Adjusted Preferential Adsorption of Intermediates via Regulation of the Electronic Structure during the Electrocatalytic CO Reduction Process.

The surface electronic structures of catalysts play a crucial role in CO adsorption and activation. Here, sulfur vacancies are introduced into CuInS nanosheets (V-CuInS) to evaluate the effect of electronic structures at the surface-active sites on the electrochemical CO reduction reaction (CORR). V-CuInS exhibits a significant disparity in the highest FE/FE (6.

Electrochemically stable frustrated Lewis pairs on dual-metal hydroxides for electrocatalytic CO reduction.

The sluggish kinetics of CO activation and reduction severely limit the energy conversion efficiency of electrocatalytic CO reduction into fuels. Here, ZnSn(OH) with an alternating arrangement of Zn(OH) and Sn(OH) octahedral units and SrSn(OH) with an alternating arrangement of SrO and Sn(OH) octahedral units were adopted to check the effects of frustrated Lewis pairs (FLPs) on electrochemical CO reduction. The FLPs were electrochemically reconstructed on ZnSn(OH) by reducing the electrochemically unstable Sn-OH to Sn-oxygen vacancies (Sn-O) as a Lewis acid site, which are able to create strong interactions with the adjacent electrochemically stable Zn-OH, a Lewis base site.

Regulated Surface Electronic States of CuNi Nanoparticles through Metal-Support Interaction for Enhanced Electrocatalytic CO Reduction to Ethanol.

Developing stable catalysts with higher selectivity and activity within a wide potential range is critical for efficiently converting CO to ethanol. Here, the carbon-encapsulated CuNi nanoparticles anchored on nitrogen-doped nanoporous graphene (CuNi@C/N-npG) composite are designedly prepared and display the excellent CO reduction performance with the higher ethanol Faradaic effiency (FE  ≥ 60%) in a wide potential window (600 mV). The optimal cathodic energy efficiency (47.

Highly Effective Photocatalytic Radical Reactions Triggered by a Photoactive Metal-Organic Framework.

On account of their inherent reactive properties, radical reactions play an important role in organic syntheses. The booming photochemistry provides a feasible approach to trigger the generation of radical intermediates in organic reaction processes. Thus, developing effective photocatalysts becomes the key step in radical reactions.

Oxygen vacancy and nitrogen doping collaboratively boost performance and stability of TiO-supported Pd catalysts for CO photoreduction: a DFT study.

The regulation of interfacial charge transfer, optimization of active sites, and maintenance of stability are effective strategies for improving catalytic performance. The effect of the oxygen vacancy (V) and nitrogen doping on these parameters for CO photoreduction on Pd/TiO(101) was studied using density functional theory calculations. The results demonstrate that introduction of the V could trigger reversed electron transfer, making the V and Pd atoms the active center for CO reduction.

Amorphous TiO as a multifunctional interlayer for boosting the efficiency and stability of the CdS/cobaloxime hybrid system for photocatalytic hydrogen production.

The construction of both highly efficient and stable hybrid artificial photosynthetic systems comprising semiconductors as photosensitizers and abundant metal-based molecular complexes as cocatalysts for photocatalytic H2 generation remains challenging. Herein, we report an effective and stable CdS/cobaloxime hybrid system prepared by inserting an amorphous TiO2 (a-TiO2) interlayer with adjustable thickness and by covalently-surface-attaching molecular cobaloxime catalysts. This hybrid system displayed outstanding photocatalytic H2 production and reached a maximum rate of ∼25 mmol g-1 h-1, which was ∼20.

ZnGeO/ZnS heterojunctions fabricated via in situ etching sulfurization for Pt-free photocatalytic hydrogen evolution: interface roughness and defect engineering.

Interface engineering has been regarded as a promising strategy for enhancing the catalytic activities of heterojunction photocatalysts. Herein, we have adopted an in situ etching sulfurization method to construct a Zn2GeO4-x/ZnS intimate heterojunction, which exhibited excellent photocatalytic H2 production in the absence of a Pt co-catalyst. Distinctively, TEM and HRTEM measurements showed that the interface of the Zn2GeO4-x/ZnS heterojunction became rough (topologically) due to in situ etching sulfurization, and etching was found to be strongly dependent on the crystal orientation.

Synergistic engineering of architecture and composition in NiCoMoO@CoMoO nanobrush arrays towards efficient overall water splitting electrocatalysis.

Implementing the hierarchical structures of non-noble-metal-based electrocatalysts and modulating their composition can help accelerate surface reactions and fulfill the promise of renewable energy devices via water splitting. Herein, molybdenum-based compounds are constructed on activated nickel foam (act-NF) by a one-step hydrothermal growth. The product generated on the act-NF is NiCoMoO@CoMoO, with a novel 3D hierarchical heterostructure, wherein the one-dimensional CoMoO nanorods are hierarchically integrated with the two-dimensional NiCoMoO nanosheets (NCMO@CMO/act-NF).

Bimetallic NiMoN Nanowires with a Preferential Reactive Facet: An Ultraefficient Bifunctional Electrocatalyst for Overall Water Splitting.

Faceted nanomaterials with highly reactive exposed facets have been the target of intense researches owing to their significantly enhanced catalytic performance. NiMoN nanowires with the (100) facet preferentially exposed were prepared by an in situ N/O exchange and the morphology tuned by using a rationally designed NiMoO precursor. The facet-tuned NiMoN nanowires exhibited excellent electrocatalytic activity for the hydrogen evolution reaction (HER) under both alkaline and acidic conditions that was comparable to that of noble metal platinum.

Solid-Solution Anion-Enhanced Electrochemical Performances of Metal Sulfides/Selenides for Sodium-Ion Capacitors: The Case of FeSSe .

Transition-metal sulfides/selenides are explored as advanced electrode materials for nonaqueous sodium-ion capacitors, using FeSSe as an example. A solid solution of S/Se in FeSSe allows it to combine the high capacity of FeS and the good diffusion kinetics of FeSe together, thereby exhibiting excellent cycle stability (∼220 mA h g after 6000 cycles at 2 A g) and superior rate capability (∼210 mA h g at 40 A g) within 0.8-3.

Critical Role of Water and Oxygen Defects in C-O Scission during CO Reduction on ZnGeO(010).

Exploration of catalyst structure and environmental sensitivity for C-O bond scission is essential for improving the conversion efficiency because of the inertness of CO. We performed density functional theory calculations to understand the influence of the properties of adsorbed water and the reciprocal action with oxygen vacancy on the CO dissociation mechanism on ZnGeO(010). When a perfect surface was hydrated, the introduction of HO was predicted to promote the scission step by two modes based on its appearance, with the greatest enhancement from dissociative adsorbed HO.

Biphase-Interface Enhanced Sodium Storage and Accelerated Charge Transfer: Flower-Like Anatase/Bronze TiO/C as an Advanced Anode Material for Na-Ion Batteries.

Flower-like assembly of ultrathin nanosheets composed of anatase and bronze TiO embedded in carbon is successfully synthesized by a simple solvothermal reaction, followed with a high-temperature annealing. As an anode material in sodium-ion batteries, this composite exhibits outstanding electrochemical performances. It delivers a reversible capacity of 120 mA h g over 6000 cycles at 10 C.

Conductive Polymer-Coated VS4 Submicrospheres As Advanced Electrode Materials in Lithium-Ion Batteries.

VS4 as an electrode material in lithium-ion batteries holds intriguing features like high content of sulfur and one-dimensional structure, inspiring the exploration in this field. Herein, VS4 submicrospheres have been synthesized via a simple solvothermal reaction. However, they quickly degrade upon cycling as an anode material in lithium-ion batteries.

A theoretical study of O2 activation by the Au7-cluster on Mg(OH)2: roles of surface hydroxyls and hydroxyl defects.

Using density functional theory (DFT) calculations, we investigated O2 activation by the Au7-cluster supported on the perfect and hydroxyl defective Mg(OH)2(0001) surface. It is revealed that hydroxyl groups on the perfect Mg(OH)2(0001) surface can not only enhance the stability of the Au7-cluster, but also help the adsorption of the O2 molecule through hydrogen-bonding interactions with the 2nd-layered interfacial Au sites. Density of states (DOS) analysis shows that the d-band centers of the 2nd-layered interfacial Au atoms are very close to the Fermi level, which thereby reduce the Pauli repulsion and promote the O2 adsorption.

Exploring the effects of nanocrystal facet orientations in g-C₃N₄/BiOCl heterostructures on photocatalytic performance.

Effective separation and migration of photogenerated electron-hole pairs are two key factors to determine the performance of photocatalysts. It has been widely accepted that photocatalysts with heterojunctions usually exhibit excellent charge separation. However, the migration process of separated charges in the heterojunction structures has not been fully investigated.

Structural diversities and related properties of four coordination polymers synthesized from original ligand of 3,3',5,5'-azobenzenetetracarboxylic acid.

Four new coordination polymers, namely [Co(H2O2abtc)(bibp)]n (), {[Mn1.5(Oabtc)(H2O)2]·(H2bmib)0.5·H2O}n (), {[Cd1.

Structural diversity and magnetic properties of six metal-organic polymers based on semirigid tricarboxylate ligand of 3,5-bi(4-carboxyphenoxy)benzoic acid.

Solvothermal reactions of the semirigid 3,5-bi(4-carboxyphenoxy)benzoic acid (H3BCP) and transitional metal cations with the help of three ancillary bridging imidazole linkers afforded six coordination polymers, namely, [Co(HBCP)(1,4-bib)0.5]n (), {[Mn1.5(BCP)(1,4-bib)0.

Pressure-induced ferroelastic phase transition in SnO2 from density functional theory.

High-pressure ferroelastic transition of rutile- to CaCl2-type SnO2 is investigated within density functional theory and Landau free energy theory. The calculated Landau energy map around the ground state is successfully used to clarify the softening mechanism of B1g mode (order parameter Q) and the coupling mechanism between the soft B1g mode and the soft transverse acoustic (TA) mode (strain ɛ). It is found that the Sn-O-Sn bending induced soft B1g mode effectively slows the excess energy increase caused by bond stretching, while the coupling between the soft B1g mode and the soft TA mode further decreases the energy since the lattice distortion strain ɛ minimizes the SnO6 octahedral distortion.

Syntheses, crystal structures and UV-visible absorption properties of five metal-organic frameworks constructed from terphenyl-2,5,2',5'-tetracarboxylic acid and bis(imidazole) bridging ligands.

The solvothermal reactions of terphenyl-2,5,2',5'-tetracarboxylic acid (H4tptc) and transition metal cations (Ni(II), Mn(II)) afford five novel coordination polymers (CPs) in the presence of four bis(imidazole) bridging ligands (1,3-bimb = 1,3-bis(imidazol-1-ylmethyl)benzene, 1,4-bmib = 1,4-bis(2-methylimidazol-1-ylmethyl)benzene, 4,4'-bibp = 4,4'-bis(imidazol-1-yl)biphenyl, 4,4'-bimbp = 4,4'-bis(imidazol-1-ylmethyl)biphenyl), namely, [M(tptc)(0.5)(1,3-bimb)(H2O)]n (M = Ni for 1, Mn for 2), {[Ni(tptc)(0.5)(1,4-bmib)]·0.

The roles of surface structure, oxygen defects, and hydration in the adsorption of CO(2) on low-index ZnGa(2)O(4) surfaces: a first-principles investigation.

The effects of the surface atomic and electronic structures, oxygen defects, and hydration on CO2 adsorption on ZnGa2O4(100), (110), and (111) surfaces were studied using density functional theory (DFT) slab calculations. For the perfect (100) surface, the most stable adsorption state involved the Zn-O-Ga bridge site, with an adsorption energy of 0.16 eV.

Enhanced visible-light photocatalytic activity of g-C3N4/Zn2GeO4 heterojunctions with effective interfaces based on band match.

Fabricating heterojunction photocatalysts is an important strategy for speeding up the separation rate of photogenerated charge carriers, which is attracting greater interest. However, the choice of three factors, individual materials, band offsets, and effective interfaces, is still important for fabricating efficient heterojunction photocatalysts. Herein, efficient g-C3N4/Zn2GeO4 photocatalysts with effective interfaces were designed by controlling the surface charges of the two individual materials inside the same aqueous dispersion medium, making use of the electrostatic attraction between oppositely charged particles.

A highly photocatalytic polyoxomolybdate compound constructed from novel-type triple helix {Mo4O12}n chains and copper(I)-organic nets.

A novel-type 3D polyoxomolybdate-organic framework, {[Cu3(H3tpb)2(tpb)(Mo4O12)]·4H2O}n (1, H3tpb = 1,3,5-tri(1H-pyrazol-3-yl)benzene), was prepared and characterized by elemental analysis, IR spectroscopy, and luminescence analysis. Single-crystal X-ray diffraction analysis reveals that novel neutral triple helix {Mo4O12}n chains are encased in bowl-like 2D [Cu3(H3tpb)2(tpb)]n intervals via bond interactions between terminal oxygen atoms and cations of Cu(I), leaving an unprecedented (3,3,5,8)-connected (3·4·6(8))3(3(6)·4(6)·8(6)·9(6)·10(4))(4(3))2(6(3)) topology. Moreover, compound 1 exhibits remarkable photocatalytic activities for decomposition of methylene orange (MO), methylene red (MR), methylene blue (MB), methylene violet (MV), and rhodamine B (RhB) under UV light.

Theoretical study of H2O adsorption on Zn2GeO4 surfaces: effects of surface state and structure-activity relationships.

We employed the density functional theory to investigate the interaction of H2O with Zn2GeO4 surfaces, considering both perfect and defective surfaces. The results revealed that the interaction of H2O with Zn2GeO4 surfaces was dependent on the structure of the latter. For perfect surfaces, H2O adsorbed at the Ge3c···O2c site of a (010) surface could spontaneously dissociate into an H atom and an OH group, whereas H2O tended to adsorb at the O2c-M3c-O3c site of a (001) surface by molecular adsorption.

A new thiophenyl pyrazoline fluorescent probe for Cu2+ in aqueous solution and imaging in live cell.

A new thiophenyl pyrazoline probe for Cu(2+) in aqueous solution was synthesized and characterized by IR, NMR, HRMS and X-ray analysis. The probe displays remarkably high selectivity and sensitivity for Cu(2+) with a detection limit of 1.919 × 10(-7) M in aqueous solution (EtOH:HEPES = 1:1, v/v, 0.