State Key Laboratory of Inorganic Synthesis and Preparative Chemistry

Sustainable hydrogen production is an essential prerequisite of a future hydrogen economy. Water electrolysis driven by renewable resource-derived electricity and direct solar-to-hydrogen conversion based on photochemical and photoelectrochemical water splitting are promising pathways for sustainable hydrogen production. All these techniques require, among many things, highly active noble metal-free hydrogen evolution catalysts to make the water splitting process more energy-efficient and economical. In this review, we highlight the recent research efforts toward the synthesis of noble metal-free electrocatalysts, especially at the nanoscale, and their catalytic properties for the hydrogen evolution reaction (HER). We review several important kinds of heterogeneous non-precious metal electrocatalysts, including metal sulfides, metal selenides, metal carbides, metal nitrides, metal phosphides, and heteroatom-doped nanocarbons. In the discussion, emphasis is given to the synthetic methods of these HER electrocatalysts, the strategies of performance improvement, and the structure/composition-catalytic activity relationship. We also summarize some important examples showing that non-Pt HER electrocatalysts could serve as efficient cocatalysts for promoting direct solar-to-hydrogen conversion in both photochemical and photoelectrochemical water splitting systems, when combined with suitable semiconductor photocatalysts.

The applications of copper (Cu) and Cu-based nanoparticles, which are based on the earth-abundant and inexpensive copper metal, have generated a great deal of interest in recent years, especially in the field of catalysis. The possible modification of the chemical and physical properties of these nanoparticles using different synthetic strategies and conditions and/or via postsynthetic chemical treatments has been largely responsible for the rapid growth of interest in these nanomaterials and their applications in catalysis. In addition, the design and development of novel support and/or multimetallic systems (e.g., alloys, etc.) has also made significant contributions to the field. In this comprehensive review, we report different synthetic approaches to Cu and Cu-based nanoparticles (metallic copper, copper oxides, and hybrid copper nanostructures) and copper nanoparticles immobilized into or supported on various support materials (SiO2, magnetic support materials, etc.), along with their applications in catalysis. The synthesis part discusses numerous preparative protocols for Cu and Cu-based nanoparticles, whereas the application sections describe their utility as catalysts, including electrocatalysis, photocatalysis, and gas-phase catalysis. We believe this critical appraisal will provide necessary background information to further advance the applications of Cu-based nanostructured materials in catalysis.

Elaborate design of highly active and stable catalysts from Earth-abundant elements has great potential to produce materials that can replace the noble-metal-based catalysts commonly used in a range of useful (electro)chemical processes. Here we report, for the first time, a synthetic method that leads to in situ growth of {2̅10} high-index faceted Ni3S2 nanosheet arrays on nickel foam (NF). We show that the resulting material, denoted Ni3S2/NF, can serve as a highly active, binder-free, bifunctional electrocatalyst for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Ni3S2/NF is found to give ∼100% Faradaic yield toward both HER and OER and to show remarkable catalytic stability (for >200 h). Experimental results and theoretical calculations indicate that Ni3S2/NF's excellent catalytic activity is mainly due to the synergistic catalytic effects produced in it by its nanosheet arrays and exposed {2̅10} high-index facets.

Metal-organic framework (MOF) materials, which are constructed from metal ions or metal ion clusters and bridging organic linkers, exhibit regular crystalline lattices with relatively well-defined pore structures and interesting properties. As a new class of porous solid materials, MOFs are attractive for a variety of industrial applications including separation membranes - a rapidly developing research area. Many reports have discussed the synthesis and applications of MOFs and MOF thin films, but relatively few have addressed MOF membranes. This critical review provides an overview of the diverse MOF membranes that have been prepared, beginning with a brief introduction to the current techniques for the fabrication of MOF membranes. Gas and liquid separation applications with different MOF membranes are also included (175 references).

Diamonds are forever: A diamond-like framework in which the C–C bonds are replaced with rigid phenyl rings (see picture) is not only structurally stable but also has a large internal surface area. This porous aromatic framework (PAF-1) demonstrates high uptake capacities of hydrogen and carbon dioxide as well as benzene and toluene vapors, and has an unprecedented surface area of 7100 m2 g−1. Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Three-dimensional porous crystalline polyimide covalent organic frameworks (termed PI-COFs) have been synthesized. These PI-COFs feature non- or interpenetrated structures that can be obtained by choosing tetrahedral building units of different sizes. Both PI-COFs show high thermal stability (>450 °C) and surface area (up to 2403 m(2) g(-1)). They also show high loading and good release control for drug delivery applications.

Metal-organic frameworks (MOFs) are an interesting and useful class of coordination polymers, constructed from metal ion/cluster nodes and functional organic ligands through coordination bonds, and have attracted extensive research interest during the past decades. Due to the unique features of diverse compositions, facile synthesis, easy surface functionalization, high surface areas, adjustable porosity, and tunable biocompatibility, MOFs have been widely used in hydrogen/methane storage, catalysis, biological imaging and sensing, drug delivery, desalination, gas separation, magnetic and electronic devices, nonlinear optics, water vapor capture, etc. Notably, with the rapid development of synthetic methods and surface functionalization strategies, smart MOF-based nanocomposites with advanced bio-related properties have been designed and fabricated to meet the growing demands of MOF materials for biomedical applications. This work outlines the synthesis and functionalization and the recent advances of MOFs in biomedical fields, including cargo (drugs, nucleic acids, proteins, and dyes) delivery for cancer therapy, bioimaging, antimicrobial, biosensing, and biocatalysis. The prospects and challenges in the field of MOF-based biomedical materials are also discussed.

Despite being technically possible, splitting water to generate hydrogen is still practically unfeasible due mainly to the lack of sustainable and efficient catalysts for the half reactions involved. Herein we report the synthesis of cobalt-embedded nitrogen-rich carbon nanotubes (NRCNTs) that 1) can efficiently electrocatalyze the hydrogen evolution reaction (HER) with activities close to that of Pt and 2) function well under acidic, neutral or basic media alike, allowing them to be coupled with the best available oxygen-evolving catalysts-which also play crucial roles in the overall water-splitting reaction. The materials are synthesized by a simple, easily scalable synthetic route involving thermal treatment of Co(2+) -embedded graphitic carbon nitride derived from inexpensive starting materials (dicyandiamide and CoCl2 ). The materials' efficient catalytic activity is mainly attributed to their nitrogen dopants and concomitant structural defects.

Covalent organic frameworks (COFs), as an emerging class of crystalline porous polymers connected by dynamic covalent bonds, have been well studied over the past decade. Recently, three dimensional (3D) COFs have attracted extensive interest for the synthesis and applications of novel COFs. The principal reason for this rising trend is based on their unique porous features and excellent performances compared to previously reported two dimensional (2D) frameworks with the layered AA-stacking mode. This critical review describes the current state-of-the-art development of 3D COFs in the design principles, synthetic methods, functionalization strategies, and potential applications. Some major challenges associated with future perspectives are further discussed, inspiring the development of 3D COFs.

Conventional synthesis of inorganic materials relies heavily on water and organic solvents. Alternatively, the synthesis of inorganic materials using, or in the presence of, ionic liquids represents a burgeoning direction in materials chemistry. Use of ionic liquids in solvent extraction and organic catalysis has been extensively studied, but their use in inorganic synthesis has just begun. Ionic liquids are a family of non-conventional molten salts that can act as templates and precursors to inorganic materials, as well as solvents. They offer many advantages, such as negligible vapor pressures, wide liquidus ranges, good thermal stability, tunable solubility for both organic and inorganic molecules, and much synthetic flexibility. In this Review, the use of ionic liquids in the preparation of several categories of inorganic and hybrid materials (i.e., metal structures, non-metal elements, silicas, organosilicas, metal oxides, metal chalcogenides, metal salts, open-framework structures, ionic liquid-functionalized materials, and supported ionic liquids) is summarized. The status quo of the research field is assessed, and some future perspectives are furnished.

In our efforts to obtain electrocatalysts with improved activity for water splitting, meticulous design and synthesis of the active sites of the electrocatalysts and deciphering how exactly they catalyze the reaction are vitally necessary. Herein, we report a one-step facile synthesis of a novel precious-metal-free hydrogen-evolution nanoelectrocatalyst, dubbed Mo2 C@NC that is composed of ultrasmall molybdenum carbide (Mo2 C) nanoparticles embedded within nitrogen-rich carbon (NC) nanolayers. The Mo2 C@NC hybrid nanoelectrocatalyst shows remarkable catalytic activity, has great durability, and gives about 100 % Faradaic yield toward the hydrogen-evolution reaction (HER) over a wide pH range (pH 0-14). Theoretical calculations show that the Mo2 C and N dopants in the material synergistically co-activate adjacent C atoms on the carbon nanolayers, creating superactive nonmetallic catalytic sites for HER that are more active than those in the constituents.

Hydrogen production through electrochemical process is at the heart of key renewable energy technologies including water splitting and hydrogen fuel cells. Despite tremendous efforts, exploring cheap, efficient and durable electrocatalysts for hydrogen evolution still remains as a great challenge. Here we synthesize a nickel-carbon-based catalyst, from carbonization of metal-organic frameworks, to replace currently best-known platinum-based materials for electrocatalytic hydrogen evolution. This nickel-carbon-based catalyst can be activated to obtain isolated nickel atoms on the graphitic carbon support when applying electrochemical potential, exhibiting highly efficient hydrogen evolution performance with high exchange current density of 1.2 mA cm(-2) and impressive durability. This work may enable new opportunities for designing and tuning properties of electrocatalysts at atomic scale for large-scale water electrolysis.

The key to soc-cess: The trimer building block [In3O(CO2)6] and a tetracarboxylate organic linker assemble into a novel porous metal–organic framework (see picture; In green, C gray, N blue, O red; cavity: yellow sphere) having an unprecedented soc topology (soc=square–octahedron) and high H2 uptake. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2007/z604306_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Abstract In our efforts to obtain electrocatalysts with improved activity for water splitting, meticulous design and synthesis of the active sites of the electrocatalysts and deciphering how exactly they catalyze the reaction are vitally necessary. Herein, we report a one‐step facile synthesis of a novel precious‐metal‐free hydrogen‐evolution nanoelectrocatalyst, dubbed Mo 2 C@NC that is composed of ultrasmall molybdenum carbide (Mo 2 C) nanoparticles embedded within nitrogen‐rich carbon (NC) nanolayers. The Mo 2 C@NC hybrid nanoelectrocatalyst shows remarkable catalytic activity, has great durability, and gives about 100 % Faradaic yield toward the hydrogen‐evolution reaction (HER) over a wide pH range (pH 0–14). Theoretical calculations show that the Mo 2 C and N dopants in the material synergistically co‐activate adjacent C atoms on the carbon nanolayers, creating superactive nonmetallic catalytic sites for HER that are more active than those in the constituents.

Using commercially activated carbon, we developed a simple and effective direct chemical oxidation route to prepare good biocompatible multicolor photoluminescent carbon dots.

A historical overview of the activation and porosity of MOFs including strategies to design and preserve permanent porosity in MOFs.

Reactive oxygen species (ROS) plays a key role in therapeutic effects as well as side effects of platinum drugs. Cisplatin mediates activation of nicotinamide adenine dinucleotide phosphate (NADPH) oxidase (NOX), which triggers oxygen (O2) to superoxide radical (O2•–) and its downstream H2O2. Through the Fenton’s reaction, H2O2 could be catalyzed by Fe2+/Fe3+ to the toxic hydroxyl radicals (•OH), which cause oxidative damages to lipids, proteins, and DNA. By taking the full advantage of Fenton’s chemistry, we herein demonstrated tumor site-specific conversion of ROS generation induced by released cisplatin and Fe2+/Fe3+ from iron-oxide nanocarriers with cisplatin(IV) prodrugs for enhanced anticancer activity but minimized systemic toxicity.

Well-dispersed and ultrasmall Pd clusters in nanosized silicalite-1 (MFI) zeolite have been prepared under direct hydrothermal conditions using [Pd(NH2CH2CH2NH2)2]Cl2 as precursor. High-resolution scanning transmission electron microscopy studies indicate that the Pd clusters are encapsulated within the intersectional channels of MFI, and the Pd clusters in adjacent channels visually aggregate, forming nanoparticles (NPs) of ∼1.8 nm. The resultant catalysts show an excellent activity and highly efficient H2 generation toward the complete decomposition of formic acid (FA) under mild conditions. Notably, thanks to the further reduced Pd NP size (∼1.5 nm) and the additionally introduced basic sites, the Pd/S-1-in-K catalyst affords turnover frequency values up to 856 h(-1) at 25 °C and 3027 h(-1) at 50 °C. The easy in situ confinement synthesis of metal clusters in zeolites endows the catalysts with superior catalytic activities, excellent recyclability, and high thermal stability, thus opening new perspectives for the practical application of FA as a viable and effective H2 storage material for use in fuel cells.

The design and synthesis of 3D covalent organic frameworks (COFs) have been considered a challenge, and the demonstrated applications of 3D COFs have so far been limited to gas adsorption. Herein we describe the design and synthesis of two new 3D microporous base-functionalized COFs, termed BF-COF-1 and BF-COF-2, by the use of a tetrahedral alkyl amine, 1,3,5,7-tetraaminoadamantane (TAA), combined with 1,3,5-triformylbenzene (TFB) or triformylphloroglucinol (TFP). As catalysts, both BF-COFs showed remarkable conversion (96% for BF-COF-1 and 98% for BF-COF-2), high size selectivity, and good recyclability in base-catalyzed Knoevenagel condensation reactions. This study suggests that porous functionalized 3D COFs could be a promising new class of shape-selective catalysts.

The search for new zeolites is of continuous interest in the field of zeolite science because of their widespread application in catalysis and adsorption-separation. To this end, considerable efforts have been devoted to the preparation of new zeolites with novel porous architectures and compositions. Taking account of the key factors governing the formation of zeolites (e.g., guest species, framework elements, construction processes, etc.), several synthetic strategies have been developed recently. These allow the discovery of many new zeolites with unprecedented structural features, such as hierarchical pores, odd-ring numbers (11-, 15-rings), extra-large pores (16-, 18-, 20-, 28-, and 30-rings), chiral pores, and extremely complex framework topologies, etc. In this review, we will present the advances in the synthesis of new zeolite structures in the last decade, which are achieved by utilization of the synthetic strategies based on pre-designed structure-directing agents, heteroatom substitution, and topotactic transformations.