Renzhi Ma

Nanosheets of Oxides and Hydroxides: Ultimate 2D Charge‐Bearing Functional Crystallites

A wide variety of cation-exchangeable layered transition metal oxides and their relatively rare counterparts, anion-exchangeable layered hydroxides, have been exfoliated into individual host layers, i.e., nanosheets. Exfoliation is generally achieved via a high degree of swelling, typically driven either by intercalation of bulky organic ions (quaternary ammonium cations, propylammonium cations, etc.) for the layered oxides or by solvation with organic solvents (formamide, butanol, etc.) for the hydroxides. Ultimate two-dimensional (2D) anisotropy for the nanosheets, with thickness of around one nanometer versus lateral size ranging from submicrometer to several tens of micrometers, allows them to serve either as an ideal quantum system for fundamental study or as a basic building block for functional assembly. The charge-bearing inorganic macromolecule-like nanosheets can be assembled or organized through various solution-based processing techniques (e.g., flocculation, electrostatic sequential deposition, or the Langmuir-Blodgett method) to produce a range of nanocomposites, multilayer nanofilms, and core-shell nanoarchitectures, which have great potential for electronic, magnetic, optical, photochemical, and catalytic applications.

Exfoliating layered double hydroxides in formamide: a method to obtain positively charged nanosheets

Exfoliation of layered double hydroxides (LDHs) into single layers provides a new type of nanosheet with ultimate two-dimensional anisotropy and positive charge. In this Highlight article, we briefly review the latest advances in this emerging field. In comparison with the previous studies, we show that micrometer-sized and well-defined LDH nanosheets can be readily attained by synthesizing large crystals of LDH-carbonate via so-called homogeneous precipitation and subsequent exfoliation of the nitrate form in formamide. Some general aspects including the exfoliating process and characterization, a plausible delaminating mechanism, and future challenges, are presented and discussed.

A Superlattice of Alternately Stacked Ni–Fe Hydroxide Nanosheets and Graphene for Efficient Splitting of Water

Cost-effective electrocatalysts based on nonprecious metals for efficient water splitting are crucial for various technological applications represented by fuel cell. Here, 3d transition metal layered double hydroxides (LDHs) with varied contents of Ni and Fe were successfully synthesized through a homogeneous precipitation. The exfoliated Ni-Fe LDH nanosheets were heteroassembled with graphene oxide (GO) as well as reduced graphene oxide (rGO) into superlattice-like hybrids, in which two kinds of oppositely charged nanosheets are stacked face-to-face in alternating sequence. Heterostructured composites of Ni2/3Fe1/3 LDH nanosheets and GO (Ni2/3Fe1/3-GO) exhibited an excellent oxygen evolution reaction (OER) efficiency with a small overpotential of about 0.23 V and Tafel slope of 42 mV/decade. The activity was further improved via the combination of Ni2/3Fe1/3 LDH nanosheets with more conductive rGO (Ni2/3Fe1/3-rGO) to achieve an overpotential as low as 0.21 V and Tafel plot of 40 mV/decade. The catalytic activity was enhanced with an increased Fe content in the bimetallic Ni-Fe system. Moreover, the composite catalysts were found to be effective for hydrogen evolution reaction. An electrolyzer cell powered by a single AA battery of 1.5 V was demonstrated by using the bifunctional catalysts.

General Synthesis and Structural Evolution of a Layered Family of Ln8(OH)20Cl4·nH2O (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Y)

The synthesis process and crystal structure evolution for a family of stoichiometric layered rare-earth hydroxides with general formula Ln(8)(OH)(20)Cl(4) x nH(2)O (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Y; n approximately 6-7) are described. Synthesis was accomplished through homogeneous precipitation of LnCl(3) x xH(2)O with hexamethylenetetramine to yield a single-phase product for Sm-Er and Y. Some minor coexisting phases were observed for Nd(3+) and Tm(3+), indicating a size limit for this layered series. Light lanthanides (Nd, Sm, Eu) crystallized into rectangular platelets, whereas platelets of heavy lanthanides from Gd tended to be of quasi-hexagonal morphology. Rietveld profile analysis revealed that all phases were isostructural in an orthorhombic layered structure featuring a positively charged layer, [Ln(8)(OH)(20)(H(2)O)(n)](4+), and interlayer charge-balancing Cl(-) ions. In-plane lattice parameters a and b decreased nearly linearly with a decrease in the rare-earth cation size. The interlamellar distance, c, was almost constant (approximately 8.70 A) for rare-earth elements Nd(3+), Sm(3+), and Eu(3+), but it suddenly decreased to approximately 8.45 A for Tb(3+), Dy(3+), Ho(3+), and Er(3+), which can be ascribed to two different degrees of hydration. Nd(3+) typically adopted a phase with high hydration, whereas a low-hydration phase was preferred for Tb(3+), Dy(3+), Ho(3+), Er(3+), and Tm(3+). Sm(3+), Eu(3+), and Gd(3+) samples were sensitive to humidity conditions because high- and low-hydration phases were interconvertible at a critical humidity of 10%, 20%, and 50%, respectively, as supported by both X-ray diffraction and gravimetry as a function of the relative humidity. In the phase conversion process, interlayer expansion or contraction of approximately 0.2 A also occurred as a possible consequence of absorption/desorption of H(2)O molecules. The hydration difference was also evidenced by refinement results. The number of coordinated water molecules per formula weight, n, changed from 6.6 for the high-hydration Gd sample to 6.0 for the low-hydration Gd sample. Also, the hydration number usually decreased with increasing atomic number; e.g., n = 7.4, 6.3, 7.2, and 6.6 for high-hydration Nd, Sm, Eu, and Gd, and n = 6.0, 5.8, 5.6, 5.4, and 4.9 for low-hydration Gd, Tb, Dy, Ho, and Er. The variation in the average Ln-O bond length with decreasing size of the lanthanide ions is also discussed. This family of layered lanthanide compounds highlights a novel chemistry of interplay between crystal structure stability and coordination geometry with water molecules.

Two-Dimensional Oxide and Hydroxide Nanosheets: Controllable High-Quality Exfoliation, Molecular Assembly, and Exploration of Functionality

CONSPECTUS: Two-dimensional (2D) materials, represented by graphene, have attracted tremendous interest due to their ultimate structural anisotropy and fascinating resultant properties. The search for 2D material alternatives to graphene, molecularly thin with diverse composition, structure, and functionality, has become a hot research topic. A wide variety of layered metal oxides and hydroxides have been exfoliated into the form of individual host layers, that is, 2D nanosheets. This Account presents an overview of 2D oxide and hydroxide nanosheets on the following subtopics: (1) controllable preparation of high-quality nanosheets and (2) molecular assembly and the exploration of functionality of the nanosheets. High-quality exfoliation is generally achieved via a multistep soft chemical process, comprised of ion-exchange, osmotic swelling, and exfoliation. A high degree of hydration-induced swelling, typically triggered by intercalation of organo-ammonium ions, is a critical stage leading to the high-yield production of molecularly thin nanosheets. Recent studies reveal that massive swelling, an astounding ∼100 times the original size, can be induced by a range of amine solutions. The degree of swelling is controlled by the balance of osmotic pressure between the inner gallery and the outer electrolyte solution, which is strongly influenced by amine molarity. Conversely, the stability of the resultant swollen structure is dependent on the chemical nature of the amine/ammonium ions. Particular species of lower polarity and bulky size, for example, quaternary ammonium ions, are beneficial in promoting exfoliation. Rational design and tuning of the lateral dimension, chemical composition, and structure of nanosheets are vital in exploring diverse functionalities. The lateral dimension of the nanosheets can be tuned by controlling the crystal size of the parent layered compounds, as well as the kinetics of the exfoliating reaction, for example, the type of amine/ammonium ions, their concentration, and the mode of exfoliation (manual versus mechanical shaking, etc.). Employing optimum conditions enables the production of high-quality nanosheets with a lateral size as large as several tens of micrometers. A couple of examples tailoring the nanosheets have been demonstrated with a highlight on a novel class of 2D perovskite-type oxide nanosheets with a finely tuned composition and a progressively increasing thickness at a step of 0.4-0.5 nm (corresponding to the height of the MO6 octahedron). The charge-bearing nanosheets can be organized through solution-based molecular assembly techniques (e.g., electrostatic layer-by-layer deposition, Langmuir-Blodgett method) to produce highly organized nanofilms, superlattices, etc., the exploration of which holds great potential for the development of various electronic and optical applications, among others.

Anion-exchangeable layered materials based on rare-earth phosphors: unique combination of rare-earth host and exchangeable anions.

Layered materials, three-dimensional crystals built from stacking two-dimensional components, are attracting intense interest because of their structural anisotropy and the fascinating properties that result. However, the range of such layered materials that can exchange anions is quite small. Continuing efforts have been underway to identify a new class of anion-exchangeable materials. One major goal is the incorporation of rare-earth elements within the host because researchers expect that the marriage of rare-earth skeleton host and the exchangeable species within the interlayer will open up new avenues both for the assembly of layered materials and for the understanding of rare-earth element chemistry. Such lanthanide layered solids have industrial potential. These materials are also of academic importance, serving as an ideal model for studying the cationic size effect on structure stability associated with lanthanide contraction. In this Account, we present the work done by ourselves and others on this novel class of materials. We examine the following four subtopics regarding these layered anionic materials: (1) synthesis strategy and composition diversity, (2) structural features, (3) structure stability with relative humidity, and (4) applications. These materials can be synthesized either by hydrothermal reactions or by homogeneous precipitation, and a variety of anions can be intercalated into the gallery. Although only cations with a suitable size can form the layered structure, the possible range is wide, from early to late lanthanides. We illustrate the effect of lanthanide contraction on properties including morphology, lattice dimensions, and coordination numbers. Because each lanthanide metal ion coordinates water molecules, and the water molecules point directly into the gallery space, this feature plays a critical role in stabilizing the layered structure. In the 9-fold monocapped square antiprism structure, the humidity-triggered transition between high- and low-hydrated phases corresponds to the uptake of H(2)O molecules at the capping site, which provides further evidence of the importance of water coordination. Applications using this unique combination of rare-earth element chemistry and layered materials include ion-exchange, photoluminescence, catalysis, and biomedical devices. Further exploration of the compounds and new methods for functional modification would dramatically enrich the junction of these two fields, leading to a new generation of layered materials with desirable properties.

A General Strategy to Layered Transition‐Metal Hydroxide Nanocones: Tuning the Composition for High Electrochemical Performance

A general and facile strategy for the synthesis of a large family of monometallic (Co, Ni) and bimetallic (Co-Ni, Co-Cu and Co-Zn) hydroxide nanocones (NCs) intercalated with DS ions is demonstrated. The basal spacing of the NCs can be varied by adjusting the intercalated DS amount. Especially, electrochemical characterizations reveal that bimetallic Co-Ni hydroxide NCs have a higher specific capacitance than their monometallic counterpart. These results suggest the importance of rational designing layered hydroxide NCs with tuned transition-metal composition for high-performance energy storage devices.

New Layered Rare‐Earth Hydroxides with Anion‐Exchange Properties

We report the synthesis of a new series of layered hydroxides based on rare-earth elements with a composition of RE(OH)2.5Cl(0.5).0.8 H2O (RE: Eu, Tb, etc.) through the homogeneous precipitation of RECl3.x H2O with hexamethylenetetramine (HMT). Rietveld analysis combined with direct methods revealed an orthorhombic layered structure comprising a positively charged layer of [RE(OH)2.5-(H2O)0.8]0.5+ and interlayer Cl- ions. The Cl- ions were readily exchangeable for various anions (NO3-, SO4(2-), dodecylsulfonate, etc.) at ambient temperature. Photoluminescence studies showed that the compounds display typical RE3+ emission. With rare-earth-based host layers and tunable interlayer guests, the new compounds may be of interest for optoelectronic, magnetic, catalytic, and biomedical materials.

Topochemical synthesis of Co-Fe layered double hydroxides at varied Fe/Co ratios: unique intercalation of triiodide and its profound effect.

Co-Fe layered double hydroxides at different Fe/Co ratios were synthesized from brucite-like Co(2+)(1-x)Fe(2+)(x)(OH)(2) (0 ≤ x ≤ 1/3) via oxidative intercalation reaction using an excess amount of iodine as the oxidizing agent. A new redoxable species: triiodide (I(3)(-)), promoted the formation of single-phase Co-Fe LDHs. The results point to a general principle that LDHs with a characteristic ratio of total trivalent and divalent cations (M(3+)/M(2+)) at 1/2 may be the most stable in the oxidative intercalation procedure. At low Fe content, e.g., starting from Co(2+)(1-x)Fe(2+)(x)(OH)(2) (x < 1/3), partial oxidation of Co(2+) to Co(3+) takes place to reach the M(3+)/M(2+) threshold of 1/2 in as-transformed Co(2+)(2/3)-(Co(3+)(1/3-x)-Fe(3+)(x)) LDHs. Also discovered was the cointercalation of triiodide and iodide into the interlayer gallery of as-transformed LDH phase, which profoundly impacted the relative intensity ratio of basal Bragg peaks as a consequence of the significant X-ray scattering power of triiodide. In combination with XRD simulation, the LDH structure model was constructed by considering both the host layer composition/charge and the arrangement of interlayer triiodide/iodide. The work provides a clear understanding of the thermodynamic and kinetic factors associated with the oxidative intercalation reaction and is helpful in elucidating the formation of LDH structure in general.

Oriented Monolayer Film of Gd2O3:0.05 Eu Crystallites: Quasi‐Topotactic Transformation of the Hydroxide Film and Drastic Enhancement of Photoluminescence Properties

Caught on film: A semitransparent and intensely luminescent monolayer film of oriented Gd(2)O(3):0.05 Eu platelet crystallites is fabricated by annealing the precursor hydroxide film (see scheme). The photoluminescence properties of the as-transformed film are greatly improved over those of the hydroxide film, and are much more pronounced than those of the corresponding Gd(2)O(3):0.05 Eu powder.