate-based polyelectrolyte, polystyrene sulfonate (PSS), enables to reconstruct the electrode-electrolyte interface to significantly enhance the acidic CO2 electrolysis. Mechanistic studies reveal that PSS induces high local K+ concentrations through electrostatic interaction between PSS anions and K+. In situ spectroscopy reveals that PSS reshapes the interfacial hydrogen-bond (H-bond) network, which is attributed to the H-bonds between PSS anions and hydrated proton as well as the steric hindrance of the additive molecules. This greatly weakens proton transfer kinetics and leads to the suppression of undesirable HER. As a result, a Faradaic efficiency of 93.9% for CO can be achieved at 250 mA cm-2, simultaneous with a high single-pass carbon efficiency of 72.2% on commercial Ag catalysts in acid. This study highlights the important role of the electrode-electrolyte interface induced by polyelectrolyte additives in promoting electrocatalytic reactions.

Polyelectrolyte Additive‐Modulated Interfacial Microenvironment Boosting CO2 Electrolysis in Acid

Acidic CO2 electrolysis offers a promising strategy to achieve high carbon utilization and high energy efficiency. However, challenges remain in suppressing the competitive hydrogen evolution reaction (HER) and improving product selectivity. High concentrations of potassium ions (K+) can suppress HER and accelerate CO2 reduction, but they still inevitably suffer from salt precipitation problems. In this study, we demonstrate that the sulfonate‐based polyelectrolyte, polystyrene sulfonate (PSS), enables to reconstruct the electrode‐electrolyte interface to significantly enhance the acidic CO2 electrolysis. Mechanistic studies reveal that PSS induces high local K+ concentrations through electrostatic interaction between PSS anions and K+. In situ spectroscopy reveals that PSS reshapes the interfacial hydrogen–bond (H–bond) network, which is attributed to the H–bonds between PSS anions and hydrated proton as well as the steric hindrance of the additive molecules. This greatly weakens proton transfer kinetics and leads to the suppression of undesirable HER. As a result, a Faradaic efficiency of 93.9% for CO can be achieved at 250 mA cm–2, simultaneous with a high single‐pass carbon efficiency of 72.2% on commercial Ag catalysts in acid. This study highlights the important role of the electrode‐electrolyte interface induced by polyelectrolyte additives in promoting electrocatalytic reactions.

P-d Orbital Hybridization in Ag-based Electrocatalysts for Enhanced Nitrate-to-Ammonia Conversion.

Considering the substantial role of ammonia, developing highly efficient electrocatalysts for nitrate-to-ammonia conversion has attracted increasing interest. Herein, we proposed a feasible strategy of p-d orbital hybridization via doping p-block metals in an Ag host, which drastically promotes the performance of nitrate adsorption and disassociation. Typically, a Sn-doped Ag catalyst (SnAg) delivers a maximum Faradaic efficiency (FE) of 95.5±1.85 % for NH3 at -0.4 V vs. RHE and reaches the highest NH3 yield rate to 482.3±14.1 mg h-1 mgcat. -1. In a flow cell, the SnAg catalyst achieves a FE of 90.2 % at an ampere-level current density of 1.1 A cm-2 with an NH3 yield of 78.6 mg h-1 cm-2, during which NH3 can be further extracted to prepare struvite as high-quality fertilizer. A mechanistic study reveals that a strong p-d orbital hybridization effect in SnAg is beneficial for nitrite deoxygenation, a rate-determining step for NH3 synthesis, which as a general principle, can be further extended to Bi- and In-doped Ag catalysts. Moreover, when integrated into a Zn-nitrate battery, such a SnAg cathode contributes to a superior energy density of 639 Wh L-1, high power density of 18.1 mW cm-2, and continuous NH3 production.

Electrochemical CO2 Reduction in the Presence of Flue Gas Impurities: Effect of NOx, SOx and O2

Electrochemically converting CO2 to valuable chemical products using renewable energy sources may present solutions to alter current increasing CO2 emission trends. Currently, electrolyzer research is almost exclusively done with pure CO2 streams that - in practice - would originate from carbon capture units that prevent CO2 release to the atmosphere [1]. The capture and purification steps are cost intensive processes which is why direct usage of flue gases that contain impurities is a highly interesting approach. For this reason, the performance of CO2 electrolyzers equipped with state-of-the-art Bi2O3 or Ag catalysts is investigated in this work with an impure CO2 feed stream containing SO2, NO or O2. The short-term effect of highly concentrated SO2 (10 000 ppm) and NO (8 300 ppm) impurities during CO2 electrolysis was previously described [2,3]. Our work [4] elaborates further on this matter through 20 h experiments with flue gas-like concentrations of 200 ppm SO2 or NO. The results show a stable operation without severe FE losses (remains >90%) and structural adaptations to neither Ag nor Bi2O3 by these impurities. The presence of oxygen in flue gas streams at concentrations of several percent is common and causes a major decrease in FE to the target products (CO or HCOO-) during electrolysis. This is a result of the competition between the ORR and CO2RR with the former occurring more preferentially. To overcome this, we have discovered two possible strategies, which allow high FE’s to CO2RR products even in the presence of oxygen. (1) By operating the electrolyzer at a sufficiently high overall current density, all of the O2 entering and reaching the electrode surface gets reduced, allowing the CO2RR to become the dominant reaction. Although this approach has a higher electricity penalty, the extra cost is negligible compared to the cost otherwise associated with the CO2 purification for CO2 streams with an O2 content below 3%. (2) Given that the ORR is mostly occurring at the carbon-based gas diffusion layers another approach to improve CO2RR efficiency in the presence of oxygen is to replace this conventional support with ultra hydrophobic PTFE membrane filters. Since they are inefficient oxygen reduction catalysts, CO2RR again takes up the major fraction of the applied current density. A downside of using PTFE is that an additional conductive layer is required in case the catalyst itself (e.g. for bismuth oxide) is not conductive enough. These results thus not only offer new insights into the impact of gaseous impurities during CO2 electrolysis, but also suggest a strategy to improve electrolyzer performance with O2-containing feed streams. Bibliography [1] Lee M.Y., Environ. Sci. and Technol.; DOI: 10.1080/10643389.2019.1631991[2] Luc W.; JACS, DOI: 10.1021/jacs.9b03215[3] Ko B., Nature Comm. DOI : 10.1038/s41467-020-19731-8[4] Van Daele S ., J. Appl. Catal. B, Environ.; DOI: 10.1016/J.APCATB.2023.123345 Figure 1

Cascade Catalysis Systems That Use a 3-Terminal Tandem Architecture

The 3 terminal tandem (3TT) photovoltaic architecturea is ideal for driving cascade catalysis systems for conversion of CO2 into more complex products because it provides the flexibility to hold 2 different catalytic regions at different potentials, optimized to drive sequential reaction steps. In this work, we explore how this architecture can be adapted to heterogeneous CO2 reduction using Ag and Cu catalyst regions coupled by diffusion within the boundary layer adjacent to the electrodes using stochastic kinetics simulations. The goal is to evaluate the geometric and voltage requirements of the two parts of cascade, and identify useful layouts. The calculations take into account the full chemistry of the interfacial reactions as well as that of the electrolyte, providing insights to how the two catalytic regions interact. We anticipate that the resulting model will provide a platform for generalizing cascades to other catalyst systems involving operation at 2 different voltages. a Warren et al, ACS Energy Lett 5 (2020) 1233.

Cost-Effective Microfabricated Silver-Based Paper Cathodes for High-Discharge-Rate Aluminum-Air Batteries

We report a cost-effective microfabricated silver-based air-cathode for high-discharge-rate aluminum-air batteries which are suitable for micro-drone applications. A challenge for batteries for aerial drones is that both high gravimetric energy density and power density are required for extended operation. While air batteries can address the energy density issue, achieving high power density necessitates high loadings of expensive catalytic materials such as platinum (Pt), which can constitute over 99% of the cost in commercial air batteries. [1] Building upon prior research that studied the power performance of an aluminum-air battery (AAB) system with a silver-based cathode, this study further explores the influence of silver (Ag) sputtering conditions and Ag loadings on AAB power performance. [2]The power performance of AAB is significantly influenced by both air flux through the air cathode and electrochemically active catalyst surface area ratio (ECSA). The ECSA is the ratio of the electrochemically active catalyst surface area to its cathode area. Sputtered Ag cathodes with catalyst loadings ranging from 0.03 mg-Ag/cm2 to 0.3 mg-Ag/cm2 consistently show high porosity, indicating good air flux for the microfabricated cathode. Increasing the loading of the sputtered Ag catalyst further can lead to particle agglomeration. To improve power performance and ECSA, a silver-copper (AgCu) co-sputtering technique has been developed, significantly increasing the surface area and power performance.Figure 1 shows cathodes with Ag loadings ranging from 0.038 mg-Ag/cm2 to 0.267 mg-Ag/cm2 under two silver sputtering conditions: 400W+5mTorr and 100W+10mTorr. Within the examined range, the latter sputtering condition shows superior power performance compared to the former. For Ag loadings exceeding 0.1 mg-Ag/cm2, both conditions show decreasing power performance as Ag loading increases, and the 100W+10mTorr curve shows a maximum power at 0.088 mg-Ag/cm2. Figure 2 shows SEM images of 0.038 mg-Ag/cm2, 0.088 mg-Ag/cm2, and 0.19 mg-Ag/cm2 films, using the 100W+10mTorr sputtering condition. Ag particle size increases with higher Ag loading, which can result from particle agglomeration. Figure 3 shows the catalyst layer porosity and the ECSA calculated from the SEM images. All samples show porosity over 90%, indicating good air flux for the microfabricated Ag cathode. The trend of ECSA for different Ag loading correlates well with the power performance, suggesting that the power performance of the microfabricated Ag cathode primarily depends on the ECSA.Further enhancement of the ECSA through AgCu co-deposition is investigated, involving two parent alloy compositions (at%): Ag28Cu72 and Ag16Cu84. Following the co-sputtering, the parent alloy undergoes selective etching of Cu using hydrochloric acid (HCl). Figure 4 compares power performance between Ag28Cu72 and Ag16Cu84. Both curves exhibit an upward trend as the silver loading increases from 0.09 mg-Ag/cm2 to 0.4 mg-Ag/cm2, with Ag28Cu72 samples showing superior power performance. Figure 5 shows an SEM image of Ag28Cu72 parent alloy with 0.32 mg-Ag/cm2 loading after Cu etching, demonstrating that the ECSA increased to 47.52 while maintaining a high porosity of 90.2%. The peak power of Ag28Cu72 0.32 mg-Ag/cm2 sample is increased to 200 mW/cm2. By comparison, a 4mg-Pt/cm2 commercial cathode shows a peak power of 280 mW/cm2.Figure 6 compares the discharge performance of the 0.088 mg-Ag/cm2 cathode with a commercial 4 mg-Pt/cm2 cathode. Both cells can discharge under 1.1 Amp with a power density exceeding 500 W/kgbattery, a threshold sufficient to lift a quadrotor drone. [3] Battery weight encompasses anode, cathode, electrolyte and battery packaging. The 0.088 mg-Ag/cm2 cathode shows a discharge power plateau above 600 W/kgbattery (86% of the 4 mg-Pt/cm2) and an energy density of 228 Wh/kgbattery when discharge power density exceeding 500 W/kgbattery (95% of the 4 mg-Pt/cm2). Remarkably, the material cost of the 0.088 mg-Ag/cm2 cathode is 5000 times less than the 4 mg-Pt/cm2 cathode.

Material Changes of Bimetallic Ag–Cr, Fe, Co, Ni, Cu, Sn Electrocatalysts during Alkaline Oxygen Reduction in Fundamental Versus Alkaline Membrane Exchange Fuel Cell Conditions

The more apparent challenges of climate change drastically increase the global demand for sustainable fuel production and usage.1 In this context, hydrogen fuel cells (FCs) powered by renewable electricity are among the promising technologies.2 Addressing the sluggish cathode reaction in FCs, the oxygen reduction reaction (ORR), these devices hold immense potential for sustainable energy conversion and storage. An alkaline environment allows for the utilization of more abundant and cost-effective metals in contrast to current platinum-based catalysts. Silver (Ag), for instance, exhibits high selectivity for the ORR, i.e., forming hydroxide instead of peroxide.3 When combined with secondary metals, bimetallic Ag catalysts show enhanced activity, making them viable alternatives to platinum-group materials for ORR.In our highly collaborative research, we investigated the material transformations of bimetallic Ag thin films with chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and tin (Sn) as secondary metals for ORR electrocatalysis in fundamental rotating disk electrode (RDE) setups and the application device, anion-exchange membrane FC (AEMFC). Grazing-incidence X-ray diffraction (GI-XRD) conducted prior to electrochemical testing reveals no evidence of alloying except for the Ag-Sn bimetallic thin film. However, X-ray photoelectron spectroscopy (XPS) indicates a shift of the Ag 3d peaks to higher binding energies for all catalysts, suggesting a hybridization of Ag and the secondary metals. The composition of the metal surface, native oxide formation, ORR performance, and material changes post-RDE testing vary distinctly among the Ag bimetallic catalysts depending on the secondary metal. Intriguingly, performance is either enhanced (Ag-Co, Ag-Sn), maintained with reduced Ag content (Ag-Fe, Ag-Cr), or falls in between the two monometallic materials (Ag-Ni) compared to monometallic Ag thin films. Density functional theory (DFT) calculations offer insights into the catalyst performances and changes in metal oxidation states and surface composition prior and post electrocatalysis. AEMFC tests reveal promising performances under device conditions contradicting our fundamental RDE measurements. The integration of fundamental and application device tests, along with material characterization and DFT calculations, enables a comprehensive exploration of material changes under varying electrochemical conditions. This underscores the complexity of bimetallic catalysts and the importance of testing under device conditions, positioning Ag-bimetallic catalysts as highly promising alternatives to platinum-group metal catalysts for alkaline ORR.

Efficient hydrolytic dehydrogenation of ammonia borane catalyzed by ultrafine Pt clusters confined in Ni–Ti layered double hydroxides with closo-dodecaborate

Ammonia borane (NH3BH3, AB) is a highly promising candidate for hydrogen storage. Nevertheless, there is an urgent need to develop an efficient and stable catalyst that can control hydrogen generation under mild conditions. The use of catalysts with numerous surface atoms anchored to a carrier to achieve a synergistic effect is an appealing approach in catalysis. In this work, a series of highly dispersed metal clusters NiTi-LDH@B12H12@M (M = Au, Pd, Pt, Ag) catalysts were successfully synthesized at room temperature by leveraging the reductivity of [closo-B12H12]2- immobilized in the layered double hydroxide (LDH) laminate, along with the spatial confinement and anion exchange capabilities of LDH. Specifically, utilizing the optimal catalyst NiTi-LDH@B12H12@Pt 2.4% (wt. Pt), the AB hydrolysis reaction exhibited extraordinary catalytic activity. It exhibited a first-order reaction rate with respect to Pt and a near zero-order reaction rate with respect to AB concentration. The AB hydrolysis can be achieved in a mere 29 s at 25 °C with a conversion rate of 100%. The corresponding turnover frequency (TOF) attains a value of 454.06 molH2molPtmin−1, and the apparent activation energy (Ea) is 41.8 kJ mol−1, surpassing numerous previously reported Pt-based catalysts. The outstanding catalytic performance can be ascribed to the uniform distribution of ultrafine Pt clusters, along with the synergistic effect conferred by NiTi-LDH and intercalated anions ([closo-B12H12]2-).

Ag-TiO2 Photovoltaic Synergistic Field-catalyzed Degradation Performance of Tetracycline

Background: Tetracycline (TC), a commonly used antibiotic, is extensively utilized in the medical sector, leading to a significant annual discharge of tetracycline effluent into the water system, which harms both human health and the environment. Objective: A novel technique was developed to address the issues of photogenerated carrier complexation and photocatalyst immobilization. Compared to traditional photocatalytic photoelectrodes, the suspended catalyst used in the photovoltaic synergy field is more stable and increases the solidliquid contact area between the catalyst and the pollutant. Methods: This paper uses sol-gel-prepared Ag-TiO2 materials for the photoelectric synergistic fieldcatalyzed degradation of TC. The study examined how the Ag doping ratio, calcination conditions, catalyst injection, pH, electrolytes, and electrolyte injection affected photoelectric synergistic fieldcatalyzed degradation. The experiments were performed in a photocomposite field with a constant 50 mA current and a 357 nm UV lamp for 60 minutes. The composites underwent characterization using XRD, TEM, and XPS techniques. Results: Ag-TiO2 photoelectric synergistic field-catalyzed reaction with 357 nm ultraviolet lamp irradiation for 60 min and a constant current of 50 mA degraded 5 mg/LTC under preparation conditions of molar doping ratio of Ti: Ag=100:0.5, roasting temperature of 500 °C, and roasting time of 2 h. The photoelectric synergistic field-catalyzed degradation process achieved a degradation rate of 90.49% for 5 mg/L TC, surpassing the combined degradation rates of electrocatalysis and photocatalysis. The quenching experiments demonstrated that the degradation rate of TC decreased from 90.49% in the absence of a quencher to 53.23%, 42.58%, and 74.52%. The presence of •OH had a more significant impact than h+ and •O2 -. Conclusion: The findings suggest that Ag-TiO2 significantly enhanced the efficacy of photoelectric synergistic field-catalyzed degradation and can be employed to treat high-saline and lowconcentration TC. This establishes a benchmark for using photoelectrocatalytic materials based on titanium in treating organic wastewater.

P‐d Orbital Hybridization in Ag‐based Electrocatalysts for Enhanced Nitrate‐to‐Ammonia Conversion

Considering the substantial role of ammonia, developing highly efficient electrocatalysts for nitrate‐to‐ammonia conversion has attracted increasing interest. Herein, we proposed a feasible strategy of p‐d orbital hybridization via doping p‐block metals in an Ag host, which drastically promotes the performance of nitrate adsorption and disassociation. Typically, a Sn‐doped Ag catalyst (SnAg) delivers a maximum Faradaic efficiency (FE) of 95.5 ± 1.85 % for NH3 at ‐0.4 V vs. RHE and reaches the highest NH3 yield rate to 482.3 ± 14.1 mg h‐1 mgcat.‐1. In a flow cell, the SnAg catalyst achieves a FE of 90.2 % at an ampere‐level current density of 1.1 A cm‐2 with an NH3 yield of 78.6 mg h‐1 cm‐2, during which NH3 can be further extracted to prepare struvite as high‐quality fertilizer. A mechanistic study reveals that a strong p‐d orbital hybridization effect in SnAg is beneficial for nitrite deoxygenation, a rate‐determining step for NH3 synthesis, which as a general principle, can be further extended to Bi‐ and In‐doped Ag catalysts. Moreover, when integrated into a Zn‐nitrate battery, such a SnAg cathode contributes to a superior energy density of 639 Wh L‐1, high power density of 18.1 mW cm‐2, and continuous NH3 production.

Design of efficient benzimidazole-derived N-heterocyclic carbene Ag(I) catalysts for aldehyde–amine–alkyne coupling

A mild catalytic protocol for aldehyde, amine, and alkyne coupling (A3-coupling) allows for the selective synthesis of propargyl amines using 5,6-dimethylbenzimidazole-derived N-heterocyclic carbene (BNHC) silver(I) catalysts. A series of BNHC Ag(Ⅰ) halide complexes were synthesized and their structures have been elucidated through the use of multinuclear NMR and FT-IR spectroscopy. Furthermore, the pseudo-linear geometry of two different compounds was substantiated by single-crystal X-ray diffraction. Silver-based A3-coupling was achieved for both acyclic and cyclic secondary amines using a diverse set of alkynes to afford propargyl amines with yields of up to 95 %. The present approach is environmentally benign and water is generated as the sole byproduct.

The temperature dependence of electrochemical CO2 reduction on Ag and CuAg alloys

Ag is often studied as catalyst for electrochemical CO2 reduction as it shows high selectivity towards CO and is easily alloyed with Cu to enhance performance using CuAg catalysts. In this study, we investigated the effect of temperature on Ag and CuAg catalysts and compare these with previous results on Au and Cu catalysts. We show that the temperature effect is complicated as it shows an interplay with CO2 concentration, potential and mass transport. It is therefore crucial to deconvolute these parameters and study the effect of temperature under different conditions. Moreover, we show that alloying Ag with Cu can inhibit some of the deactivation effects observed at high temperatures on pure Cu. CuAg alloys can prevent the dominance of hydrogen evolution at elevated temperatures, although an optimum of C2+ products with temperature is still observed.

Interfacial effects in Ni(OH)2/MnO@Ni aerogel heterostructures promote highly efficient electrooxidation of ethylene glycol to formate and hydrogen

The sluggish oxygen evolution reaction (OER: 4OH− → O2 + 2H2O + 4e−, E = 1.23 V vs RHE) retards the large-scale hydrogen production. Replacing OER with low-potential ethylene glycol oxidation reaction (EGOR) to drive water splitting is a promising approach to solve the high energy consumption in hydrogen production. Herein, we report an energy-efficient electrocatalytic water splitting system by using a heterostructure Ni(OH)2/MnO aerogel catalyst (NiMn AG) that replaces OER with ethylene glycol oxidation reaction (EGOR), resulting in the co-production of value-added formate and green hydrogen. Owing to the optimized electron distribution on the heterostructure interface, the NiMn AG catalyst exhibits excellent EGOR catalytic performance, with an overpotential of only 290 mV at 100 mA cm−2. The open-circuit potential of the reaction is reduced to 0.86 V for EGOR, rendering an earlier occurrence of electron transfer. The ion chromatography (IC) result demonstrates a highly selectivity (96%) for formate in EGOR. The density functional theory (DFT) calculations show that the interfacial effects between Ni(OH)2 and MnO optimizes the surface energy states of NiMn AG, improving the adsorption efficiency of the reaction intermediates for EGOR and further promoting the efficient cleavage of C–C to form formate. Additionally, the incorporation of MnO stabilizes the overall energy state during violent bond-breaking processes. This work sheds light on a new methodology to design bimetallic catalysts assisted by EGOR for decoupled green hydrogen production.

Indium Metal Oxide Tandem Ag Catalyst toward Highly Selective CO2 Electroreduction to CO over a Wide Potential Window

Indium Metal Oxide Tandem Ag Catalyst toward Highly Selective CO₂ Electroreduction to CO over a Wide Potential Window

Effect of Ag Addition to Au Catalysts for the Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Furandicarboxylic Acid

AbstractThe addition of Ag to Au nanocatalysts is known to improve several catalytic reduction and oxidation reactions. Until now, bimetallic AuAg catalysts have not been studied in detail in liquid phase oxidation reactions. We investigated the activity, selectivity, and stability of silica supported Au, Ag and AuAg catalysts in the oxidation of 5‐hydroxymethylfurfural (HMF) to 2,5‐furandicarboxylic acid (FDCA), an important reaction to produce bio‐based polymers. We demonstrate that addition of an optimum amount of inactive Ag to the active Au catalyst substantially increases the overall selectivity and yield of the desired FDCA. Interestingly, Ag addition decreased the conversion rate of the reactant HMF to the intermediate HMFCA, but improved (up to 10–20 % Ag addition) much the conversion of the intermediate product to the desired final product. This is probably due to tuning the electronic properties of the nanoparticles to achieve an optimum adsorption strength of the intermediate on the surface of AuAg catalysts. Moreover, particle growth was suppressed by the bimetallic AuAg catalyst, ultimately leading to superior stability compared to its monometallic counterparts.

Seeding Atomic Silver into Internal Lattice Sites of Transition Metal Oxide for Advanced Electrocatalysis.

Transition metal oxides (TMOs) are widely studied for loading of various catalysts due to their low cost and high structure flexibility. However, the prevailing close-packed nature of most TMOs crystals has restricted the available loading sites to surface only, while their internal bulk lattice remains unactuated due to the inaccessible narrow space that blocks out most key reactants and/or particulate catalysts. Herein, using tunnel-structured MnO2, this study demonstrates how TMO's internal lattice space can be activated as extra loading sites for atomic Ag in addition to the conventional surface-only loading, via which a dual-form Ag catalyst within MnO2 skeleton is established. In this design, not only faceted Ag nanoparticles are confined onto MnO2 surface by coherent lattice-sharing, Ag atomic strings are also seeded deep into the sub-nanoscale MnO2 tunnel lattice, enriching the catalytically active sites. Tested for electrochemical CO2 reduction reaction (eCO2RR), such dual-form catalyst exhibits a high Faradaic efficiency (94%), yield (67.3mol g-1 h-1) and durability (≈48h) for CO production, exceeding commercial Ag nanoparticles and most Ag-based electrocatalysts. Theoretical calculations further reveal the concurrent effect of such dual-form catalyst featuring facet-dependent eCO2RR for Ag nanoparticles and lattice-confined eCO2RR for Ag atomic strings, inspiring the future design of catalyst-substrate configuration.

Sulfidation-Induced Surface Local Electronic and Atomic Structures in a Silver Catalyst Enables Silicon Photocathode for Selective and Efficient Photoelectrochemical CO2 Reduction.

Converting CO2 to value-added chemicals through a photoelectrochemical (PEC) system is a creative approach toward renewable energy utilization and storage. However, the rational design of appropriate catalysts while being effectively integrated with semiconductor photoelectrodes remains a considerable challenge for achieving single-carbon products with high efficiency. Herein, we demonstrate a novel sulfidation-induced strategy for in situ grown sulfide-derived Ag nanowires on a Si photocathode (denoted as SD-Ag/Si) based on the standard crystalline Si solar cells. Such an exquisite design of the SD-Ag/Si photocathode not only provides a large electrochemically active surface area but also endows abundant active sites of Ag2S/Ag interfaces and high-index Ag facets for PEC CO production. The optimized SD-Ag/Si photocathode displays an ideal CO Faradic efficiency of 95.2% and an onset potential of +0.26 V versus the reversible hydrogen electrode, ascribed to the sulfidation-induced synergistic effect of the surface atomic arrangement and electronic structure in Ag catalysts that promote charge transfer, facilitate CO2 adsorption and activation, and suppress hydrogen evolution reaction. This sulfidation-induced strategy represents a scalable approach for designing high-performance catalysts for electrochemical and PEC devices with efficient CO2 utilization.

Ionic Liquid‐Silver Catalysts For Acetylene Acetoxylation At Tow‐Temperature

It was crucial to develop a catalyst with high catalytic activity at iow temperatures, as the zinc‐based catalysts were prone to deactivation in the high‐temperature reaction of acetylene acetoxylation, and ionic liquid (IL)‐silver (Ag) catalysts were synthesized and applied in acetylene acetoxylation. The X‐ray diffraction, transmission electron microscopy, and X‐ray photoelectron spectroscopy characterizations displayed that Ag species were stabilized in the state of Ag+, and the dispersion of the Ag active species was effectively improved in supported‐ionic‐liquid‐phase (SILP) system. Furthermore, we prepared Ag‐IL liquid phase catalysts for catalyzing acetylene acetoxylation in liquid phase systems. It was demonstrated that the presence of ILs could effectively stabilize the Ag+ active site. The catalytic performance of the Ag‐IL/AC catalyst prepared in this article at a low temperature of 180 °C was 2.5 times that of the traditional Zn/AC catalyst. The development of low‐temperature catalysts would play a driving role in the development of acetylene acetoxylation.