Nondissociative Activated Dihydrogen Binding on CeO2 Revealed by High-Pressure Operando Solid-State NMR Spectroscopy.

Dihydrogen complexes, which retain the H-H bond, have been extensively studied in molecular science and found to be prevalent in homogeneous and enzymatic catalysis. However, their counterparts in heterogeneous catalysis, specifically nondissociative chemisorbed dihydrogen binding on the catalyst surface, are rarely reported experimentally. This scarcity is due to the complexity of typical material surfaces and the lack of effective characterization techniques to prove and distinguish various dihydrogen binding modes. Herein, using high-pressure operando solid-state NMR technology, we report the first unambiguous experimental observation of activated dihydrogen binding on a reduced ceria catalyst through interactions with surface oxygen vacancies. By employing versatile NMR structural and dynamical analysis methods, we establish a proportional relationship between the degree of ceria surface reduction and dihydrogen binding, as evidenced by NMR observations of H-D through-bond coupling (JHD), T1 relaxation, and proton isotropic chemical shifts. In situ NMR analysis further reveals the participation of bound dihydrogen species in a room-temperature ethylene hydrogenation reaction. The remarkable similarities between surface-activated dihydrogen in heterogeneous catalysis and dihydrogen model molecular complexes can provide valuable insights into the hydrogenation mechanism for many other solid catalysts, potentially enhancing hydrogen utilization.

A Supramolecular Reinforced Gel Fracturing Fluid with Low Permeability Damage Applied in Deep Reservoir Hydraulic Fracturing.

Gel fracturing fluid is the optimum fracturing fluid for proppant suspension, which is commonly applied in deep reservoir hydraulic fracturing. The content of polymers and crosslinkers in gel fracturing fluid is usually high to meet the needs of high-temperature resistance, leading to high costs and reservoir permeability damage caused by incomplete gel-breaking. In this paper, a supramolecular reinforced gel (SRG) fracturing fluid was constructed by strengthening the supramolecular force between polymers. Compared with single network gel (SNG) fracturing fluid, SRG fracturing fluid could possess high elasticity modulus (G' = 12.20 Pa) at lower polymer (0.4 wt%) and crosslinker (0.1 wt%) concentrations. The final viscosity of SRG fracturing fluid was 72.35 mPa·s, meeting the temperature resistance requirement of gel fracturing fluid at 200 °C. The gel-breaking time could be extended to 90-120 min using an encapsulated gel breaker. Gel particles are formed after the gel fracturing fluid is broken. The median particle size of gel particles in the SRG-breaking solution was 126 nm, which was much smaller than that in the industrial gel (IDG) breaking fluid (587 nm). The damage of the SRG-breaking solution to the core permeability was much less than the IDG-breaking solution. The permeability damage of cores caused by the SRG-breaking solutions was only about half that of IDG-breaking solutions at 1 mD.