Electronic communications between active sites on individual metallic nanoparticles in catalysis.

Catalytic activity of metal particles is reported to originate from the appearance of nonmetallic states, but conductive metallic particles, as an electron reservoir, should render electron delivery between reactants more favorably so as to have higher activity. We present that metallic rhodium particle catalysts are highly active in the low-temperature oxidation of carbon monoxide, whereas nonmetallic rhodium clusters or monoatoms on alumina remain catalytically inert. Experimental and theoretical results evidence the presence of electronic communications in between vertex atom active sites of individual metallic particles in the reaction.

Restructuring and Hydrogen Evolution on Sub-Nanosized PdB Clusters.

As a Pt-group element, Pd has been regarded as one of the alternatives to Pt-based catalysts for the hydrogen evolution reaction (HER). Herein, we performed density functional theory (DFT) computations to explore the most stable structures of PdB ( = 6, 19, 44), revealed the in situ structural reconstruction of these clusters under acidic conditions, and evaluated their HER activity. We found that the presence of B can prevent underpotential hydrogen adsorption and activate the H atoms on the cluster surface for the HER.

A stacked transmembrane electro-chemisorption system connected by hydrophobic gas permeable membranes for on-site utilization of authigenic acid and base to enhance ammonia recovery from wastewater.

The ammonia recovery from wastewater via electrochemical technologies represents a promising way for wastewater treatment, resource recovery, and carbon emissions reduction. However, chemicals consumption and reactors scalability of the existing electrochemical systems have become the key challenges for their development and application. In this study, a stacked transmembrane electro-chemisorption (sTMECS) system was developed to utilize authigenic acid and base on site for enhancing ammonia recovery from wastewater.

Enabling Logistics Automation in Nanofactory: Cobalt Phosphide Embedded Metal-Organic Frameworks for Efficient Electrocatalytic Nitrate Reduction to Ammonia.

Electrocatalytic nitrate reduction reaction (NitRR) in neutral condition offers a promising strategy for green ammonia synthesis and wastewater treatment, the rational design of electrocatalysts is the cornerstone. Inspired by modern factory design where both machines and logistics matter for manufacturing, it is reported that cobalt phosphide (CoP) nanoparticles embedded in zinc-based zeolite imidazole frameworks (Zn-ZIF) function as a nanofactory with high performance. By selective phosphorization of ZnCo bimetallic zeolite imidazole framework (ZnCo-ZIF), the generated CoP nanoparticles act as "machines" (active sites) for molecular manufacturing (NO to NH conversion).

Robust Covalent Organic Framework Photocatalysts for HO Production: Linkage Position Matters.

Covalent organic frameworks (COFs) are promising photocatalysts for hydrogen peroxide (HO) synthesis. However, the nature of organic polymers makes the balance between high activity and stability challenging. We demonstrate that the linkage position matters in the design of robust COF photocatalysts with durable high activity without sacrificial reagents.

Three-Dimensional Hydrogen-Bonded Porous Metal-Organic Framework for Natural Gas Separation with High Selectivity.

A 3D hydrogen-bonded metal-organic framework, [Cu(apc)] (, Hapc = 2-aminopyrimidine-5-carboxylic acid), was synthesized via a solvothermal reaction. The activated with permanent porosity exhibits a moderate uptake of 1.52 wt% of hydrogen gas at 77 K.

Epitaxial growth of metal-organic framework nanosheets into single-crystalline orthogonal arrays.

Construction of two-dimensional nanosheets into three-dimensional regular structures facilitates the mass transfer and exploits the maximum potential of two-dimensional building blocks in applications such as catalysis. Here, we report the synthesis of metal-organic frameworks with an orthogonal nanosheet array. The assembly involves the epitaxial growth of single crystalline metal-organic framework nanosheets with a naturally non-preferred facet exposure as the shell on a cubic metal-organic framework as the core.

Highly-Exposed Co-CoO Derived from Nanosized ZIF-67 on N-Doped Porous Carbon Foam as Efficient Electrocatalyst for Zinc-Air Battery.

Non-precious-metal based electrocatalysts with highly-exposed and well-dispersed active sites are crucially needed to achieve superior electrocatalytic performance for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) toward zinc-air battery (ZAB). Herein, Co-CoO heterostructures derived from nanosized ZIF-67 are densely-exposed and strongly-immobilized onto N-doped porous carbon foam (NPCF) through a self-sacrificial pyrolysis strategy. Benefited from the high exposure of Co-CoO heterostructures and the favorable mass and electron transfer ability of NPCF, the Co-CoO/NPCF electrocatalyst exhibits remarkable performance for both ORR (E  = 0.

Crystal Engineering Enables Cobalt-Based Metal-Organic Frameworks as High-Performance Electrocatalysts for HO Production.

Metal-organic frameworks (MOFs) with highly adjustable structures are an emerging family of electrocatalysts in two-electron oxygen reduction reaction (2e-ORR) for HO production. However, the development of MOF-based 2e-ORR catalysts with high HO selectivity and production rate remains challenging. Herein, an elaborate design with fine control over MOFs at both atomic and nano-scale is demonstrated, enabling the well-known Zn/Co bimetallic zeolite imidazole frameworks (ZnCo-ZIFs) as excellent 2e-ORR electrocatalysts.

Toward Large Second-Harmonic Generation and Deep-UV Transparency in Strongly Electropositive Transition Metal Sulfates.

The development of deep-ultraviolet (DUV)/solar-blind UV nonlinear optical (NLO) crystals simultaneously possessing wide UV transparency, strong second-harmonic generation (SHG) response, and suitable birefringence is a major challenge in advanced laser technology. We herein propose a "cation compensation" strategy for strong optical nonlinearity in inorganic solids that is exemplified by the introduction of strongly electropositive transition metals (TMs). Following this strategy, the first d TM UV-transparent NLO sulfates, MF(SO) (M = Zr (ZFSO), Hf (HFSO)), have been synthesized.

Additive-Triggered Polar Polymorph Formation: β-Sc(IO ) , a Promising Next-Generation Mid-Infrared Nonlinear Optical Material.

Noncentrosymmetric (NCS) solids have attracted interest for their potential in ferroelectric, piezoelectric, and nonlinear optical (NLO) devices, but their synthesis remains a major challenge. In this study, the additive Li CO triggers formation of an NCS precursor at an early nucleation stage, and plays a crucial role in the successful polymorphism transformation. The resultant metastable β-Sc(IO ) is a promising mid-infrared NLO crystal, with the strongest second-harmonic generation responses (2.

Preferential and efficient degradation of phenolic pollutants with cooperative hydrogen-bond interactions in photocatalytic process.

Phenolic pollutants as highly toxic and hazardous organics are widely generated from industrial and domestic process. Phenolic pollutants with different hydroxyl position (catechol, resorcinol, hydroquinone, phenol) were preferentially and efficiently oxidized in photocatalytic process (PC) by designing boron-doped TiO (B-TiO).The key role for enhancing the photocatalytic activity of B-TiO was the formation of abundant Ti species.

Efficient photocatalytic removal of phthalates easily implemented over a bi-functional {001}TiO surface.

It is stubborn to remove the lowly concentrated phthalic acid esters (PAEs) that usually coexist with other highly concentrated but low-toxic pollutants in municipal sewage. Herein, we report a novel strategy for completely removing the PAEs over a bi-functional {001}TiO surface (with highly exposed {001} facet), which not only serve as functional sites to specifically adsorb the target PAEs pollutants, but also contribute to an enhanced oxidation ability. The adsorption behavior of PAEs on {001}TiO is analyzed deeply through kinetic experiments combining with in situ ATR-FTIR spectroscopy and theoretical calculations.

Simply closing the reactor improves the electron efficiency of zerovalent iron toward various metal(loid)s removal.

The controlled corrosion of zerovalent iron (ZVI) is crucial for the favorable performance of ZVI toward metal(loid)s removal, and dissolved oxygen (DO) plays an important role in the process of ZVI corrosion. However, few efforts have been made to control the concentration of DO in real practice. In this study, we found that the electron efficiency and the specific removal capacity of ZVI toward the removal of four metal(loid)s were increased by 1.

Overlooked Role of Fe(IV) and Fe(V) in Organic Contaminant Oxidation by Fe(VI).

Fe(VI) has received increasing attention since it can decompose a wide range of trace organic contaminants (TrOCs) in water treatment. However, the role of short-lived Fe(IV) and Fe(V) in TrOC decomposition by Fe(VI) has been overlooked. Using methyl phenyl sulfoxide (PMSO), carbamazepine, and caffeine as probe TrOCs, we observed that the apparent second-order rate constants () between TrOCs and Fe(VI) determined with the initial kinetics data were strongly dependent on the initial molar ratios of TrOCs to Fe(VI).

Hierarchical Mesoporous MXene-NiCoP Electrocatalyst for Water-Splitting.

The utilization of nonprecious metal electrocatalysts for water-splitting may be the ultimate solution for sustainable and clean hydrogen energy. MXene, an emerging two-dimensional material, exhibits many unique properties such as possible metal-like conductivity, hydrophilic surface, and rich chemistry, rendering a group of promising catalysts and catalyst support materials. In this study, exfoliated TiC MXenes serve as a substrate to perpendicularly grow uniform mesoporous NiCoP nanosheets through an in situ interface-growth strategy and subsequent phosphorization.

Revisiting the NaNiMnO Cathode: Oxygen Redox Chemistry and Oxygen Release Suppression.

Sodium layered transition metal oxides have been considered as promising cathode materials for sodium ion batteries due to their large capacity and high operating voltage. However, mechanism investigations of chemical evolution and capacity failure at high voltage are inadequate. As a representative cathode, NaNiMnO, the capacity contribution at a 4.

Insights into the Oxidation of Organic Cocontaminants during Cr(VI) Reduction by Sulfite: The Overlooked Significance of Cr(V).

Literature works reported that organic cocontaminants could be degraded during Cr(VI), a contaminant, reduction by sulfite (Cr(VI)/sulfite process). However, the role of Cr(V) and Cr(IV) intermediates in the Cr(VI)/sulfite process has been overlooked. In this study, we confirmed the generation of Cr(V) and proposed a new mechanism for the decomposition of coexisting organic contaminants during Cr(VI)/sulfite reactions occurring in oxygenated solutions at pH 4.

Synthesis of orthogonally assembled 3D cross-stacked metal oxide semiconducting nanowires.

Assemblies of metal oxide nanowires in 3D stacks can enable the realization of nanodevices with tailored conductivity, porous structure and a high surface area. Current fabrication methods require complicated multistep procedures that involve the initial preparation of nanowires followed by manual assembly or transfer printing, and thus lack synthesis flexibility and controllability. Here we report a general synthetic orthogonal assembly approach to controllably construct 3D multilayer-crossed metal oxide nanowire arrays.

Amorphous Metal-Organic Framework-Dominated Nanocomposites with Both Compositional and Structural Heterogeneity for Oxygen Evolution.

Amorphous metal-organic frameworks (aMOFs) are an emerging family of attractive materials with great application potential, however aMOFs are usually prepared under harsh conditions and aMOFs with complex compositions and structures are rarely reported. In this work, an aMOF-dominated nanocomposite (aMOF-NC) with both structural and compositional complexity has been synthesized using a facile approach. A ligand-competition amorphization mechanism is proposed based on experimental and density functional theory calculation results.

Mechanistic insight into the generation of reactive oxygen species in sulfite activation with Fe(III) for contaminants degradation.

Since the reactive species during the sulfite activation by Fe(III) (Fe(III)/sulfite process) had not been directly determined and the role of in-situ generated Fe(II) was overlooked, this study evaluated the oxidation performance of the Fe(III)/sulfite process, identified the reactive species, and investigated the role of in-situ generated Fe(II) in this process. The results demonstrated that carbamazepine (CBZ) could be degraded at different sulfite concentrations. Compared to the single-dosing mode, sulfite applied with multiple-dosing mode was beneficial to CBZ removal in this process when the same amount of sulfite was dosed.

In Situ Generation of an N-Heterocyclic Carbene Functionalized Metal-Organic Framework by Postsynthetic Ligand Exchange: Efficient and Selective Hydrosilylation of CO.

The reported metal-organic framework (MOF) catalyst realizes CO to methanol transformation under ambient conditions. The MOF is one rare example containing metal-free N-heterocyclic carbene (NHC) moieties, which are installed using an in situ generation strategy involving the incorporation of an imidazolium bromide based linker into the MOF by postsynthetic ligand exchange. Importantly, the resultant NHC-functionalized MOF is the first catalyst capable of performing quantitative hydrogen transfer from silanes to CO , thus achieving quantitative (>99 %) methanol yield.