Sinopec (China)

Abstract Dinitrogen reduction to ammonia using transition metal catalysts is central to both the chemical industry and the Earth's nitrogen cycle. In the Haber–Bosch process, a metallic iron catalyst and high temperatures (400 °C) and pressures (200 atm) are necessary to activate and cleave NN bonds, motivating the search for alternative catalysts that can transform N 2 to NH 3 under far milder reaction conditions. Here, the successful hydrothermal synthesis of ultrathin TiO 2 nanosheets with an abundance of oxygen vacancies and intrinsic compressive strain, achieved through a facile copper‐doping strategy, is reported. These defect‐rich ultrathin anatase nanosheets exhibit remarkable and stable performance for photocatalytic reduction of N 2 to NH 3 in water, exhibiting photoactivity up to 700 nm. The oxygen vacancies and strain effect allow strong chemisorption and activation of molecular N 2 and water, resulting in unusually high rates of NH 3 evolution under visible‐light irradiation. Therefore, this study offers a promising and sustainable route for the fixation of atmospheric N 2 using solar energy.

How green was my valley: Green carbon science focuses on the transformations of carbon-containing compounds in the entire carbon cycle. The ultimate aim is to use carbon resources efficiently and minimize the net CO2 emission. This holistic view also has ramifications for related fields including petroleum refining and the production of liquid fuels and chemicals from coal, methane, CO2, and biomass.

Oxygen vacancy on the surface of metal oxides is one of the most important defects which acts as the reactive site in a variety of catalytic reactions. In this work, operando spectroscopy methodology was employed to study the CO2 methanation reaction catalyzed by Ru/CeO2 (with oxygen vacancy in CeO2) and Ru/α-Al2O3 (without oxygen vacancy), respectively, so as to give a thorough understanding on active site dependent reaction mechanism. In Ru/CeO2 catalyst, operando XANES, IR, and Raman were used to reveal the generation process of Ce(3+), surface hydroxyl, and oxygen vacancy as well as their structural evolvements under practical reaction conditions. The steady-state isotope transient kinetic analysis (SSITKA)-type in situ DRIFT infrared spectroscopy undoubtedly substantiates that CO2 methanation undergoes formate route over Ru/CeO2 catalyst, and the formate dissociation to methanol catalyzed by oxygen vacancy is the rate-determining step. In contrast, CO2 methanation undergoes CO route over Ru surface in Ru/α-Al2O3 with the absence of oxygen vacancy, demonstrating active site dependent catalytic mechanism toward CO2 methanation. In addition, the catalytic activity evaluation and the oscillating reaction over Ru/CeO2 catalyst further prove that the oxygen vacancy catalyzes the rate-determining step with a much lower activation temperature compared with Ru surface in Ru/α-Al2O3 (125 vs 250 °C).

The Silurian Longmaxi shale gas play in Jiaoshiba Structure in the southeast margin of the Sichuan Basin is studied to discuss the key controlling factors of shale gas enrichment in complex tectonic zone with high evolution. Jiaoshiba Structure is a faulted anticline which experienced multiphase tectonic movements. The Longmaxi Formation has high thermal evolution degree with Ro more than 2.2%, 35-45 meters thick high-quality shale (TOC > 2%) in its lower part. The reservoir is overpressure with a pressure coefficient of 1.55, and the shale gas production and pressure are stable. Structure type, evolution and geochemical analyses show that there are several stages of hydrocarbon generation, migration and accumulation in the Longmaxi Formation. The joint action of two groups (two stages) of fault systems and the detachment surface at the bottom of the Longmaxi Formation control the development of reticular cracks and overpressure preservation, and it is the key to the shale gas accumulation and high yield. The sealed box-like system in the Longmaxi Formation ensures the gas reservoir dynamic balance. The model of high yield and enrichment of Jiaoshiba shale gas play is “ladder migration, anticline accumulation, fault–slip plane controlling fractures, and box shape reservoiring”. Like in conventional gas plays, good preservation and tectonic conditions are also required to form high yield shale plays in areas which have complex structures, multi-stage tectonic movements, and have high evolution shale.

Abstract Selective hydrogenolysis of biomass-derived glycerol to propanediol is an important reaction to produce high value-added chemicals but remains a big challenge. Herein we report a PtCu single atom alloy (SAA) catalyst with single Pt atom dispersed on Cu nanoclusters, which exhibits dramatically boosted catalytic performance (yield: 98.8%) towards glycerol hydrogenolysis to 1,2-propanediol. Remarkably, the turnover frequency reaches up to 2.6 × 10 3 mol glycerol ·mol PtCu–SAA −1 ·h −1 , which is to our knowledge the largest value among reported heterogeneous metal catalysts. Both in situ experimental studies and theoretical calculations verify interface sites of PtCu–SAA serve as intrinsic active sites, in which the single Pt atom facilitates the breakage of central C–H bond whilst the terminal C–O bond undergoes dissociation adsorption on adjacent Cu atom. This interfacial synergistic catalysis based on PtCu–SAA changes the reaction pathway with a decreased activation energy, which can be extended to other noble metal alloy systems.

Abstract Green carbon science is defined as the “study and optimization of the transformation of carbon‐containing compounds and the relevant processes involved in the entire carbon cycle from carbon resource processing, carbon energy utilization, CO 2 fixation, and carbon recycling to utilize carbon resources efficiently and minimize the net CO 2 emission.” [1] Green carbon science is related closely to carbon neutrality, and relevant fields have developed quickly in the last decade. In this Minireview, we propose the concept of carbon energy index, and the recent progress in petroleum refining, and the production of liquid fuels, chemicals, and materials using coal, methane, CO 2 , biomass, and waste plastics is highlighted in combination with green carbon science. An outlook for these important fields is provided in the final section.

Abstract Electrochemical alcohols oxidation offers a promising approach to produce valuable chemicals and facilitate coupled H 2 production. However, the corresponding current density is very low at moderate cell potential that substantially limits the overall productivity. Here we report the electrooxidation of benzyl alcohol coupled with H 2 production at high current density (540 mA cm −2 at 1.5 V vs . RHE) over a cooperative catalyst of Au nanoparticles supported on cobalt oxyhydroxide nanosheets (Au/CoOOH). The absolute current can further reach 4.8 A at 2.0 V in a more realistic two-electrode membrane-free flow electrolyzer. Experimental combined with theoretical results indicate that the benzyl alcohol can be enriched at Au/CoOOH interface and oxidized by the electrophilic oxygen species (OH*) generated on CoOOH, leading to higher activity than pure Au. Based on the finding that the catalyst can be reversibly oxidized/reduced at anodic potential/open circuit, we design an intermittent potential (IP) strategy for long-term alcohol electrooxidation that achieves high current density (>250 mA cm −2 ) over 24 h with promoted productivity and decreased energy consumption.

Abstract The Puguang gas field is the largest gas field found in marine carbonates in China. Marine carbonate reservoirs in this field were buried to a depth of about 7000 m (22,966 ft) and experienced maximum temperature up to 220°C before uplift to the present-day depth of 5000–5500 m (16,404–18,045 ft), with present-day thermal maturity between 2.0 and 3.0% equivalent vitrinite reflectance (Ro). Sulfur-rich pyrobitumens with reflectance up to 3.5% are widespread in the reservoirs and resulted from thermal cracking of crude oils most likely generated from Upper Permian source rocks and thermochemical sulfate reduction (TSR). Natural gases in the Puguang gas field have wide variations in nonhydrocarbon gas contents, with H2S contents between 5.1 and 58.3% and CO2 contents between 7.9 and 18.0%. The hydrocarbon gases originated mainly from thermal cracking of accumulated oil but were altered by TSR. Thermochemical sulfate reduction in the study area exerted different effects on the isotope compositions of different hydrocarbon gas components at different TSR stages. The differential increase of δ13C values for different gas components reflects transformation from a heavy-hydrocarbon-gas–dominated TSR stage to a methane-dominated TSR stage. This caused a decrease of δ13Cmethane−δ13Cethane values and a corresponding conversion from reversed to normal isotope distributions. Thermochemical sulfate reduction in the study area appears to have been limited by sulfate concentrations in the reservoirs. A successive, three-stage TSR series, namely, liquid-hydrocarbon–involved TSR, heavy-hydrocarbon-gas–dominated TSR, and methane-dominated TSR, occurred in reservoirs with sufficient sulfate concentration. Methane can be the dominant organic reactant for TSR, but only at elevated temperature and after most C2+ hydrocarbons are exhausted.

The modulation of strong metal–support interaction (SMSI) plays a key role and remains a challenge in achieving the desired catalytic performance in many important chemical reactions. Herein, we report a TiO2–x-modified Ni nanocatalyst with tunable Ni–TiO2–x interaction via a two-step procedure: preparation of Ni/Ti mixed metal oxide (NiTi–MMO) from NiTi-layered double hydroxide (NiTi–LDH) precursor, followed by a further reduction treatment at different temperatures. A combination study (XRD, TEM, H2-TPR, XPS, and in situ EXAFS) verifies that a high reduction temperature enhances the Ni–TiO2–x interaction, which results in an increased coverage degree of Ni nanoparticles by TiO2–x as well as electron density of interfacial Ni (Niδ−). Moreover, the creation of a Niδ−–Ov–Ti3+ interface site (Ov denotes oxygen vacancy) induced by strong Ni–TiO2–x interaction serves as dual-active site to efficiently catalyze the water–gas shift reaction (WGSR). The optimized catalyst (Ni@TiO2–x(450)) via tuning Ni–TiO2–x interaction gives a TOF value of 3.8 s–1, which is ∼7 times larger than the conventional 15%Ni/TiO2(450) catalyst. Such a high catalytic efficiency is attributed to the interfacial site (Niδ−–Ov–Ti3+) with medium strength of metal–support interaction, as revealed by in situ diffuse reflectance Fourier transform infrared spectroscopy (in situ DRIFTS), which promotes the synergic catalysis between Niδ− and oxygen vacancy toward WGSR.

Abstract Solar‐driven interfacial desalination (SDID), which is based on localized heating and interfacial evaporation, provides an opportunity for developing environmentally friendly and cost‐effective seawater thermal desalination. However, localized heating and rapidly generated interfacial steam may cause salt to accumulate on the evaporator's surface and block the channel of steam evaporation. Salt accumulation inevitably reduces the light absorption and service period of the solar absorber, resulting in a significant decrease in evaporation efficiency over time. Salt accumulation makes it difficult to produce SDID devices with high energy efficiency and long‐term stability for large‐scale use in remote poverty‐stricken areas. Therefore, the exploration of novel and effective strategies for addressing salt accumulation through both material design and structural engineering has attracted more attention in recent years. This review presents an overview of the state‐of‐the‐art advancements in salt‐resistant photothermal evaporation and discusses the critical issues for achieving salt mitigation SDID, focusing on the classification of salt mitigation strategies based on photothermal evaporation configurations, the basic mechanism of salt mitigation, and the architectural design of photothermal materials. Finally, the important challenges and prospects of SDID are discussed to providing a meaningful roadmap to efficient salt mitigation SDID.

The most widely used catalysts and processes for H2S-selective catalytic oxidation are overviewed in this review. Two kinds of catalysts have been investigated intensively: carbon-based catalysts (active carbon catalyst, carbon nanotube catalyst, and carbon nanofiber catalyst), metal oxide-based catalysts (metal oxide catalyst, oxide-supported catalyst, and clay-supported catalyst). Among them, carbon-based catalysts are utilized mainly in discontinuous processes at relatively low temperatures, whereas metal oxide catalysts are the most widely used in practice. However, the reaction temperature is relatively high. Fortunately, a MgAlVO catalyst derived from LDH materials and intercalated clay-supported catalysts exhibit excellent catalytic activities at relatively lower temperatures. According to various studies, the catalytic behaviors mainly obey the Mars–van Krevelen mechanism; however, the catalyst deactivation mechanism differs, depending on the catalyst. In practice, the mobil direct oxidation process (MODOP), super-Claus and Euro-Claus processes were developed for H2S-selective catalytic oxidation. Nevertheless, MODOP has to proceed under water-free conditions. The super-Claus process can operate in up to 30% water content. The Euro-Claus process is a modified version of the super-Claus process, which was developed to eliminate recovery losses of escaped SO2.

The kaleidoscopic applications of zeolite catalysts (zeo-catalysts) in petrochemical processes has been considered as one of the major accomplishments in recent decades. About twenty types of zeolite have been industrially applied so far, and their versatile porous architectures have contributed their most essential features to affect the catalytic efficiency. This review depicts the evolution of pore models in zeolite catalysts accompanied by the increase in industrial and environmental demands. The indispensable roles of modulating pore models are outlined for zeo-catalysts for the enhancement of their catalytic performances in various industrial processes. The zeolites and related industrial processes discussed range from the uni-modal micropore system of zeolite Y (12-ring micropore, 12-R) in fluid catalytic cracking (FCC), zeolite ZSM-5 (10-R) in xylene isomerization and SAPO-34 (8-R) in olefin production to the multi-modal micropore system of MCM-22 (10-R and 12-R pocket) in aromatic alkylation and the hierarchical pores in FCC and catalytic cracking of C4 olefins. The rational construction of pore models, especially hierarchical features, is highlighted with a careful classification from an industrial perspective accompanied by a detailed analysis of the theoretical mechanisms.

Abstract Dual‐atom site catalysts (DACs) have emerged as a new frontier in heterogeneous catalysis because the synergistic effect between adjacent metal atoms can promote their catalytic activity while maintaining the advantages of single‐atom site catalysts (SACs), like 100 % atomic utilization efficiency and excellent selectivity. Herein, a supported Pd 2 DAC was synthesized and used for electrochemical CO 2 reduction reaction (CO 2 RR) for the first time. The as‐obtained Pd 2 DAC exhibited superior CO 2 RR catalytic performance with 98.2 % CO faradic efficiency at −0.85 V vs. RHE, far exceeding that of Pd 1 SAC, and coupled with long‐term stability. The density functional theory (DFT) calculations revealed that the intrinsic reason for the superior activity of Pd 2 DAC toward CO 2 RR was the electron transfer between Pd atoms at the dimeric Pd sites. Thus, Pd 2 DAC possessed moderate adsorption strength of CO*, which was beneficial for CO production in CO 2 RR.

The mechanism on interfacial synergistic catalysis for supported metal catalysts has long been explored and investigated in several important heterogeneous catalytic processes (e.g., water–gas shift (WGS) reaction). The modulation of metal–support interactions imposes a substantial influence on activity and selectivity of catalytic reaction, as a result of the geometric/electronic structure of interfacial sites. Although great efforts have validated the key role of interfacial sites in WGS over metal catalysts supported on reducible oxides, direct evidence at the atomic level is lacking and the mechanism of interfacial synergistic catalysis is still ambiguous. Herein, Ni nanoparticles supported on TiO2–x (denoted as Ni@TiO2–x) were fabricated via a structure topotactic transformation of NiTi-layered double hydroxide (NiTi-LDHs) precursor, which showed excellent catalytic performance for WGS reaction. In situ microscopy was carried out to reveal the partially encapsulated structure of Ni@TiO2–x catalyst. A combination study including in situ and operando EXAFS, in situ DRIFTS spectra combined with TPSR measurements substantiates a new redox mechanism based on interfacial synergistic catalysis. Notably, interfacial Ni species (electron-enriched Niδ− site) participates in the dissociation of H2O molecule to generate H2, accompanied by the oxidation of Niδ−–Ov–Ti3+ (Ov: oxygen vacancy) to Niδ+–O–Ti4+ structure. Density functional theory calculations further verify that the interfacial sites of Ni@TiO2–x catalyst serve as the optimal active site with the lowest activation energy barrier (∼0.35 eV) for water dissociation. This work provides a fundamental understanding on interfacial synergistic catalysis toward WGS reaction, which is constructive for the rational design and fabrication of high activity heterogeneous catalysts.

Through detailed analyses of the distribution characteristics of organic-rich shale, appearance features of high-quality shale, microscopic characteristics of shale reservoir rocks, fracability, and the relationship between preservation conditions and shale gas enrichment in Upper Ordovician Wufeng Formation−Lower Silurian Longmaxi Formation in Sichuan Basin, theoretical understandings and specific suggestions with respect to the exploration and development of shale gas in China are summarized and proposed respectively. Important geological understandings in the exploration and development of shale gas of the Wufeng Formation–Longmaxi Formation in the Sichuan Basin can be summarized into the following aspects: depositional environment and depositional process control the distribution of organic-rich shale; high quality shale in “sweet spot segments” are commonly characterized by high content of organic carbon, high brittleness, high porosity and gas content; organic pores are important storage space for the enrichment of shale gas; preservation conditions are the key factor for the geological evaluation of shale gas in structurally complex regions; shale gas can be considered as “artificial gas reservoirs” and the fracability assessment is essential for high-production; nanoscale storage space and the mode of occurrence control the special seepage characteristics of shale gas. The following suggestions are proposed for the development of China's shale gas industry: (1) focus more on fundamental research to achieve new breakthrough in the geological theory of shale gas; (2) emphasize exploration practices to have all-round discoveries in multiple strata; (3) study the regularities of development and production to establish new models of shale gas development; (4) think creatively to invent new technologies to tackle key problems; (5) explore the management innovation to create new mechanisms in shale gas development.

Abstract Ruthenium dioxide is presently the most active catalyst for the oxygen evolution reaction (OER) in acidic media but suffers from severe Ru dissolution resulting from the high covalency of Ru-O bonds triggering lattice oxygen oxidation. Here, we report an interstitial silicon-doping strategy to stabilize the highly active Ru sites of RuO 2 while suppressing lattice oxygen oxidation. The representative Si-RuO 2 −0.1 catalyst exhibits high activity and stability in acid with a negligible degradation rate of ~52 μV h −1 in an 800 h test and an overpotential of 226 mV at 10 mA cm −2 . Differential electrochemical mass spectrometry (DEMS) results demonstrate that the lattice oxygen oxidation pathway of the Si-RuO 2 −0.1 was suppressed by ∼95% compared to that of commercial RuO 2 , which is highly responsible for the extraordinary stability. This work supplied a unique mentality to guide future developments on Ru-based oxide catalysts’ stability in an acidic environment.

Abstract The giant Puguang gas field, with a proven original in-place gas volume of 350 × 109 m3 (12.36 TCFG), was discovered in 2003 in the eastern Sichuan fold-thrust belt of the mature Sichuan Basin, southwest China. The field is a combination structural-stratigraphic trap closed by lateral depositional change and fault closure. The trap evolved from a paleo-oil reservoir originating in the Triassic–Jurassic. The entrapment of thermal gas, which was derived from Lower–middle Silurian and Permian source rocks, occurred during deep burial in the Jurassic–Cretaceous. Tertiary–Quaternary compression transformed the paleotrap into the present gas reservoir. Gas is contained in the Lower Triassic Feixianguan and the Upper Permian Changxing reservoirs, which consist predominantly of dolomitized oolites deposited in shelf and platform-margin shoal and backreef environments. Reservoir quality is characterized by porosity of 1–29% and permeability of 0.01–9664 md, with buried depth greater than 5000 m (16,400 ft). The discovery of the Puguang field exemplifies the successful application of a new play concept and new technology in a mature basin. The discovery resulted from a shift in exploration strategy from structures to stratigraphic traps in reef and shoal dolomites and benefited from advanced high-resolution seismic techniques. The discovery will not only broaden the exploration scope in the Sichuan Basin, but also provide an excellent analog for exploration in other fold-thrust belts worldwide.

We demonstrate a one-pot hydrothermal cohydrolysis-carbonization process using glucose and iron nitrate as starting materials for the fabrication of carbonaceous spheres embedded with iron oxide nanoparticles. It is verified by TEM, (57)Fe Mossbauer, and Fe K-edge XAS that iron oxide nanoparticles are highly dispersed in the carbonaceous spheres, leading to a unique microstructure. A formation mechanism is also proposed. This route is also applicable to a range of other naturally occurring saccharides and metal nitrates. A catalytic study revealed the remarkable stability and selectivity of the reduced Fe(x)O(y)@C spheres in the Fischer-Tropsch synthesis, which clearly exemplifies the promising application of such materials.

A [(C(18)H(37))(2)N(+)(CH(3))(2)](3)[PW(12)O(40)] catalyst, assembled in an emulsion in diesel, can selectively oxidize the sulfur-containing molecules present in diesel into their corresponding sulfones by using H(2)O(2) as the oxidant under mild conditions. The sulfones can be readily separated from the diesel using an extractant, and the sulfur level of the desulfurized diesel can be lowered from about 500 ppm to 0.1 ppm without changing the properties of the diesel. The catalyst demonstrates high performance (>/=96 % efficiency of H(2)O(2), is easily recycled, and approximately 100 % selectivity to sulfones). Metastable emulsion droplets (water in oil) act like a homogeneous catalyst and are formed when the catalyst (as the surfactant) and H(2)O(2) (30 %) are mixed in the diesel. However, the catalyst can be separated from the diesel after demulsification.

The purpose of this article was to quantitatively investigate the pore structure and fractal characteristics of different lithofacies in the upper Permian Dalong Formation marine shale. Shale samples in this study were collected from well GD1 in the Lower Yangtze region for mineral composition, X-ray diffraction (XRD), and nitrogen adsorption–desorption analysis, as well as broad-ion beam scanning electron microscopy (BIB-SEM) observation. Experimental results showed that the TOC (total organic carbon) content and vitrinite reflectance (Ro) of the investigated shale samples were in the ranges 1.18–6.45% and 1.15–1.29%, respectively, showing that the Dalong Formation shale was in the mature stage. XRD results showed that the Dalong Formation shale was dominated by quartz ranging from 38.4% to 54.3%, followed by clay minerals in the range 31.7–37.5%, along with carbonate minerals (calcite and dolomite), with an average value of 9.6%. Based on the mineral compositions of the studied samples, the Dalong Formation shale can be divided into two types of lithofacies, namely siliceous shale facies and clay–siliceous mixed shale facies. In siliceous shale facies, which were mainly composed of organic pores, the surface area (SA) and pore volume (PV) were in the range of 5.20–10.91 m2/g and 0.035–0.046 cm3/g, respectively. Meanwhile, the pore size distribution (PSD) and fractal dimensions were in the range 14.2–26.1 nm and 2.511–2.609, respectively. I/S (illite-smectite mixed clay) was positively correlated with SA, PV, and fractal dimensions, while illite had a negative relationship with SA, PV, and fractal dimensions. I/S had a strong catalytic effect on organic matter for hydrocarbon generation, which was beneficial to the development of organic micropores, so I/S was conducive to pore structure complexity and the increase in SA and PV, while illite easily filled organic pores, which was not beneficial to the improvement of pore space. In clay–siliceous mixed shale facies, which mainly develop inorganic pores such as intergranular pores, SA and PV were in the range of 6.71–11.38 m2/g and 0.030–0.041 cm3/g, respectively. Meanwhile, PSD and fractal dimensions were in the range of 14.3–18.9 nm and 2.563–2.619, respectively. Quartz and I/S showed weak positive correlations with SA, PV, and fractal dimensions. The various compact modes between quartz particles and the disorder of I/S were conducive to the complexity of pore structure and the improvement of SA and PV. The research findings can provide a reference for the optimization and evaluation of shale gas favorable area of the Lower Yangtze Platform.