Hydration Characteristics and Early Strength Evolution of Classified Fine Tailings Cemented Backfill.

To explore the hydration characteristics and early strength evolution of classified fine tailings cemented backfill (CFTCB), a nuclear magnetic resonance (NMR) analysis and a volume resistivity test were performed on classified fine tailings filling slurry (CFTFS). The early hydration products of CFTCB were studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD) phase analysis. Uniaxial compressive strength (UCS) test was carried out, and the microscopic characteristics and strength rules of the hydration reaction of CFTCB were analyzed. Based on the experiment, we found the law of water content change and porosity evolution. The early hydration reaction can be divided into the dissolution, setting, and hardening stages. The volume resistivity test results show that the volume resistance of filling slurry increases slowly at first then decreases, and finally increases rapidly. The variation trend of volume resistivity is related to the degree of hydration reaction. When combined with the hydration characteristics of backfill materials, the hydration reaction rate determines the growth rate of early strength of backfill, and the formation of hydration products is the reason for the early strength increase in backfill. The research conclusion has an important theoretical guiding value and engineering significance in mine filling production organization and filling ratio parameter optimization.

Selective Production of Linear Aldehydes and Alcohols from Alkenes using Formic Acid as Syngas Surrogate.

Performing carbonylation without the use of carbon monoxide for high-value-added products is an attractive yet challenging topic in sustainable chemistry. Herein, effective methods for producing linear aldehydes or alcohols selectively with formic acid as both carbon monoxide and hydrogen source have been described. Linear-selective hydroformylation of alkenes proceeds smoothly with up to 88 % yield and >30 regioselectivity in the presence of single Rh catalyst. Strikingly, introducing Ru into the system, the dual Rh/Ru catalysts accomplish efficient and regioselective hydroxymethylation in one pot. The present processes utilizing formic acid as syngas surrogate operate simply under mild condition, which opens a sustainable way for production of linear aldehydes and alcohols without the need for gas cylinders and autoclaves. As formic acid can be readily produced via CO2 hydrogenation, the protocols represent indirect approaches for chemical valorization of CO2 .

Effectively Regulating the Microenvironment of Atomically Dispersed Rh through Co and Pi to Promote the Selectivity in Olefin Hydroformylation.

In the study of heterogeneity of homogeneous processes, effective control of the microenvironment of active sites is a reliable means to improve the selectivity of products. Here, we develop a high-performance Rh-based atomically dispersed catalyst for olefin hydroformylation by controlling the electronic environment and spatial distribution of active metals on the supports, which is achieved through wet impregnation of Rh on ZnO modified with Pi and Co. Various characterizations demonstrate that Co weakens Rh-CO interactions and Pi promotes the formation of atomically dispersed Rh, which thereby improves the selectivity of linear aldehydes in hydroformylation. This strategy of rationally designing the local microenvironment of active metals is important to optimize the catalytic performance.

Optimization of a Decatungstate-Catalyzed C(sp3)-H Alkylation Using a Continuous Oscillatory Millistructured Photoreactor.

Tetrabutylammonium decatungstate (TBADT) has emerged as an efficient and versatile photocatalyst for hydrogen atom transfer (HAT) processes that enables the cleavage of both activated and unactivated aliphatic C-H bonds. Using a recently developed oscillatory millistructured continuous-flow photoreactor, investigations of a decatungstate-catalyzed C(sp3)-H alkylation protocol were carried out, and the results are presented here. The performance of the reactor was evaluated in correlation to several chemical and process parameters, including residence time, light intensity, catalyst loading, and substrate/reagent concentration. In comparison with previously reported batch and flow protocols, conditions were found that led to considerably higher productivity, achieving a throughput up to 36.7 mmol/h with a residence time of only 7.5 min.

C(sp3)-H functionalizations of light hydrocarbons using decatungstate photocatalysis in flow.

Direct activation of gaseous hydrocarbons remains a major challenge for the chemistry community. Because of the intrinsic inertness of these compounds, harsh reaction conditions are typically required to enable C(sp3)-H bond cleavage, barring potential applications in synthetic organic chemistry. Here, we report a general and mild strategy to activate C(sp3)-H bonds in methane, ethane, propane, and isobutane through hydrogen atom transfer using inexpensive decatungstate as photocatalyst at room temperature. The corresponding carbon-centered radicals can be effectively trapped by a variety of Michael acceptors, leading to the corresponding hydroalkylated adducts in good isolated yields and high selectivity (38 examples).

Iron-Catalyzed Cross-Coupling of Alkynyl and Styrenyl Chlorides with Alkyl Grignard Reagents in Batch and Flow.

Transition-metal-catalyzed cross-coupling chemistry can be regarded as one of the most powerful protocols to construct carbon-carbon bonds. While the field is still dominated by palladium catalysis, there is an increasing interest to develop protocols that utilize cheaper and more sustainable metal sources. Herein, we report a selective, practical, and fast iron-based cross-coupling reaction that enables the formation of Csp-Csp3 and Csp2 -Csp3 bonds. In a telescoped flow process, the reaction can be combined with the Grignard reagent synthesis. Moreover, flow allows the use of a supporting ligand to be avoided without eroding the reaction selectivity.

Disulfide-Catalyzed Visible-Light-Mediated Oxidative Cleavage of C=C Bonds and Evidence of an Olefin-Disulfide Charge-Transfer Complex.

A photocatalytic method for the aerobic oxidative cleavage of C=C bonds has been developed. Electron-rich aromatic disulfides were employed as photocatalyst. Upon visible-light irradiation, typical mono- and multi-substituted aromatic olefins could be converted into ketones and aldehydes at ambient temperature. Experimental and computational studies suggest that a disulfide-olefin charge-transfer complex is possibly responsible for the unconventional dissociation of S-S bond under visible light.