Stabilizing High-Valence Copper(I) Sites with Cu-Ni Interfaces Enhances Electroreduction of CO2 to C2+ Products.

In this study, the copper-nickel (Cu-Ni) bimetallic electrocatalysts for electrochemical CO2 reduction reaction(CO2RR) are fabricated by taking the finely designed poly(ionic liquids) (PIL) containing abundant Salen and imidazolium chelating sites as the surficial layer, wherein Cu-Ni, PIL-Cu and PIL-Ni interaction can be readily regulated by different synthetic scheme. As a proof of concept, Cu@Salen-PIL@Ni(NO3)2 and Cu@Salen-PIL(Ni) hybrids differ significantly in the types and distribution of Ni species and Cu species at the surface, thereby delivering distinct Cu-Ni cooperation fashion for the CO2RR. Remarkably, Cu@Salen-PIL@Ni(NO3)2 provides a C2+ faradaic efficiency (FEC2+) of 80.9% with partial current density (jC 2+) of 262.9 mA cm-2 at -0.80 V (versus reversible hydrogen electrode, RHE) in 1 m KOH in a flow cell, while Cu@Salen-PIL(Ni) delivers the optimal FEC2+ of 63.8% at jC2+ of 146.7 mA cm-2 at -0.78 V. Mechanistic studies indicates that the presence of Cu-Ni interfaces in Cu@Salen-PIL@Ni(NO3)2 accounts for the preserve of high-valence Cu(I) species under CO2RR conditions. It results in a high activity of both CO2-to-CO conversion and C-C coupling while inhibition of the competitive HER.

Scalable Palladium-Catalyzed Alkoxycarbonylation of Conjugated Dienes.

The Pd(cod)Cl2-catalyzed alkoxycarbonylation of conjugated dienes to ß,γ-unsaturated esters was approached by both intramolecular phosphinesulfonate L1 and intermolecular PPh3/PTSA in this study. However, the poor solubility of the Pd/L1 complex and the labile monodentate Pd/PPh3 structure restricts the system efficiency, especially for the scale-up application. By contrast, the stable and well-soluble bidentate Xantphos system allows for the quantitative formation of 3-pentenoate (96%) on a gram scale within 6 h in weakly alkaline N-methylpyrrolidone (NMP), which also functions as a basic site to promote the rate-limiting alcoholysis step while reducing the dosage of ligand to a theoretical value.

Effects of serum estrogen levels before frozen-thawed blastocyst transfer on pregnancy outcomes in hormone replacement cycles.

We investigated the effects of serum estrogen levels before frozen-thawed blastocyst transfer on pregnancy outcomes in hormone replacement cycles. Clinical data of 708 hormone replacement cycles with frozen-thawed blastocyst were retrospectively analyzed. According to quartile (P25) of serum estrogen levels on the endometrium transformation day, the 708 cycles were divided into group A1 (E2 < 157.5 pg/ml), group A2 (157.5 pg/ml ≤ E2 < 206.4 pg/ml), group A3 (206.4 pg/ml ≤ E2 < 302.3 pg/ml) and group A4 (E2 ≥ 302.3 pg/ml). According to quartile (P25) of serum estrogen levels on the frozen-thawed blastocyst transfer day, the 708 cycles were divided into group B1 (E2 < 147 pg/ml), group B2 (147 pg/ml ≤ E2 < 200.4 pg/ml), group B3 (200.4 pg/ml ≤ E2 < 323 pg/ml) and group B4 (E2 ≥ 323 pg/ml). According to different clinical outcomes, the 708 cycles were divided into clinical pregnant group and non-clinical pregnant group. The group A4 (E2 ≥ 302.3 pg/ml on the endometrium transformation day) was significantly lower than other groups in blastocyst implantation rate and multiple-pregnancy rate (P < 0.05). The days of taking progynova was significantly different among groups on both endometrium transformation day and frozen-thawed blastocyst transfer day (P < 0.05), but there were no statistical differences in the mean age, endometrial thickness and number of high-quality blastocysts transferred among groups (P > 0.05). The mean age was significantly younger and the number of high-quality blastocysts transferred was significantly higher in the clinical pregnant group than in the non-clinical pregnant group (P < 0.05), but endometrial thickness, days of taking progynova, progesterone level on the blastocyst transfer day, and E2 level were not significantly different between both groups (P > 0.05). Multivariate regression analysis indicated that age was an independent factor affecting clinical pregnancy (P < 0.05). Correlation analysis displayed that the serum estrogen levels did not affect clinical pregnancy (P > 0.05). The days of taking progynova and serum estrogen levels before frozen-thawed blastocyst transfer do not affect pregnancy outcomes in hormone replacement cycles.

Covalent Organic Frameworks Boost the Silver-Electrocatalyzed Reduction of CO2: The Electronic and Confinement Effect.

The electrocatalytic reduction of CO2 to CO with high efficiency is one of the most promising approaches for CO2 conversion due to its considerable economic feasibility and broad application prospects. In this study, three Ag@COF-R (R = -H, -OCH3, -OH) hybrids were facilely fabricated by impregnating silver acetate (AgOAc) into respective covalent organic frameworks (COFs) prepared in advance. They differ significantly in the crystallinity, porosity, distribution, size, and electronic configuration of AgOAc species, which thereby influences both the activity and the selectivity of electrolytic CO2-to-CO transformation. Impressively, Ag@COF-OCH3 provided a high FECO of 93.0% with a high jCO of 213.9 mA cm-2 at -0.87 V (vs reversible hydrogen electrode, RHE) in 1 M KOH using a flow cell. In addition, it exhibited long-term durability at 100 mA cm-2 for 30 h.

Dehydrative Formation of Isosorbide from Sorbitol over Poly(ionic liquid)-Covalent Organic Framework Hybrids.

In this study, the covalent bonding of linear poly(ionic liquid)s (PILs) with covalent organic frameworks (COFs) was accessed by copolymerization of a vinyl-decorated COF with 4-vinylbenzyl chloride, followed by quaternization with tertiary amines. The resultant PIL-COF composite by anchoring a proper content of vinyl sites on the COF-based comonomer retains the crystallinity and porosity, thereby facilitating access of the reactants to the catalytic active sites. As a proof of concept, the dehydrative transformation of sorbitol into isosorbide was selected as a benchmark reaction, whose rate improved significantly in the presence of PIL-COF-0.33 compared with those of individual components and the mesoporous PIL counterpart due to uniform pore sizes and flexible linear catalytic chains. In addition, the hybrids bearing a chemical cross-linkage between PILs and COFs are robust, and PIL-COF-0.33 can be recovered and reused for 10 runs without significant reactivity loss. These findings provide the basis for a novel design concept for achieving both efficient and stable IL catalysis.

Tris(pyrazolyl)borate Cobalt-Catalyzed Hydrogenation of C═O, C═C, and C═N Bonds: An Assistant Role of a Lewis Base.

The combination of tris(pyrazolyl)borate cobalt complexes and Lewis base is developed as an efficient catalyst precursor in the homogeneous hydrogenation. A broad substrate scope including carbonyls, alkenes, enamines, and imines is reduced with 60 atm of H2 at 60 °C. Mechanistic studies support the hydrogenation operates through a frustrated Lewis pair (FLP)-like reduction process. These results highlight the development of novel non-noble metal catalytic processes, when combined with the diverse small molecule activation chemistry associated with FLPs.