Optimizing the Spatial Density of Single Co Sites via Molecular Spacing for Facilitating Sustainable Water Oxidation.

Advances in single-atom (-site) catalysts (SACs) provide a new solution of atomic economy and accuracy for designing efficient electrocatalysts. In addition to a precise local coordination environment, controllable spatial active structure and tolerance under harsh operating conditions remain great challenges in the development of SACs. Here, we show a series of molecule-spaced SACs (msSACs) using different acid anhydrides to regulate the spatial density of discrete metal phthalocyanines with single Co sites, which significantly improve the effective active-site numbers and mass transfer, enabling one of the msSACs connected by pyromellitic dianhydride to exhibit an outstanding mass activity of (1.63 ± 0.01) × 105 A·g-1 and TOFbulk of 27.66 ± 1.59 s-1 at 1.58 V (vs RHE) and long-term durability at an ultrahigh current density of 2.0 A·cm-2 under industrial conditions for oxygen evolution reaction. This study demonstrates that the accessible spatial density of single atom sites can be another important parameter to enhance the overall performance of catalysts.

Atomically Dispersed Dual-Metal Sites Showing Unique Reactivity and Dynamism for Electrocatalysis.

The real structure and in situ evolution of catalysts under working conditions are of paramount importance, especially for bifunctional electrocatalysis. Here, we report asymmetric structural evolution and dynamic hydrogen-bonding promotion mechanism of an atomically dispersed electrocatalyst. Pyrolysis of Co/Ni-doped MAF-4/ZIF-8 yielded nitrogen-doped porous carbons functionalized by atomically dispersed Co-Ni dual-metal sites with an unprecedented N8V4 structure, which can serve as an efficient bifunctional electrocatalyst for overall water splitting. More importantly, the electrocatalyst showed remarkable activation behavior due to the in situ oxidation of the carbon substrate to form C-OH groups. Density functional theory calculations suggested that the flexible C-OH groups can form reversible hydrogen bonds with the oxygen evolution reaction intermediates, giving a bridge between elementary reactions to break the conventional scaling relationship.

Molecule-Enhanced Electrocatalysis of Sustainable Oxygen Evolution Using Organoselenium Functionalized Metal-Organic Nanosheets.

Remolding the reactivity of metal active sites is critical to facilitate renewable electricity-powered water electrolysis. Doping heteroatoms, such as Se, into a metal crystal lattice has been considered an effective approach, yet usually suffers from loss of functional heteroatoms during harsh electrocatalytic conditions, thus leading to the gradual inactivation of the catalysts. Here, we report a new heteroatom-containing molecule-enhanced strategy toward sustainable oxygen evolution improvement. An organoselenium ligand, bis(3,5-dimethyl-1H-pyrazol-4-yl)selenide containing robust C-Se-C covalent bonds equipped in the precatalyst of ultrathin metal-organic nanosheets Co-SeMON, is revealed to significantly enhance the catalytic mass activity of the cobalt site by 25 times, as well as extend the catalyst operation time in alkaline conditions by 1 or 2 orders of magnitude compared with these reported metal selenides. A combination of various in situ/ex situ spectroscopic techniques, ab initio molecular dynamics, and density functional theory calculations unveiled the organoselenium intensified mechanism, in which the nonclassical bonding of Se to O-containing intermediates endows adsorption-energy regulation beyond the conventional scaling relationship. Our results showcase the great potential of molecule-enhanced catalysts for highly efficient and economical water oxidation.

Flexible Cuprous Triazolate Frameworks as Highly Stable and Efficient Electrocatalysts for CO2 Reduction with Tunable C2 H4 /CH4 Selectivity.

Cu-based metal-organic frameworks have attracted much attention for electrocatalytic CO2 reduction, but they are generally instable and difficult to control the product selectivity. We report flexible Cu(I) triazolate frameworks as efficient, stable, and tunable electrocatalysts for CO2 reduction to C2 H4 /CH4 . By changing the size of ligand side groups, the C2 H4 /CH4 selectivity ratio can be gradually tuned and inversed from 11.8 : 1 to 1 : 2.6, giving C2 H4 , CH4 , and hydrocarbon selectivities up to 51 %, 56 %, and 77 %, respectively. After long-term electrocatalysis, they can retain the structures/morphologies without formation of Cu-based inorganic species. Computational simulations showed that the coordination geometry of Cu(I) changed from triangular to tetrahedral to bind the reaction intermediates, and two adjacent Cu(I) cooperated for C-C coupling to form C2 H4 . Importantly, the ligand side groups controlled the catalyst flexibility by the steric hindrance mechanism, and the C2 H4 pathway is more sensitive than the CH4 one.

Graphene-Like Hydrogen-Bonded Melamine-Cyanuric Acid Supramolecular Nanosheets as Pseudo-Porous Catalyst Support.

Behaving as structural protectors and electronic modulators, catalyst supports such as graphene derivatives are generally constructed by covalent bonds. Here, hydrogen-bonded ultrathin nanosheets are reported as a new type of catalyst support. Melamine (M) and cyanuric acid (CA) molecules self-assemble to form the graphite-like hydrogen-bonded co-crystal M-CA, which can be easily exfoliated by ultrasonic treatment to yield ultrathin nanosheets with thickness of ≈1.6 nm and high stability at pH = 0. The dynamic nanosheets form adaptive defects/pores in the synthetic process of CoP nanoparticles, giving embedded composite with high hydrogen evolution activity (overpotential of 66 mV at 10 mA cm-2 ) and stability. Computational calculations, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy unveil the electron modulation effects of the nanosheets. This pseudo-porous catalyst support also can be applied to other metal phosphides.

On-surface isostructural transformation from a hydrogen-bonded network to a coordination network for tuning the pore size and guest recognition.

Rational manipulation of supramolecular structures on surfaces is of great importance and challenging. We show that imidazole-based hydrogen-bonded networks on a metal surface can transform into an isostructural coordination network for facile tuning of the pore size and guest recognition behaviours. Deposition of triangular-shaped benzotrisimidazole (H3btim) molecules on Au(111)/Ag(111) surfaces gives honeycomb networks linked by double N-H⋯N hydrogen bonds. While the H3btim hydrogen-bonded networks on Au(111) evaporate above 453 K, those on Ag(111) transform into isostructural [Ag3(btim)] coordination networks based on double N-Ag-N bonds at 423 K, by virtue of the unconventional metal-acid replacement reaction (Ag reduces H+). The transformation expands the pore diameter of the honeycomb networks from 3.8 Å to 6.9 Å, giving remarkably different host-guest recognition behaviours for fullerene and ferrocene molecules based on the size compatibility mechanism.

Effects of winter and spring housing on growth performance and blood metabolites of Pengbo semi-wool sheep in Tibet.

Objective: Sixty Pengbo semi-wool sheep ewes (approximately 1.5-years-old; 31.33 ± 0.43 kg) were randomly assigned to two groups, either G (grazing) or D (dry lot feeding), to examine the effects of traditional daily grazing and dry lot feeding on performance and blood metabolites during the cold season in Tibetan Plateau. Methods: The ewes in the G group were grazed continuously each day and housed in one shed each evening, while the ewes in the D group were housed in another shed all day. All animals were fed 400 g/day of commercial concentrate, and grass hay was available freely throughout the experimental period. Results: Compared with the G group, the ewes in the D group had higher (p < 0.05) live weight and weight gain. The D group ewes had greater (p < 0.05) numbers of white blood cells and platelets, while they had lower (p < 0.05) platelet-large cell ratios, cholesterol, high-density lipoprotein cholesterol and glutathione peroxidase, as compared with the G group ewes. Additionally, three serum metabolites, abscisic acid, xanthoxin and 3,4-dihydroxy-5-polypren, were upregulated (p < 0.05) in the D group in comparison with the G group. Conclusion: In conclusion, a dry lot feeding regime during the winter and spring period will increase the productivity of sheep and improve blood physiological and biochemical profiles.

Non-3d Metal Modulation of a Cobalt Imidazolate Framework for Excellent Electrocatalytic Oxygen Evolution in Neutral Media.

Cobalt imidazolate frameworks are classical electrocatalysts for the oxygen evolution reaction (OER) but suffer from the relatively low activity. Here, a non-3d metal modulation strategy is presented for enhancing the OER activity of cobalt imidazolate frameworks. Two isomorphous frameworks [Co4 (MO4 )(eim)6 ] (M=Mo or W, Heim=2-ethylimidazole) having Co(eim)3 (MO4 ) units and high water stabilities were designed and synthesized. In different neutral media, the Mo-modulated framework coated on a glassy carbon electrode shows the best OER performances (1 mA cm-2 at an overpotential of 210 mV in CO2 -saturated 0.5 m KHCO3 electrolyte and 2/10/22 mA cm-2 at overpotential of 388/490/570 mV in phosphate buffer solution) among non-precious metal catalysts and even outperforms RuO2 . Spectroscopic measurements and computational simulations revealed that the non-3d metals modulate the electronic structure of Co for optimum reactant/product adsorption and tailor the energy of rate-determining step to a more moderate value.

Modular and Stepwise Synthesis of a Hybrid Metal-Organic Framework for Efficient Electrocatalytic Oxygen Evolution.

The paddle-wheel type cluster Co2(RCOO)4(LT)2 (R = substituent group, LT = terminal ligand), possessing unusual metal coordination geometry compared with other cobalt compounds, may display high catalytic activity but is highly unstable especially in water. Here, we show that with judicious considerations of the host/guest geometries and modular synthetic strategies, the labile dicobalt clusters can be immobilized and stabilized in a metal-organic framework (MOF) as coordinative guests. The Fe(na)4(LT) fragment in the MOF [{Fe3(µ3-O)(bdc)3}4{Fe(na)4(LT)}3] (H2bdc = 1,4-benzenedicaboxylic acid, Hna = nicotinic acid) can be removed to give [{Fe3(µ3-O)(bdc)3}4] with a unique framework connectivity possessing suitable distribution of open metal sites for binding the dicobalt cluster in the form of Co2(na)4(LT)2. After two-step, single-crystal to single-crystal, postsynthetic modifications, a thermal-, water-, and alkaline-stable MOF [{Fe3(µ3-O)(bdc)3}4{Co2(na)4(LT)2}3] containing the desired dicobalt cluster was obtained, giving extraordinarily high electrocatalytic oxygen evolution activity in water at pH = 13 with overpotential as low as 225 mV at 10.0 mA cm-2.

Bimetal-Organic Framework Derived CoFe2 O4 /C Porous Hybrid Nanorod Arrays as High-Performance Electrocatalysts for Oxygen Evolution Reaction.

Porous CoFe2 O4 /C NRAs supported on nickel foam@NC (denoted as NF@NC-CoFe2 O4 /C NRAs) are directly fabricated by the carbonization of bimetal-organic framework NRAs grown on NF@poly-aniline(PANI), and they exhibit high electrocatalytic activity, low overpotential, and high stability for the oxygen evolution reaction in alkaline media.

An Alkaline-Stable, Metal Hydroxide Mimicking Metal-Organic Framework for Efficient Electrocatalytic Oxygen Evolution.

Postsynthetic ion exchange of [Co2(µ-Cl)2(btta)] (MAF-X27-Cl, H2bbta =1H,5H-benzo(1,2-d:4,5-d')bistriazole) possessing open metal sites on its pore surface yields a material [Co2(µ-OH)2(bbta)] (MAF-X27-OH) functionalized by both open metal sites and hydroxide ligands, giving drastically improved electrocatalytic activities for the oxygen evolution reaction (an overpotential of 292 mV at 10.0 mA cm(-2) in 1.0 M KOH solution). Isotope tracing experiments further confirm that the hydroxide ligands are involved in the OER process to provide a low-energy intraframework coupling pathway.

[Distribution characteristics of soil organic carbon, nitrogen and phosphorus in densely populated village landscapes of different hilly regions of China].

Based on high spatial resolution remote sensing map (1 m) and sampling with a stratified design on different site types, the effects of fine-scale land use patterns in villages on top soil (0-30 cm) organic carbon (OC), total nitrogen (TN) and total phosphorus (TP) within and across the densely populated hilly landscapes, i. e., Sichuan Hilly Region (SIHR; Jintang County, Sichuan Province), Subtropical Hilly Region (SUHR; Yiyang County, Hunan Province), and Tropical Hilly Region (THR; Dianbai County, Guangdong Province), were investigated. The results showed that soil OC density was decreased in the order of SUHR (2.72 +/- 0.76 kg x m(-2)) > THR (2.65 +/- 0.73 kg x m(-2)) > SIHR (2.15 +/- 0.57 kg x m(-2)), TN density was in the order of SUHR (0.28 +/- 0.06 kg x m(-2)) > SIHR (0.27 +/- 0.06 kg x m(-2) > THR (0.21 +/- 0.06 kg x m(-2)), and TP density was in the order of SIHR (0.19 +/- 0.04 kg x m(-2)) > SUHR (0.11 +/- 0.03 kg x m(-2)) > THR (0.08 +/- 0.04 kg x m(-2)). The fine-scale landscape units (ecotopes) with the highest soil OC, TN and/or TP stocks were rainfed annual crops in SIHR, paddy rice in SUHR, and open canopy trees and brush in THR, respectively. In all hilly regions, paddy and forest land use classes had the highest soil OC and TN density, while mined areas had the lowest soil OC and TN density, with the distribution of TP density showing a more complicated pattern than that of OC and TN. Ecotope level analysis could reflect the soil organic carbon, nitrogen and phosphorus distribution in densely populated village landscape of hilly regions more comprehensively than land use or land cover analysis.