Multiply Confined Nickel Nanocatalysts Produced by Atomic Layer Deposition for Hydrogenation Reactions

To design highly efficient catalysts, new concepts for optimizing the metal–support interactions are desirable. Here we introduce a facile and general template approach assisted by atomic layer deposition (ALD), to fabricate a multiply confined Ni‐based nanocatalyst. The Ni nanoparticles are not only confined in Al₂O₃ nanotubes, but also embedded in the cavities of Al₂O₃ interior wall. The cavities create more Ni–Al₂O₃ interfacial sites, which facilitate hydrogenation reactions. The nanotubes inhibit the leaching and detachment of Ni nanoparticles. Compared with the Ni‐based catalyst supported on the outer surface of Al₂O₃ nanotubes, the multiply confined catalyst shows a striking improvement of catalytic activity and stability in hydrogenation reactions. Our ALD‐assisted template method is general and can be extended for other multiply confined nanoreactors, which may have potential applications in many heterogeneous reactions.     

Stabilization of Copper Catalysts for Liquid‐Phase Reactions by Atomic Layer Deposition

Atomic layer deposition (ALD) of an alumina overcoat can stabilize a base metal catalyst (e.g., copper) for liquid‐phase catalytic reactions (e.g., hydrogenation of biomass‐derived furfural in alcoholic solvents or water), thereby eliminating the deactivation of conventional catalysts by sintering and leaching. This method of catalyst stabilization alleviates the need to employ precious metals (e.g., platinum) in liquid‐phase catalytic processing. The alumina overcoat initially covers the catalyst surface completely. By using solid state NMR spectroscopy, X‐ray diffraction, and electron microscopy, it was shown that high temperature treatment opens porosity in the overcoat by forming crystallites of γ‐Al₂O₃. Infrared spectroscopic measurements and scanning tunneling microscopy studies of trimethylaluminum ALD on copper show that the remarkable stability imparted to the nanoparticles arises from selective armoring of under‐coordinated copper atoms on the nanoparticle surface.     

Atomic Layer Deposition Overcoating: Tuning Catalyst Selectivity for Biomass Conversion

The terraces, edges, and facets of nanoparticles are all active sites for heterogeneous catalysis. These different active sites may cause the formation of various products during the catalytic reaction. Here we report that the step sites of Pd nanoparticles (NPs) can be covered precisely by the atomic layer deposition (ALD) method, whereas the terrace sites remain as active component for the hydrogenation of furfural. Increasing the thickness of the ALD‐generated overcoats restricts the adsorption of furfural onto the step sites of Pd NPs and increases the selectivity to furan. Furan selectivities and furfural conversions are linearly correlated for samples with or without an overcoating, though the slopes differ. The ALD technique can tune the selectivity of furfural hydrogenation over Pd NPs and has improved our understanding of the reaction mechanism. The above conclusions are further supported by density functional theory (DFT) calculations.     

原子层沉积构筑Pd/TiO2限域催化剂及其在1,4-丁炔二醇加氢的应用

利用ALD制备了TiO₂限域的Pd催化剂, 研究了限域空间内Pd纳米颗粒与TiO₂的界面作用对1,4-丁炔二醇(BYD)加氢性能的影响. 相比于管外负载型催化剂, 限域催化剂在催化1,4-丁炔二醇选择性加氢反应中体现出非常高的催化活性和1,4-丁烯二醇的选择性. HR-TEM、 EDX-Mapping、 XRD、 XPS和H₂-TPR表征说明, 限域体系中Pd-TiO₂的界面相互作用强于传统TiO₂表面负载型Pd催化剂, 这种强界面作用不仅能够提高BYD的加氢活性, 也可抑制半加氢产物1,4-丁烯二醇的异构化和深度加氢, 提高1,4-丁烯二醇的选择性, 而且限域结构也可阻止管内壁Pd纳米颗粒的脱落, 提高催化剂的稳定性.     

A Tandem Catalyst with Multiple Metal Oxide Interfaces Produced by Atomic Layer Deposition

Ideal heterogeneous tandem catalysts necessitate the rational design and integration of collaborative active sites. Herein, we report on the synthesis of a new tandem catalyst with multiple metal‐oxide interfaces based on a tube‐in‐tube nanostructure using template‐assisted atomic layer deposition, in which Ni nanoparticles are supported on the outer surface of the inner Al₂O₃ nanotube (Ni/Al₂O₃ interface) and Pt nanoparticles are attached to the inner surface of the outer TiO₂ nanotube (Pt/TiO₂ interface). The tandem catalyst shows remarkably high catalytic efficiency in nitrobenzene hydrogenation over Pt/TiO₂ interface with hydrogen formed in situ by the decomposition of hydrazine hydrate over Ni/Al₂O₃ interface. This can be ascribed to the synergy effect of the two interfaces and the confined nanospace favoring the instant transfer of intermediates. The tube‐in‐tube tandem catalyst with multiple metal‐oxide interfaces represents a new concept for the design of highly efficient and multifunctional nanocatalysts.     

FeOx Coating on Pd/C Catalyst by Atomic Layer Deposition Enhances the Catalytic Activity in Dehydrogenation of Formic Acid

Hydrogen generation from formic acid (FA) has received significant attention.The challenge is to obtain a highly active catalyst under mild conditions for practical applications.Here atomic layer deposition (ALD) of FeO_x was performed to deposit an ultrathin oxide coating layer to a Pd/C catalyst,therein the FeO_x coverage was precisely controlled by ALD cycles.Transmission electron microscopy and powder X-ray diffraction measurements suggest that the FeO_x coating layer improved the thermal stability of Pd nanoparticles (NPs).X-ray photoelectron spectroscopy measurement showed that deposition of FeO_x on the Pd NPs caused a positive shift of Pd3d binding energy.In the FA dehydrogenation reaction,the ultrathin FeO_x layer on the Pd/C could considerably improve the catalytic activity,and Pd/C coated with 8 cycles of FeO_x showed an optimized activity with turnover frequency being about 2 times higher than the uncoated one.The improved activities were in a volcanoshape as a function of the number of FeO_x ALD cycles,indicating the coverage of FeO_x is critical for the optimized activity.In summary,simultaneous improvements of activity and thermal stability of Pd/C catalyst by ultra-thin FeO_x overlayer suggest to be an effective way to design active catalysts for the FA dehydrogenation reaction.     

Atomic and Molecular Layer Deposition as Surface Engineering Techniques for Emerging Alkali Metal Rechargeable Batteries

Alkali metals (lithium, sodium, and potassium) are promising as anodes in emerging rechargeable batteries, ascribed to their high capacity or abundance. Two commonly experienced issues, however, have hindered them from commercialization: the dendritic growth of alkali metals during plating and the formation of solid electrolyte interphase due to contact with liquid electrolytes. Many technical strategies have been developed for addressing these two issues in the past decades. Among them, atomic and molecular layer deposition (ALD and MLD) have been drawing more and more efforts, owing to a series of their unique capabilities. ALD and MLD enable a variety of inorganic, organic, and even inorganic-organic hybrid materials, featuring accurate nanoscale controllability, low process temperature, and extremely uniform and conformal coverage. Consequently, ALD and MLD have paved a novel route for tackling the issues of alkali metal anodes. In this review, we have made a thorough survey on surface coatings via ALD and MLD, and comparatively analyzed their effects on improving the safety and stability of alkali metal anodes. We expect that this article will help boost more efforts in exploring advanced surface coatings via ALD and MLD to successfully mitigate the issues of alkali metal anodes.     

Atomic-Scale Designing of Zeolite Based Catalysts by Atomic Layer Deposition

Zeolite-supported catalysts have been widely used in the field of heterogeneous catalysis. Atomic-scale governing the metal or acid sites on zeolites still encounters great challenge in controllable synthesis and developing of novel catalysts. Atomic layer deposition (ALD), owing to its unique character of self-limiting surface reactions, becomes one of the most promising and controllable strategies to tailor the metallic deposition sites in atomic scale precisely. In this review, we present a comprehensive summary and viewpoint of recent research in designing and engineering the structural of zeolite-based catalysts via ALD method. A prior focus is laid on the deposition of metals on the zeolites with emphasis on the isolated states of metals, followed by introducing the selected metals into channels of zeolites associates with identifying the location of metals in and/or out of the channels. Subsequently, detailed analysis of tailoring the acid sites of different zeolites is provided. Assisted synthesis of zeolite and the regioselective deposition of metal on special sites to modify the structures of zeolites are also critically discussed. We further summarize the challenges of ALD with respect to engineering the active sites in heterogeneous zeolite-based catalysts and provide the perspectives on the development in this field.     

Enhanced Electrochemical Performance of Supercapacitors via Atomic Layer Deposition of ZnO on the Activated Carbon Electrode Material

Fabricating electrical double-layer capacitors (EDLCs) with high energy density for various applications has been of great interest in recent years. However, activated carbon (AC) electrodes are restricted to a lower operating voltage because they suffer from instability above a threshold potential window. Thus, they are limited in their energy storage. The deposition of inorganic compounds’ atomic layer deposition (ALD) aiming to enhance cycling performance of supercapacitors and battery electrodes can be applied to the AC electrode materials. Here, we report on the investigation of zinc oxide (ZnO) coating strategy in terms of different pulse times of precursors, ALD cycles, and deposition temperatures to ensure high electrical conductivity and capacitance retention without blocking the micropores of the AC electrode. Crystalline ZnO phase with its optimal forming condition is obtained preferably using a longer precursor pulse time. Supercapacitors comprising AC electrodes coated with 20 cycles of ALD ZnO at 70 °C and operated in TEABF₄/acetonitrile organic electrolyte show a specific capacitance of 23.13 F g⁻¹ at 5 mA cm⁻² and enhanced capacitance retention at 3.2 V, which well exceeds the normal working voltage of a commercial EDLC product (2.7 V). This work delivers an additional feasible approach of using ZnO ALD modification of AC materials, enhancing and promoting stable EDLC cells under high working voltages.     

Nanoscale Structuring of Surfaces by Using Atomic Layer Deposition

Controlled structuring of surfaces is interesting for a wide variety of areas, including microelectronic device fabrication, optical devices, bio(sensing), (electro‐, photo)catalysis, batteries, solar cells, fuel cells, and sorption. A unique feature of atomic layer deposition (ALD) is the possibility to form conformal uniform coatings on arbitrarily shaped materials with controlled atomic‐scale thickness. In this Minireview, we discuss the potential of ALD for the nanoscale structuring of surfaces, highlighting its versatile application to structuring both planar substrates and powder materials. Recent progress in the application of ALD to porous substrates has even made the nanoscale structuring of high‐surface‐area materials now feasible, thereby enabling novel applications, such as those in the fields of catalysis and alternative energy.     

Inherently Area-Selective Atomic Layer Deposition of Manganese Oxide through Electronegativity-Induced Adsorption

Manganese oxide (MnO_x) shows great potential in the areas of nano-electronics, magnetic devices and so on. Since the characteristics of precise thickness control at the atomic level and self-align lateral patterning, area-selective deposition (ASD) of the MnO_x films can be used in some key steps of nanomanufacturing. In this work, MnO_x films are deposited on Pt, Cu and SiO₂ substrates using Mn(EtCp)₂ and H₂O over a temperature range of 80–215 °C. Inherently area-selective atomic layer deposition (ALD) of MnO_x is successfully achieved on metal/SiO₂ patterns. The selectivity improves with increasing deposition temperature within the ALD window. Moreover, it is demonstrated that with the decrease of electronegativity differences between M (M = Si, Cu and Pt) and O, the chemisorption energy barrier decreases, which affects the initial nucleation rate. The inherent ASD aroused by the electronegativity differences shows a possible method for further development and prediction of ASD processes.     

Atomic Layer Deposition of the Metal Pyrites FeS2, CoS2, and NiS2

Atomic layer deposition (ALD) of the pyrite‐type metal disulfides FeS₂, CoS₂, and NiS₂ is reported for the first time. The deposition processes use iron, cobalt, and nickel amidinate compounds as the corresponding metal precursors and the H₂S plasma as the sulfur source. All the processes are demonstrated to follow ideal self‐limiting ALD growth behavior to produce fairly pure, smooth, well‐crystallized, stoichiometric pyrite FeS₂, CoS₂, and NiS₂ films. By these processes, the FeS₂, CoS₂, and NiS₂ films can also be uniformly and conformally deposited into deep narrow trenches with aspect ratios as high as 10:1, which thereby highlights the broad and promising applicability of these ALD processes for conformal film coatings on complex high‐aspect‐ratio 3D architectures in general.     

Atomic Layer Deposition of Cobalt Phosphide for Efficient Water Splitting

Transition‐metal phosphides (TMP) prepared by atomic layer deposition (ALD) are reported for the first time. Ultrathin Co‐P films were deposited by using PH₃ plasma as the phosphorus source and an extra H₂ plasma step to remove excess P in the growing films. The optimized ALD process proceeded by self‐limited layer‐by‐layer growth, and the deposited Co‐P films were highly pure and smooth. The Co‐P films deposited via ALD exhibited better electrochemical and photoelectrochemical hydrogen evolution reaction (HER) activities than similar Co‐P films prepared by the traditional post‐phosphorization method. Moreover, the deposition of ultrathin Co‐P films on periodic trenches was demonstrated, which highlights the broad and promising potential application of this ALD process for a conformal coating of TMP films on complex three‐dimensional (3D) architectures.     

十八烷基键合硅胶的原子层沉积法封尾及其在碱性化合物分离中的应用

采用原子层沉积法对十八烷基键合硅胶进行端基封尾.以六甲基二硅氮烷为封端试剂,在250 ℃下与键合硅胶样品反应6 h,制备了对碱性化合物具有高惰性的反相色谱填料.分别以吡啶/苯酚和萘/阿米替林为分子探针,考察了经原子层沉积法和传统液相有机溶剂法封尾处理的十八烷基键合硅胶的色谱性能,并与商品十八烷基硅胶Zorbax SB-C18和Kromasil C18进行对比.结果表明,原子层沉积法封尾的十八烷基硅胶对碱性化合物的分离特性明显优于传统液相法,其色谱性能已超过Zorbax SB-C18,与Kromasil C18相当.本方法无需有机溶剂,操作简便,反应耗时短,易于放大生产,封尾反应完全,应用前景良好.     

原子层沉积：一种多相催化剂“自下而上”气相制备新策略

多相催化剂是极为重要的一类催化剂,在许多重要工业反应中扮演关键角色。然而,传统的湿化学合成手段在很多情况下难以做到对催化剂活性位点的结构、组成以及其周围局部环境的原子级精细调控,继而给优化催化剂性能、理解多相催化机理带来较大的挑战。原子层沉积(ALD)是一种气相催化剂合成技术,其原理是基于两种前驱体蒸汽交替进样并在载体表面上发生分子层面上的“自限制”反应,实现目标材料在载体表面上的精准沉积。利用其分子层面上的“自限制”反应特性,并通过改变沉积周期数、次序和种类等方法可以实现对催化剂活性位结构的原子级精细控制,进而为人们提供了一种催化剂“自下而上”精细可控合成的新策略。在本文中,我们总结了利用ALD方法在负载型单金属和双金属催化剂精细设计方面的进展,讨论了ALD方法在设计高效催化剂方面的特点与优势。特别地,我们总结了利用ALD方法制备单原子和双原子结构金属催化剂的方法与策略。此外,我们总结了利用氧化物可控沉积精准调控金属催化活性中心周围的微环境,从而实现提升催化剂活性、选择性和稳定性的方法。最后我们展望了ALD技术在催化剂制备领域中应用的潜力。     

多孔氮化钛载体上铂催化剂的原子层沉积制备及其催化氧气还原性能

为有效解决铂(Pt)催化剂用于氧气还原反应(ORR)面临的催化活性及稳定性问题,本文首先合成了具有良好导电性、电化学稳定以及耐腐蚀等优点的一维多孔氮化钛(Ti N)纳米管载体材料,然后使用原子层沉积技术(ALD)在Ti N载体上沉积制备了Pt催化剂(ALD-Pt/Ti N),所得的Pt纳米颗粒尺寸均匀、高度分散且与Ti N载体之间存在着较强的相互作用。催化氧气还原活性和稳定性测试表明,所得的ALD-Pt/Ti N对ORR具有较高的催化活性,同时兼具良好的稳定性和耐久性。相比商用Pt/C,ALD-Pt/Ti N的起始电位和稳态极限电流密度与其相近,半波电位则高出了20 m V,表现出优异的电催化性能。其优良的电催化性能主要归因于ALD沉积Pt纳米颗粒的高分散性,一维多孔结构Ti N载体的高比表面积、良好导电性和抗腐蚀性能以及ALD-Pt与Ti N载体间较强的相互作用等综合影响。本工作为设计新型高催化活性、高稳定性的Pt基催化剂提供了有益借鉴。     

Deposition Mechanism and Properties of Plasma-Enhanced Atomic Layer Deposited Gallium Nitride Films with Different Substrate Temperatures

Gallium nitride (GaN) is a wide bandgap semiconductor with remarkable chemical and thermal stability, making it a competitive candidate for a variety of optoelectronic applications. In this study, GaN films are grown using a plasma-enhanced atomic layer deposition (PEALD) with trimethylgallium (TMG) and NH₃ plasma. The effect of substrate temperature on growth mechanism and properties of the PEALD GaN films is systematically studied. The experimental results show that the self-limiting surface chemical reactions occur in the substrate temperature range of 250–350 °C. The substrate temperature strongly affects the crystalline structure, which is nearly amorphous at below 250 °C, with (100) as the major phase at below 400 °C, and (002) dominated at higher temperatures. The X-ray photoelectron spectroscopy spectra reveals the unintentional oxygen incorporation into the films in the forms of Ga₂O₃ and Ga-OH. The amount of Ga-O component decreases, whereas the Ga-Ga component rapidly increases at 400 and 450 °C, due to the decomposition of TMG. The substrate temperature of 350 °C with the highest amount of Ga-N bonds is, therefore, considered the optimum substrate temperature. This study is helpful for improving the quality of PEALD GaN films.     

Potential Precursor Alternatives to the Pyrophoric Trimethylaluminium for the Atomic Layer Deposition of Aluminium Oxide

New precursor chemistries for the atomic layer deposition (ALD) of aluminium oxide are reported as potential alternatives to the pyrophoric trimethylaluminium (TMA) which is to date a widely used Al precursor. Combining the high reactivity of aluminium alkyls employing the 3-(dimethylamino)propyl (DMP) ligand with thermally stable amide ligands yielded three new heteroleptic, non-pyrophoric compounds [Al(NMe₂)₂(DMP)] ( 2 ), [Al(NEt₂)₂(DMP)] ( 3 , BDEADA) and [Al(NiPr₂)₂(DMP)] ( 4 ), which combine the properties of both ligand systems. The compounds were synthesized and thoroughly chemically characterized, showing the intramolecular stabilization of the DMP ligand as well as only reactive Al−C and Al−N bonds, which are the key factors for the thermal stability accompanied by a sufficient reactivity, both being crucial for ALD precursors. Upon rational variation of the amide alkyl chains, tunable and high evaporation rates accompanied by thermal stability were found, as revealed by thermal evaluation. In addition, a new and promising plasma enhanced (PE)ALD process using BDEADA and oxygen plasma in a wide temperature range from 60 to 220 °C is reported and compared to that of a modified variation of the TMA, namely [AlMe₂(DMP)] (DMAD). The resulting Al₂O₃ layers are of high density, smooth, uniform, and of high purity. The applicability of the Al₂O₃ films as effective gas barrier layers (GBLs) was successfully demonstrated, considering that coating on polyethylene terephthalate (PET) substrates yielded very good oxygen transmission rates (OTR) with an improvement factor of 86 for a 15 nm film by using DMAD and a factor of 25 for a film thickness of just 5 nm by using BDEDA compared to bare PET substrates. All these film attributes are of the same quality as those obtained for the industrial precursor TMA, rendering the new precursors safe and potential alternatives to TMA.