Cluster-support interactions and morphology of MoS2 nanoclusters in a graphite-supported hydrotreating model catalyst

Supported MoS(2) nanoparticles constitute the active component of the important hydrotreating catalysts used for industrial upgrading and purification of the oil feedstock for the production of fossil fuels with a low environmental load. We have synthesized and studied a model system of the hydrotreating catalyst consisting of MoS(2) nanoclusters supported on a graphite surface in order to resolve a number of very fundamental questions related to the atomic-scale structure and morphology of the active clusters and in particular the effect of a substrate used in some types of hydrotreating catalysts. Scanning tunneling microscopy (STM) is used to image the atomic-scale structure of graphite-supported MoS(2) nanoclusters in real space. It is found that the pristine graphite (0001) surface does not support a high dispersion of MoS(2), but by introducing a small density of defects in the surface, highly dispersed MoS(2) nanoclusters could be synthesized on the graphite. From high-resolution STM images it is found that MoS(2) nanoclusters synthesized at low temperature in a sulfiding atmosphere preferentially grow as single-layer clusters, whereas clusters synthesized at 1200 K grow as multilayer slabs oriented with the MoS(2)(0001) basal plane parallel to the graphite surface. The morphology of both single-layer and multilayer MoS(2) nanoclusters is found to be preferentially hexagonal, and atom-resolved images of the top facet of the clusters provide new atomic-scale information on the MoS(2)-HOPG bonding. The structure of the two types of catalytically interesting edges terminating the hexagonal MoS(2) nanoclusters is also resolved in atomic detail in STM images, and from these images it is possible to reveal the atomic structure of both edges and the location and coverage of sulfur and hydrogen adsorbates.     

基于核酸外切酶Ⅲ诱导的双重信号放大与MoS2纳米片荧光碎灭性质的核酸检测方法

将核酸外切酶Ⅲ诱导的双重信号放大技术与MoS2纳米片的荧光猝灭性质结合,构建了一种高灵敏高选择性的DNA检测方法.首先设计两条末端修饰荧光基团的探针核酸(HP1和HP2).由于两条探针核酸具有3'粘性末端,使其不会被核酸外切酶Ⅲ降解,因而被吸附于MoS2纳米片而猝灭其荧光.当目标DNA存在时,会促使核酸外切酶Ⅲ启动双重信号放大反应,并将探针核酸降解成大量的不能吸附于MoS2纳米片表面的荧光碎片.在优化条件下,目标DNA浓度在0.5~6.0 pmol/L范围内与荧光信号变化呈良好的线性关系,检出限为0.28 pmol/L.与单重信号放大技术相比,本方法极大改善了分析灵敏度和检出限,且具有良好的单碱基错配区分能力.     

Ab initio study on the noncovalent adsorption of camptothecin anticancer drug onto graphene, defect modified graphene and graphene oxide

The application of graphene and related nanomaterials like boron nitride (BN) nanosheets, BN-graphene hybrid nanomaterials, and graphene oxide (GO) for adsorption of anticancer chemotherapeutic camptothecin (CPT) along with the effect on electronic properties prior to functionalization and after functionalization has been reported using density functional theory (DFT) calculations. The inclusion of dispersion correction to DFT is instrumental in accounting for van der Waals π–π stacking between CPT and the nanomaterial. The adsorption of CPT exhibits significant strain within the nanosheets and noncovalent adsorption of CPT is thermodynamically favoured onto the nanosheets. In case of GO, surface incorporation of functional groups result in significant crumpling along the basal plane and the interaction is basically mediated by H-bonding rather than π–π stacking. Docking studies predict the plausible binding of CPT, CPT functionalized graphene and GO with topoisomerase I (top 1) signifying that CPT interacts through π stacking with AT and GC base pairs of DNA and in presence of nano support, DNA bases preferentially gets bound to the basal plane of graphene and GO rather than the edges. At a theoretical level of understanding, our studies point out the noncovalent interaction of CPT with graphene based nanomaterials and GO for loading and delivery of anticancer chemotherapeutic along with active binding to Top1 protein.     

A comparison of H+-restacked nanosheets and nano-scrolls derived from K4Nb6O17for visible-light degra-dation of dyes

H＋-restacked nanosheets and nanoscrolls peeled from K4Nb6O17 display different structures and surface characters. The two restacked samples with increased surface areas have an amazing visible-light response for the photodegradation of dyes, which is superior to commercial TiO2 （P25） and Nb205. By comparison, H＋/nanosheets have a relatively faster photodegradation rate originated from large and smooth basal plane. The work reveals that dye adsorbed on the unfolded nanosheets can effectively harvest sunlight. Due to facile preparation, low-cost and high photocatalytic efficiency, H＋/nanosheets and H＋/nanoscrolls might be used for the visible light-driven degradation of organic dyes as a substitute for TiO2 in industry.     

Fullerene-like (IF) Nb(x)Mo(1-x)S2 nanoparticles

IF-Mo1-xNbxS2 nanoparticles have been synthesized by a vapor-phase reaction involving the respective metal halides with H2S. The IF-Mo1-xNbxS2 nanoparticles, containing up to 25% Nb, were characterized by a variety of experimental techniques. Analysis of the powder X-ray powder diffraction, X-ray photoelectron spectroscopy, and different electron microscopy techniques shows that the majority of the Nb atoms are organized as nanosheets of NbS2 within the MoS2 host lattice. Most of the remaining Nb atoms (3%) are interspersed individually and randomly in the MoS2 host lattice. Very few Nb atoms, if any, are intercalated between the MoS2 layers. A sub-nanometer film of niobium oxide seems to encoat the majority of the nanoparticles. X-ray photoelectron spectroscopy in the chemically resolved electrical measurement mode (CREM) and scanning probe microscopy measurements of individual nanoparticles show that the mixed IF nanoparticles are metallic independent of the substitution pattern of the Nb atoms in the lattice of MoS2 (whereas unsubstituted IF-MoS2 nanoparticles are semiconducting). Furthermore the IF-Mo1-xNbxS2 nanoparticles are found to exhibit interesting single electron tunneling effects at low temperatures.     

Novel cage clusters of MoS2 in the gas phase

Laser evaporation of MoS(2) nanoflakes gives negatively charged magic number clusters of compositions Mo(13)S(25) and Mo(13)S(28), which are shown to have closed-cage structures. The clusters are stable and do not show fragmentation in the post-source decay analysis even at the highest laser powers. Computations suggest that Mo(13)S(25) has a central cavity with a diameter of 4.5 A. The nanosheets of MoS(2) could curl upon laser irradiation, explaining the cluster formation.     

复合半导体MoS_2/Cu_2O的制备及其光催化性能研究

采用两步法制备了MoS_2/Cu_2O催化剂,对其催化降解甲基橙(MO)性能进行了研究.首先,通过液相剥离和梯度离心获得少数层MoS_2纳米片,然后采用水热还原法在MoS_2纳米片上合成Cu_2O纳米颗粒,形成MoS_2/Cu_2O复合半导体,并分别通过扫描电子显微镜(SEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)、UV-Vis紫外可见漫反射光谱(DRS)等手段对催化剂的结构进行表征.在可见光下,MoS_2/Cu_2O复合半导体降解MO的效率明显高于纯MoS_2和Cu_2O.为了获得最佳光催化活性,探究了MoS_2质量分数(5%、10%、20%、30%、40%、50%)对MoS_2/Cu_2O复合半导体光催化降解MO的影响.最后,经过5次循环实验,MoS_2/Cu_2O降解率下降为82.5%,循环稳定性有待进一步提高.     

MoS2 nanoparticles grown on graphene: an advanced catalyst for the hydrogen evolution reaction

Advanced materials for electrocatalytic and photoelectrochemical water splitting are central to the area of renewable energy. In this work, we developed a selective solvothermal synthesis of MoS(2) nanoparticles on reduced graphene oxide (RGO) sheets suspended in solution. The resulting MoS(2)/RGO hybrid material possessed nanoscopic few-layer MoS(2) structures with an abundance of exposed edges stacked onto graphene, in strong contrast to large aggregated MoS(2) particles grown freely in solution without GO. The MoS(2)/RGO hybrid exhibited superior electrocatalytic activity in the hydrogen evolution reaction (HER) relative to other MoS(2) catalysts. A Tafel slope of ～41 mV/decade was measured for MoS(2) catalysts in the HER for the first time; this exceeds by far the activity of previous MoS(2) catalysts and results from the abundance of catalytic edge sites on the MoS(2) nanoparticles and the excellent electrical coupling to the underlying graphene network. The ～41 mV/decade Tafel slope suggested the Volmer-Heyrovsky mechanism for the MoS(2)-catalyzed HER, with electrochemical desorption of hydrogen as the rate-limiting step.     

表面暴露活性位点的MoS_2纳米催化剂催化硝基化合物的非均相氢转移反应（英文）

MoS_2具有独特的二维层状结构,被广泛用于加氢脱硫过程以及HER反应,而且可以通过减少MoS_2的颗粒尺寸以及层数来进一步改善其催化活性.通过剥离方法得到的MoS_2纳米片虽然表现出优良的加氢脱硫活性,但容易团聚使其循环使用性能很差.如果通过引入纳米碳将单层的MoS_2纳米片进行有效"隔离",则可明显降低团聚的可能性,从而改善其催化性能和稳定性.本文通过一步水热法制备出了碳嵌入的MoS_2纳米颗粒(MoS_2@C),将其应用于硝基苯类化合物的氢转移反应中表现出了非常好的催化性能.进一步通过粉末X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)和在线质谱检测等手段研究了层间距增加的MoS_2催化剂在硝基苯类化合物的氢转移反应中催化性能提升的原因.XRD,SEM和TEM结果表明,通过引入碳材料可以明显增加MoS_2的层间距,同时减小其颗粒尺寸,而且使MoS_2表现出弯曲的(002)晶面.由于存在一定的曲率,这种(002)晶面也会表现出一定的催化能力.氮气物理吸附结果表明,这种MoS_2@C复合物具有较高的比表面积(89 m~2g~(-1))和明显的介孔结构(~20 nm),在催化反应中有利于底物扩散,进而改善催化性能.XPS结果显示,与体相的MoS_2相比,MoS_2@C表面暴露出更多的不饱和Mo原子(Mo/S=0.71(MoS_2@C)vs Mo/S=0.63(MoS_2)),形成了独特的S-Mo-O结构以及缺陷结构.在硝基苯类化合物的氢转移反应中,层间距增加的MoS_2@C由于暴露出更多的活性位和具有弯曲的(002)晶面,表现出了更高的催化活性–(TOF=3.66 s~(-1) vs 1.24 s~(-1)(MoS_2)).通过质谱对反应过程的追踪发现,在只有肼存在的条件下,MoS_2@C催化肼分解的主要气相产物是氨气.这说明MoS_2@C能够使肼发生N-N键的断裂.而当肼和硝基苯同时存在的条件下,质谱检测的气相产物主要是氮气,表明硝基苯的存在可以诱导肼逐步发生N-H键断裂,在催化剂表面形成活性的H物种,进而转移到硝基苯上使其还原得到苯胺.使用偶氮苯和氧化偶氮苯作为反应底物,发现MoS_2@C很难使其还原为苯胺,这说明在该催化体系中,硝基苯的还原过程主要是沿着直接路径(硝基苯-亚硝基苯-苯胺)进行的.     

高分散超薄二硫化钼/硫、氮共掺碳复合材料的电催化析氢性能

氢气是一种清洁可再生能源,有望在未来替代化石燃料成为最主要的能源物质.电催化析氢技术是最有效的产氢途径之一.目前,电催化析氢催化剂主要是贵金属铂,由于其昂贵的价格限制了它的大规模应用.所以在不减少催化剂活性的前提下尽量减少贵金属的使用或者寻找替代物质,降低成本是工业化大规模使用析氢反应(HER)催化剂的前提.二硫化钼基催化剂因其价格低廉、资源丰富且具有优异的催化析氢性能而引起研究者的广泛关注.实验和理论研究都证明了二硫化钼的催化性能和其催化活性位点有关.所以,开发一种具有丰富的活性位点、良好的导电性的二硫化钼基催化剂可以获得高的产氢性能和良好的稳定性.因此,对于提高MoS2的电催化析氢性能的研究主要集中于增加MoS2暴露活性位点的个数和导电性.然而,二硫化钼层与层之间的相互作用可能导致其发生聚集,较低的导电率都有可能降低它的电催化活性.我们通过水热的方法直接制备出了固体的硫、氮共掺杂的、具有石墨化结构的碳复合材料(SNC).将钼酸钠加入到反应中后,多钼酸盐通过化学交互作用均匀地嵌入、分散到SNC中.经高温处理后,SNC放出S2-,多钼酸盐结合S2-生成二硫化钼.SNC有效地防止了二硫化钼聚集成大的颗粒.我们成功地制备出具有较好析氢性能的、高度分散于SNC中的二硫化钼纳米片.通过透射电子显微镜(TEM)、扫描电子显微镜(SEM)、X射线衍射(XRD)、拉曼光谱(Raman)、元素分析、X射线光电子能谱(XPS)等测试手段对材料进行了表征,通过电催化析氢、电化学阻抗以及稳定性测试等手段研究了其电催化性能.由MoS2/SNC-900-12h的TEM图片可以看出,二硫化钼纳米片高度分散于碳复合材料中,且层数只有一到几层,暴露出了更多的催化活性位点.拉曼光谱图的D带(1341 cm-1)和G带(1584 cm-1)体现出了材料具有较好的石墨化结构,提高了材料的导电性.XPS C 1s谱图中存在C–S和C–N键,S 2p谱图中存在C–S–C、C=S和C–SOx–C键,N 1s谱图中存在吡啶氮和石墨氮,结合元素分析,说明该碳材料确为硫氮共掺杂的碳;Mo谱测试显示出Mo 3d5/2(229.4 eV)和Mo 3d3/2(232.6 eV),证明了二硫化钼成功地嵌入到了碳材料中.电化学性能表征显示MoS2/SNC-900-12h在H2SO4溶液(0.5 mol/L)中展现出较低的起始电位(115 mV)以及低的过电位(237 mV).电化学阻抗测试显示在H2SO4溶液(0.5 mol/L)中过电位为?0.2 V(vs.RHE)时Rct只有124Ω.此外,在?0.3–0 V(vs.RHE)下,经5000圈稳定性测试后性能只有约2.6%(10 mA/cm2)的衰减,说明MoS2/SNC-900-12h同样具有优异的电化学稳定性.     

表面活性剂辅助水热制备形貌结构可控的MoS2及其蒽加氢性能

随着原油资源重质化和劣质化的加剧以及对清洁燃料油品需求的不断增加,将重质油加工成清洁燃料成为现代炼厂面临的挑战.悬浮床加氢是重质油转化为清洁液体燃料的先进技术,其核心难题是高效加氢催化剂的开发.MoS2在石油化工领域油品加氢提质研究中表现出非常好的催化加氢性能.MoS2晶体结构中有两种面:沿S-Mo-S层间的剥离面,又称基面,化学性质稳定;沿Mo-S的断裂面,又称棱面,具有大量的不饱和键,化学性质不稳定,可做催化活性中心.由于MoS2结构和形貌对其物理化学性能有重要影响,所以通过合理设计和调控MoS2的结构和形貌可增加暴露的催化活性位,进而改善其催化性能.本文以七钼酸铵和硫代乙酰胺为原料,水合肼做还原剂,采用不同表面活性剂(包括PEG,PVP,P123,SDS,AOT和CTAB)辅助的水热合成法制备了结构及形貌可控的MoS2,并提出不同表面活性剂条件下MoS2催化剂的生长机理,进一步研究了重油模型化合物稠环芳烃蒽的催化加氢性能.结果表明,在不同表面活性剂辅助的条件下分别制得了由MoS2纳米片组装而成的球形、块状和花状的MoS2产物;通过改变表面活性剂种类可调变MoS2纳米片的长度、堆积层数、层间距以及最终产物的形貌.在PEG或PVP辅助下得到了球形MoS2产物,其中MoS2纳米片长<15 nm,堆积层数<6.在PEG辅助下制备的球形MoS2粒径约为250 nm,尺寸均一且分散性好.在PVP辅助下MoS2粒径在200–450 nm,粒径分布范围宽且有明显团聚.在P123或SDS辅助下得到了团聚较明显的块状微米级MoS2产物.在P123辅助下得到的MoS2纳米片长<15 nm,层数<6.在SDS辅助下制备的MoS2纳米片长>20 nm,堆积层数>8.在AOT或CTAB辅助下得到团聚比较严重的花状微米级MoS2产物,其中MoS2纳米片长>20 nm,堆积层数>8.另外,水热反应过程中,高温高压的环境促进了反应体系中游离的NH4+插入到MoS2层状结构中,导致MoS2纳米片层间距增大.基于此,本文提出了不同表面活性剂辅助的水热过程中不同结构和形貌MoS2产物的形成机理.对不同结构和形貌的MoS2样品进行了悬浮床蒽加氢催化性能评价.结果表明,PEG辅助制备的MoS2催化剂具有最高催化加氢活性.该MoS2催化剂中纳米片层短,堆积层数少,暴露了更多的加氢活性位.单分散的球形MoS2颗粒粒径小,分散性好,有利于加氢活性位的充分暴露,进而表现出较好的催化性能.本文所采用的表面活性剂辅助的水热法为可控合成不同结构和形貌的过渡金属硫化物提供了有效指导和借鉴.     

A comparison of H+-restacked nanosheets and nanoscrolls derived from K4Nb6O17 for visible-light degradation of dyes

H⁺-restacked nanosheets and nanoscrolls peeled from K₄Nb₆O₁₇ display different structures and surface characters. The two restacked samples with increased surface areas have an amazing visible-light response for the photodegradation of dyes, which is superior to commercial TiO₂ (P25) and Mb₂O₅. By comparison, H⁺/nanosheets have a relatively faster photodegradation rate originated from large and smooth basal plane. The work reveals that dye adsorbed on the unfolded nanosheets can effectively harvest sunlight. Due to facile preparation, low-cost and high photocatalytic efficiency, H⁺/nanosheets and H⁺/nanoscrolls might be used for the visible light-driven degradation of organic dyes as a substitute for TiO₂ in industry.     

A versatile DNA detection scheme based on the quenching of fluorescent silver nanoclusters by MoS2 nanosheets: Application to aptamer-based determination of hepatitis B virus and of dopamine

Microchimica Acta - The authors report that the fluorescence of polymer-capped silver nanoclusters (AgNCs) is quenched by MoS2 nanosheets. However, in the presence of electrolytes such as sodium...     

Porous MoS2 synthesized by ultrasonic spray pyrolysis

The hydrodesulfurization (HDS) activity of molybdenum sulfide-based catalysts is localized to the edges of this layered solid and is, therefore, highly dependent on the technique used to prepare the material. Here, ultrasonic spray pyrolysis (USP) was used to synthesize porous, nanostructured MoS2. Low surface area powders, not useful for catalysis, are generally produced by USP. This work shows that when combined with a dissolvable template, USP is capable of producing high surface area materials. An aqueous solution of ammonium tetrathiomolybdate and colloidal silica was nebulized and pyrolyzed to give a MoS2/SiO2 composite material. Leaching with HF removed the sacrificial SiO2, resulting in a highly porous MoS2 network with surface areas as high as 250 m2/g. Cobalt-promoted MoS2 networks were also synthesized. The thiophene HDS activities of these materials were substantially higher than those of unsupported MoS2 and RuS2 standards, illustrating the enhanced dispersion of the HDS active phase achieved by this synthetic technique.     

MoS2 hierarchical hollow cubic cages assembled by bilayers: one-step synthesis and their electrochemical hydrogen storage properties

Micrometer scaled MoS2 hierarchical hollow cubic cages assembled by bilayers can be synthesized via a one-step self-assembly coupled with intermediate crystal templating process without any surfactant, in which the intermediate K2NaMoO3F3 crystal formed in-situ and then served as the self-sacrificed template based on the Kirkendall Effect; The MoS2 hierarchical hollow cubic cages were employed for electrochemical hydrogen storage with a high capacity of 375 mAh g(-1) due to the more active edges exposing on the upright-standing nanoplates.     

In‐Plane Black Phosphorus/Dicobalt Phosphide Heterostructure for Efficient Electrocatalysis

Heterostructures composed of two‐dimensional black phosphorus (2D BP) with unique physical/chemical properties are of great interest. Herein, we report a simple solvothermal method to synthesize in‐plane BP/Co₂P heterostructures for electrocatalysis. By using the reactive edge defects of the BP nanosheets as the initial sites, Co₂P nanocrystals are selectively grown on the BP edges to form the in‐plane BP/Co₂P heterostructures. Owing to disposition on the original defects of BP, Co₂P improves the conductivity and offers more active electrocatalytic sites, so that the BP/Co₂P nanosheets exhibit better and more stable electrocatalytic activities in the hydrogen evolution and oxygen evolution reactions. Our work not only extends the application of BP to electrochemistry, but also provides a new idea to improve the performance of BP by utilization of defects. Furthermore, this strategy can be extended to produce other BP heterostructures to expand the corresponding applications.     

Tunable Excitation-Dependent Photoluminescences Using Energy Gap Regulating Photogenerated Electrons Injection Rate from Excited TiO2 Nanoparticles to MoS2 Nanosheets

Russian Journal of Applied Chemistry - Control of the photogenerated electrons transfer rate from TiO2 nanoparticles to MoS2 nanosheets is an effective method for modulating the optical property of...     

Nature of the Lewis acid sites on molybdenum and ruthenium sulfides: an electrostatic potential study

The energy of formation and the Lewis acid strength of sulfur vacancies or coordinative unsaturated sites on the MoS2 edges were studied using density functional theory for periodic systems and an electrostatic potential-based methodology. The results suggest that the more energetically favorable sites are located on the sulfur edges; however, their Lewis acid strength is considerably smaller than the site acidity at the molybdenum edges. The acid strength for the reported most hydrodesulfurization active site of RuS2 was also determined. In general, the Lewis acid for the site on RuS2 is 100% smaller than the sites on the Mo edges and around 20% larger than the most favorable site on the S edges of MoS2. Binding of the pyridine molecule in the eta1 adsorption configuration on the considered sites has corroborated the trend of Lewis acidity suggested by the electrostatic potential methodology.     

Selective etching of graphene edges by hydrogen plasma

We devised a controlled hydrogen plasma reaction at 300 °C to etch graphene and graphene nanoribbons (GNRs) selectively at the edges over the basal plane. Atomic force microscope imaging showed that the etching rates for single-layer and few-layer (≥2 layers) graphene are 0.27 ± 0.05 nm/min and 0.10 ± 0.03 nm/min, respectively. Meanwhile, Raman spectroscopic mapping revealed no D band in the planes of single-layer or few-layer graphene after the plasma reaction, suggesting selective etching at the graphene edges without introducing defects in the basal plane. We found that hydrogen plasma at lower temperature (room temperature) or a higher temperature (500 °C) could hydrogenate the basal plane or introduce defects in the basal plane. Using the hydrogen plasma reaction at the intermediate temperature (300 °C), we obtained narrow, presumably hydrogen terminated GNRs (sub-5 nm) by etching of wide GNRs derived from unzipping of multiwalled carbon nanotubes. Such GNRs exhibited semiconducting characteristics with high on/off ratios (～1000) in GNR field effect transistor devices at room temperature.     

Ab initio study of sorption on pyrophyllite: structure and acidity of the edge sites

Pyrophyllite, Al2[Si4O10](OH)2, is the simplest structural prototype for 2:1 dioctahedral phyllosilicates. Since it does not possess permanent structural charge as other clay minerals do, it is used to investigate sorption properties of the clay surfaces not related to the permanent structural charge. The bulk structure and surface geometries of pyrophyllite have been modeled using an orthorhombic constrained supercell. The results of the calculations are in excellent agreement with available experimental data and earlier ab initio simulations. It is shown that the symmetry-constrained model is able to accurately reproduce the basic structural characteristic of pyrophyllite. The electrostatic potential near the (001) surface was used to analyze a possible scenario for the water sorption on the basal plane of pyrophyllite. The calculations predict a slightly hydrophobic behavior of the basal plane. The hydronium ion was found to form a strongly bonded conformation in the siloxane cavity. The relative stability and composition of lateral facets of pyrophyllite have been studied using the supercell approach. The crystals of pyrophyllite are predicted to have a prismatic habit dominated by (110) and (-110) edge facets and basal plane. On the basis of the Fukui functions and the relative protonation/deprotonation enthalpies, the relative acidity and density of the reactive surface sites have been predicted. The triple bond Al-O-Si triple bond sites have the highest proton affinity on the (100), (110), and (130) facets and three line sign Al-OH groups on the (010) edges. The deprotonation of the triple bond Al-OH2 sites is followed by triple bond Al-OH and triple bond Si-OH groups. The calculations suggest a new scale for acidities of edge sites in pyrophyllite that should facilitate the thermodynamic modeling of the sorption processes in compacted clays.