Replacement Reaction Research Articles

The Replacement of Celestine (SrSO4) by Strontianite (SrCO3) in Aqueous Solution Studied In Situ and in Real Time Using Fluid-Cell Raman Spectroscopy

The replacement of celestine (SrSO4) by strontianite (SrCO3) has extensively been studied over the past few decades. It also represents an ideal reaction to in situ study the kinetic and fundamental mechanistic details of mineral replacement reactions in aqueous solutions via fluid-cell Raman spectroscopy. This technique allows us to study the reaction process in real time by continuously analysing the solution or by imaging the solid–liquid interface where the reaction takes place and while the replacement process is ongoing. Two sets of experiments were conducted, the first of which was carried out with celestine powder and an equimolar Na2CO3 solution in a heated fluid cell between 30 and 60 °C. The progress of the reaction was followed by Raman spectroscopic in situ measurements of the solution. Another experiment was performed with a polished cuboid cut from a single celestine crystal and a 1 M Na2CO3 solution in a fluid cell at room temperature (21 °C). In this experiment, the reaction was studied in situ, spatially resolved, and in real time. The results of both types of experiments revealed that the replacement occurs via a coupled dissolution–precipitation mechanism and that the evolution of the solution composition cannot fully be explained by a single rate law derived from a shrinking core model. By applying the model-independent time-to-a-given-fraction method, three kinetic regimes could be identified and the associated activation energies quantified.

Ultrasound-assisted preparation of PdCo bimetallic nanoparticles loaded on beta zeolite for efficient catalytic hydrogen production from dodecahydro-N-ethylcarbazole

Research and development of high-performance catalysts is a key technology to realize hydrogen energy storage and transportation based on liquid organic hydrogen carriers. Co/beta was prepared using beta zeolite as a carrier via an electrostatic adsorption (ESA)-chemical reduction method, and it was used as the template and reducing agent to prepare bimetallic catalysts via an ultrasonic assisted galvanic replacement process (UGR). The fabricated PdCo/beta were characterized by TEM, XPS, FT-IR, XRD, H2-TPR, and H2-TPD. It was shown that the ultrafine PdCo nanoparticles (NPs) are evenly distributed on the surface of the beta zeolite. There is electron transfer between metal NPs and strong-metal-support-interaction (SMSI), which results in highly efficient catalytic dodecahydro-N-ethylcarbazole (12H-NEC) dehydrogenation performance of PdCo bimetallic catalysts. The dehydrogenation efficiency reached 100 % in 4 h at 180 °C and 95.3 % in 6 h at 160 °C. The TOF of 146.22 min−1 is 7 times that of Pd/beta. The apparent activation energy of the reaction is 66.6 kJ/mol, which is much lower than that of Pd/beta. Under the action of ultrasonic waves, the galvanic replacement reaction is accelerated, and the intermetal and metal-carrier interactions are enhanced, which improves the catalytic reaction performance.

Fabrication of robust superhydrophobic zinc-coated steel with anti-corrosion and self-cleaning behavior through a simple nickel galvanic replacement reaction

Zinc coating is a widely used coating for steel substrate as a galvanic protector but the corrosion rate of this coating increases when exposed to wet environment. In recent years, bioinspired superhydrophobic surfaces have received tremendous attention among various methods to enhance the corrosion resistance. In this study, superhydrophobic zinc-coated steel was fabricated based on nickel galvanic replacement reaction in NiCl2.6 H2O solution on zinc-coated steel and post modification to improve the corrosion resistance and create self-cleaning behavior. Based on the FESEM morphology and AFM topography images, galvanic replacement reaction created hierarchical micro/nanostructure that is key parameter for creating superhydrophobic surfaces. EDS, XRD, XPS and FTIR analysis confirmed the occurrence of galvanic replacement reaction and post modification of the surface with FAS- solution. The zinc-coated steel immersed in NiCl2.6 H2O solution with the concentration of 0.1 M for 10 min showed the highest water contact angle of 166.7° ± 1.6° and a contact angle hysteresis of 1.7°. In addition, it exhibited good long-term stability under various conditions, mechanical stability, self-cleaning capability, and robust adhesion which was not reported, previously. Corrosion study showed that the surface exhibit excellent charge transfer resistance and higher positive corrosion potential and a lower corrosion current density compared with the zinc coating. The results indicated that the galvanic replacement reaction is a simple, scalable, cost effective and promising method for creating multifunctional and robust superhydrophobic surfaces on zinc coatings to protect steel.

Bio-Inspired Superhydrophilic Self-Assembled Coronavirus-Like Pt-WC/CNT for Hydrogen Evolution Reaction.

This study presents a novel approach to enhance the catalytic activity of composite materials by promoting active surface exposure and improving hydrogen transfer performance. Through a self-assembly route involving tailored gas-solid and galvanic replacement reactions, Pt-WC/CNT catalysts with superhydrophilicity and coronavirus-like structure are synthesized. These unique structural features contribute to a remarkable enhancement in the electrocatalytic performance of the hydrogen evolution reaction (HER). Notably, the Pt-WC/CNT catalyst exhibits an outstanding intrinsic activity and efficient bubble transfer properties, leading to a high turnover frequency of 34.97 H2·s-1 at an overpotential of 100mV. This value is 4.8 times higher than that achieved by commercial Pt/C catalysts (7.30 H2·s-1), establishing Pt-WC/CNT as one of the most active catalysts reported to date. Moreover, the combination of gas-solid and galvanic replacement reactions in the synthesis process offers a scalable route for the production of Pt-loading controllable composite catalysts, thus challenging the dominance of commercial Pt/C catalysts.

Cellulose/GO monolith covered with Pd–Pt bimetallic nanocrystals for continuous-flow catalytic reduction of hexavalent chromium

Cellulose monolith materials have interconnected open porous structures with very high porosity, making them attractive structures for use as support materials in heterogeneous catalysis applications. In this study, we developed a highly efficient and reusable continuous-flow reactor for Cr(VI) remediation by combining the advantageous features of cellulose monoliths with suitable reinforcement techniques. We fabricated a porous monolithic cellulose/graphene oxide (GO) composite with a continuous three-dimensional skeletal framework using the thermally induced phase separation technique. Pd nanocrystals were synthesized in situ on the surface of the composite monolith, and then converted to porous Pd–Pt bimetallic nanocrystals through a galvanic replacement reaction. This approach eliminated the need for additional reductants and stabilizers, making the process simpler and more environmentally friendly. Under carefully optimized conditions, the cellulose/GO/Pd–Pt nanocomposite monolith exhibited outstanding performance in continuous-flow reactions for Cr(VI) reduction, achieving a maximum conversion rate of 98 %. Moreover, the nanocomposite monolith-based heterogeneous catalyst exhibited remarkable long-term stability, maintaining its catalytic activity even after extended periods of storage in the dried state. These findings highlight the potential of cellulose-based composite monoliths as versatile and robust support materials for heterogeneous catalysis.

Printing surface cuprous oxides featured liquid metal for non-enzymatic electrochemical glucose sensor

Electrochemical glucose sensors that rely on two-dimensional (2D) oxides have attracted significant attention owing to the strong sensing activity of 2D oxides, but their practical application is hindered by the complexity and high cost of fabrication of electrodes and integrated devices. Herein, a convenient and effective fabrication route that includes printing a Ga-based liquid metal (LM) as a current collection electrode, followed by growing electrochemically active 2D oxides directly on the surface of Ga-based LMs under mild conditions, is developed for non-enzyme-based electrochemical sensors. Specifically, 2D annealed Cu-Oxide (ACO) is successfully grown on a printed Ga electrode through a galvanic replacement reaction, resulting in the formation of a mechanically and electrically well-matched interface between the active sensing materials and the current collection substrate. Benefitting from the high quantity of 2D ACO and good charge transfer at the interface, the as-prepared ACO electrode exhibits attractive glucose sensing performance, with a wide linear range (1 μM-10 mM) of effective detection, low detection limit down to 1 μM, and high sensitivity of 0.87 μA·mM-1·cm-2. Our study highlights the potential of using LMs in bio-sensing applications and provides a non-enzyme-based electrochemical biosensor platform for effective glucose detection in diets and clinical diagnostic settings.

A Liquid‐Metal‐Assisted Competitive Galvanic Reaction Strategy Toward Indium/Oxide Core−Shell Nanoparticles with Enhanced Microwave Absorption

AbstractThe preparation of core–shell structured nanoparticles using the galvanic replacement reaction of liquid metals is a simple and efficient method. However, precise modulation of the core and shell components to regulate the microwave absorption performance still needs to be further explored. In this study, various types of indium/oxide core–shell nanoparticles are prepared based on a competitive galvanic reaction of gallium‐indium liquid metals. The prepared indium/oxide core–shell structured nanoparticles exhibit superior electromagnetic (EM) wave absorption properties with a minimum reflection loss (RL) of −40.25 dB at 1.7 mm and the widest effective absorption band of 6.12 GHz at 2.1 mm. The superior wave‐absorbing properties originate from the dielectric losses of the interfacial and dipole polarizations. In addition, an externally applied magnetic field improves the polarization loss and microwave dissipation to achieve a minimum RL of −45.65 dB at 2.4 mm. The liquid‐metal‐assisted competitive galvanic reaction strategies extend the variety of core–shell structured nanoparticles for electromagnetic wave absorption applications.

Magmatic processes forming replacement textures with fluorite alignments in feldspars in an evolved trachyte from Oki‐Dogo Island, Sea of Japan

AbstractInternal microtextures of ternary alkali feldspars in sanidine trachyte from Oki‐Dogo Island were examined using an electron microprobe analyzer, a scanning electron microscope, a transmission electron microscope and cathodoluminescence instruments, to develop the understanding of volcanic processes of alkaline magmas related to feldspar crystallization. The examined trachyte is an evolved rock of the Oki‐Dogo Pliocene trachyte group. Its phenocryst feldspars are commonly associated with lamellar‐wavy‐domain textures with scales approximately from 100 nm up to several hundreds of μm that show complex and gradual variations in composition: however, anti‐rapakivi zoning textures common in other Oki‐Dogo alkaline rocks are almost completely absent in the trachyte. These textures are produced by extensive magmatic ion‐exchange replacement reactions progressively advanced in the evolved magma. Characteristic braided fluorite alignments are developed consistently with lamellar‐wavy‐domain textures in phenocryst feldspars, and similar braided alignments are also present in groundmass feldspars with complicated microtextures. Most of fluorite grains are <100 nm in diameter, and the patterns of braided fluorite alignments vary greatly in individual feldspars. The whole occurrence of the feldspar microtextures represents an extreme example of diffusion‐controlled replacement reactions, progressively advanced in the dry (relatively anhydrous) trachyte magma. The genetic processes forming fluorite alignments in feldspars are related to magma compositions, especially F and P contents, and the crystallization of F‐bearing minerals, especially of fluorapatite.

Thermally activated persulfate (TAP)-enhanced tris(2-chloroethyl) phosphate removal in real-world waters based on a response-surface approach as well as toxicological evaluation on its degradation products

As a typical organophosphorus flame retardant, tris(2-chloroethyl) phosphate (TCEP) is refractory in aqueous environment. The application of TAP is a promising method for removing pollutants. Herein, the removal of TCEP using TAP was rigorously investigated, and the effects of some key variables were optimized by the one-factor-at-a-time approach. To further evaluate the interactions among variables, the response surface methodology (RSM) based on central composite design was employed. Under optimized conditions (pH 5, [PS]0: [TCEP]0 = 500:1), the maximum removal efficiency (RE) of TCEP reached up to 90.6%. In real-world waters, the RE of TCEP spanned the range of 56%− 65% in river water, pond water, lake water and sanitary sewage. The low-concentration Cl- (0.1 mM) promoted TCEP degradation, but the contrary case occurred when the high-concentration Cl-, NO3-, CO32-, HCO3-, HPO42-, H2PO4-, NH4+ and humic acid were present owing to their prominently quenching effects on SO4•-. Both EPR and scavenger experiments revealed that the main radicals in the TAP system were SO4•- and •OH, in which SO4•- played the most crucial role in TCEP degradation. GC-MS/MS analysis disclosed that two degradation products appeared, sourcing from the replacement, oxidation, hydroxylation and water-molecule elimination reactions. The other two products were inferred from the comprehensive literature. As for acute toxicity to fish, daphnid and green algae, product A displayed the slightly higher toxicity, whereas other three products exhibited the declining toxicity as compared to their parent molecule. These findings offer a theoretical/practical reference for high-efficiency removal of TCEP and its ecotoxicological risk evaluation.

Nano-mineral assemblages in mercury- and silver-contaminated soils: records of sequestration, transformation, and release of mercury- and silver-bearing nanoparticles.

Mercury-bearing nano-mineral assemblages (Hg-NMAs) are chemically and mineralogically heterogeneous, micrometer-sized aggregates of nanoparticles (NPs) found in contaminated soils and sediments. Although these NMAs control sequestration and release of Hg that is a global contaminant, our understanding is limited with respect to the conditions of different types of Hg-NMAs, the diversity of its minerals, the size distribution of its NPs and whether mineral replacement and alteration reactions in these NMAs result in the release of Hg-bearing NPs. For this purpose, Hg-NMAs in four sediment samples from the Guanajuato Mining District (GMD) in Mexico, a region that was polluted by Hg and silver (Ag) due to historical mining involving Hg amalgamation, are characterized at the micro- and nanoscale. Microscale examinations with SEM show that the majority of Hg-NMAs occurs in mineral surface coatings (MSC) and fillings in fractures within quartz grains and are enriched in Hg and sulfur (S) relative to Ag, and in S and selenium (Se) relative to chloride (Cl). Examinations at the nanoscale show that Hg-NMAs contain (a) residuals of the patio process such as amalgam phases and elemental Ag; (b) associations of Hg- and Ag-sulfide NPs with pyrite and marcasite; (c) associations of Hg- and Ag-sulfide NPs with goethite and clay minerals along the rims of the MSC. The latter minerals replaced the Fe-Si-rich matrix at high-water rock ratios most likely due to an increase in porosity during flooding of the Pastita River. Consequently, the rims are depleted in Hg-Ag-sulfide NPs relative to the unaltered Fe-Si-rich matrices indicating that changes in the physiochemical conditions of soils and sediments in the GMD can result in the release of Hg-Ag-bearing NPs. In this context, this study discusses whether release and dissolution of Hg-Ag-bearing NPs contribute to the recently observed elevated gaseous elemental Hg concentrations in the soil, interstitial air and ambient air, and to the fate and effects of Hg in local aquatic environments.

Fast synthesis of silver nanowires at room temperatureviaultrasonication-mediated galvanic replacement for flexible transparent electrodes

In this work, we propose a facile method for fast synthesis of Ag nanowires by an ultrasonication-mediated galvanic replacement reaction between Ag+and raspberry-like Cu nanoparticles at room temperature.

Galvanic replacement synthesis of PtPdAu hollow nanorods as peroxidase mimic with high specific activity for colorimetric detection.

Noble metal nanomaterials have been widely demonstrated to possess intrinsic enzyme-like properties and have been increasingly applied in the fields of analysis and biomedicine. However, current exploration of high-activity noble metal nanozymes is still far from adequate. The construction of hollow structures and adjustment of their elemental composition are effective ways to improve the specific activity (SA) of nanozymes. In this study, trimetallic PtPdAu hollow nanorods (HNRs) were developed using a galvanic replacement reaction and Kirkendall effect. The catalytic experiment showed that the PtPdAu HNRs possessed outstanding peroxidase-like performance and their SA value was up to 563.71 U mg-1, which is remarkable among various previously reported nanozymes and higher than that of monometallic or bimetallic counterparts with similar structure and size prepared in this study. Electron paramagnetic resonance (EPR)measurements showed that the PtPdAu HNRs could contribute to the formation of hydroxyl radicals (˙OH) in catalyzing hydrogen peroxide. When using PtPdAu HNRs as a nanozyme in the colorimetric detection of H2O2 and ascorbic acid (AA), the limits of detection were as low as 1.8 μM and 0.068 μM, respectively. This study demonstrates that PtPdAu HNRs are high-activity nanozymes and have the potential to be applied in the field of analysis.

Rapid synthesis of Pt(0) motors-microscrolls on a nickel surface via H2PtCl6-induced galvanic replacement reaction.

In this study, Pt(0) microscrolls are synthesized on polished Ni via galvanic replacement reaction (GRR). Employing in situ optical microscopy, the dynamic motion of the catalytic microscrolls as micromotors in H2O2 solutions is revealed. This method offers a rapid fabrication of scrolls from diverse noble metals and alloys.

Amalgamation-based AuHgPt Nanochains as Electrocatalysts for Hydrogen Evolution Reaction

Gold-mercury (AuHg) nanochains were successfully synthesized based on the tip effect of Au NRs. Chained gold-mercury-platinum (AuHgPt) nanoalloys were prepared by the galvanic replacement reaction (GRR) using the AuHg nanochains...

Transient crystallisation of rare earth carbonates during the hydrothermal oxidation of siderite.

The researchers investigated the interaction between multi-component rare earth element-bearing aqueous solutions and siderite grains under hydrothermal conditions. Our study investigates the interaction between multi-component rare earth element (REE; La, Ce, Pr, Nd, Dy)-bearing aqueous solutions and siderite (FeCO3) grains under hydrothermal conditions (50-205 °C). The results revealed a solution-mediated mineral replacement reaction that occurs via a multi-step crystallisation pathway involving the formation of iron oxides (goethite, α-FeO(OH), and hematite, Fe2O3), metastable REE-bearing minerals (kozoite, REE(CO3)(OH), and bastnasite, REE(CO3)(OH,F)), and cerianite (CeO2). Siderite stability, dissolution, and subsequent mineral formation are temperature and pH-dependent. At low temperatures, REE carbonate formation is inhibited by a goethite coating, creating a partial equilibrium situation. Higher temperatures increase dissolution rates and enable kozoite and bastnasite formation. The redox behaviour of Fe and Ce combined with the temperature, and the availability of CO3 2- govern this crystallisation sequence. Continued oxidation promotes decarbonation processes by acidifying the aqueous solution, dissolving all carbonates, and resulting in hematite and cerianite crystallisation as thermodynamically stable phases. Understanding iron carbonate, oxide and REE interactions can inform new resource targets and improve recovery and separation techniques.

Galvanic replacement-induced preparation of bloom-like Pt23Ni77 for methanol coupled efficient hydrogen production.

Galvanic replacement reaction (GRR) leverages the difference in metal reduction potentials to regulate the structure of nanomaterials. The crucial aspect of constructing highly active catalysts lies in the precise manipulation of both the oxidative dissolution of sacrificial template metals and reductive deposition of alternate metals. Herein, we investigated the morphological transformation of metal Ni as a sacrificial template in the presence of different amounts of H2PtCl6 solution and the Pt4+ substitution of Ni to achieve the redistribution of elements on the catalyst surface, which provides superior performance in both the methanol oxidation reaction (MOR) and hydrogen evolution reaction (HER). The uniform distribution of Pt on a three-dimensional transition metal Ni substrate allows for the complete exposure of the noble metal to the catalyst surface. This distribution increases the reaction area, facilitating easy access for reactants and promoting electron transfer. Meanwhile, Pt (1.39 Å) has a larger atomic radius compared to Ni (1.24 Å), and the substitution reaction in the transition metal phase induces strong compressive strain, which effectively regulates the electronic structure of Ni.

Multicomponent chiral plasmonic hybrid nanomaterials: recent advances in synthesis and applications.

Chiral hybrid nanomaterials with multiple components provide a highly promising approach for the integration of desired chirality with other functionalities into one single nanoscale entity. However, precise control over multicomponent chiral plasmonic hybrid nanomaterials to enable their application in diverse and complex scenarios remains a significant challenge. In this review, our focus lies on the recent advances in the preparation and application of multicomponent chiral plasmonic hybrid nanomaterials, with an emphasis on synthetic strategies and emerging applications. We first systematically elucidate preparation methods for multicomponent chiral plasmonic hybrid nanomaterials encompassing the following approaches: physical deposition approach, galvanic replacement reaction, chiral molecule-mediated, chiral heterostructure, circularly polarized light-mediated, magnetically induced, and chiral assembly. Furthermore, we highlight emerging applications of multicomponent chiral plasmonic hybrid nanomaterials in chirality sensing, enantioselective catalysis, and biomedicine. Finally, we provide an outlook on the challenges and opportunities in the field of multicomponent chiral plasmonic hybrid nanomaterials. In-depth investigations of these multicomponent chiral hybrid nanomaterials will pave the way for the rational design of chiral hybrid nanostructures with desirable functionalities for emerging technological applications.

LREE rich perovskite in antiskarn reactions - REE transfer from pyroxenites to carbonatites?

We study three ultrabasic-alkaline carbonatite complexes (UACCs: Afrikanda, Vuorijarvi, Kovdor) from the Kola Alkaline Province to focus on the comparison of REE contents from pyroxenites and carbonatites and the fate of perovskite. Pyroxenites and carbonatites have large REE variations and similar contents in all three complexes. Afrikanda and Vuorijarvi pyroxenites and carbonatites have higher REE contents compared to all Kovdor rocks. Despite their comparable LREE contents, pyroxenites and carbonatites have different REE-carrier minerals. In most studied pyroxenites, perovskite is the main REE-bearing mineral and its abundance controls the LREE enrichment of the whole rock. When perovskite is absent or in low abundance, apatite is the main REE carrier. Instead, in carbonatites and phoscorites, apatite and calcite control REE contents. REE‑carbonates - found in several carbonatite samples - do not play a substantial role in the overall REE budget because of their very low abundance and tiny grain sizes.We found large LREE variations at very low local scales (< 1 mm) in several thin sections. These large variations are related to carbonatite infiltration and associated antiskarn reactions. Perovskite near calcite is replaced by titanite that has much lower LREE contents. Most LREE released from the breakdown of perovskite were probably dissolved in the carbonatite melt because apatite and calcite that crystallized from this melt are highly enriched in LREE. Newly formed apatites and calcites show large LREE variations that probably are controlled by local factors (e.g. variations of Si, Ca, Mg activities). Y/Ho ratios are strongly fractionated in most minerals and often show large variations at local scales (mm) in these antiskarn reactions. The potential of REE remobilization from such perovskite replacement reactions is very high as perovskite contributes about 70% to the REE budget for these three UACCs. Therefore, more attention should be given to perovskite replacement reactions and its role for LREE enrichment of carbonatite melts.

Single Atom Iridium Decorated Nickel Alloys Supported on Segregated MoO2 for Alkaline Water Electrolysis.

Hetero-interface engineering has been widely employed to develop supported multicomponent catalysts for water electrolysis, but it still remains a substantial challenge for supported single atom alloys. Herein a conductive oxide MoO2 supported Ir1 Ni single atom alloys (Ir1 Ni@MoO2 SAAs) bifunctional electrocatalysts through surface segregation coupled with galvanic replacement reaction, where the Ir atoms are atomically anchored onto the surface of Ni nanoclusters via the Ir-Ni coordination accompanied with electron transfer from Ni to Ir is reported. Benefiting from the unique structure, the Ir1 Ni@MoO2 SAAs not only exhibit low overpotential of 48.6mV at 10mA cm-2 and Tafel slope of 19mV dec-1 for hydrogen evolution reaction, but also show highly efficient alkaline water oxidation with overpotential of 280mV at 10mA cm-2 . Their overall water electrolysis exhibits a low cell voltage of 1.52V at 10mA cm-2 and excellent durability. Experiments and theoretical calculations reveal that the Ir-Ni interface effectively weakens hydrogen binding energy, and decoration of the Ir single atoms boost surface reconstruction of Ni species to enhance the coverage of intermediates (OH*) and switch the potential-determining step. It is suggested that this approach opens up a promising avenue to design efficient and durable precious metal bifunctional electrocatalysts.

(Invited) Electroless Cu, Pb and Ag Monolayer Deposition – Generality of an Electroless Monolayer Deposition Phenomenon

Recent progress in fuel cell catalysis has been enabled in great part by facile methods for catalyst monolayer synthesis based on surface limited redox replacement (SLRR) of underpotentially deposited (UPD) monolayers. Although this approach has been very effective, it has shown a limited applications in majority of heterogeneous gas phase catalysis problems where substrates are oxide based materials with very limited conductivity. In this talk we point out a new possibility for catalyst monolayer synthesis via SLRR on metal surfaces which are not part of a broadly conductive substrates such as metal nanoparticles imbedded in various oxide or zeolite supports. This is enabled by discovery of an electroless (E-less) Pb, Cu and Ag monolayer deposition phenomenon. Fundamentals of the E-less monolayer deposition are reviewed, and new data illustrating Cu and Ag monolayer deposition are presented. The focus is on emphasizing generality of the E-less monolayer deposition phenomenon, its self-termination and surface selectivity towards substrates at which Cu, Ag and Pb form UPD monolayer. Examples of the thin films and catalyst monolayer deposition via SLRR of E-less Cu, Ag and Pb monolayer are presented under the auspices of a newly developed two-step electroless atomic layer deposition protocol (E-less ALD)1.1) Electroless Pb Monolayer Deposition – Prelude for Further Advances in Catalyst Monolayer Synthesis via Surface Limited Redox Replacement Reaction”, K. Ahmadi, N. Dole, D. Wu, T. Salavati‐Fard, L. C. Grabow, F. C. Robles Hernandez, and S. R. Brankovic, ACS Catalysis, 11, 4650 (2021).