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It is still a challenge to design an efficient and low-cost electrocatalyst for the hydrogen evolution reaction (HER) in an alkaline electrolyte. Herein, ultra-low amount Pt-doped Co2P/Ni2P on nickel foam (Pt/Co2P/Ni2P/NF) was facilely synthesized via an in situ controlled growth and used as an efficient electrocatalyst for electrolytic water splitting into hydrogen. Pt/Co2P/Ni2P/NF was achieved by a two-step procedure that was conducted by the hydrothermal approach to obtain the precursor, followed by a subsequent in situ phosphorization procedure. Due to the NF substrate being supermacroporous, more active sites of Pt/Co2P/Ni2P/NF could be exposed, improving electron transport and providing open-channels for the rapid release of H2. Pt/Co2P/Ni2P/NF exhibited remarkable electrocatalytic performance towards HER with an overpotential of 75 mV at 10 mA cm−2 in an alkaline electrolyte and a small Tafel slope of 64 mV dec−1. This work provided a facile and reliable synthetic approach to improve transition metal phosphides (TMPs) for electrocatalytic HER performance in alkaline electrolytes.

Pure shales in the first member of Qingshankou Formation (simplified as Qing 1 Member) in the southern Songliao Basin, i.e., the semi-deep and deep lacustrine shales, are characterized by a high content of clay minerals and poor hydrocarbon mobility, making the development of shale oil difficult. According to the drilling and testing results, the shale of Qing 1 Member can be classified into 3 lithofacies, i.e., bedded argillaceous shale, laminated diamictite shale, and interbedded felsic shale. The TOC and brittle minerals control the enrichment of shale oil, of them, TOC controls the total oil content, in other words, the total oil content increases with the increase of TOC; while the laminae made up of brittle minerals contain a large number of bigger intergranular pores which are favorable enrichment space for movable shale oil. In consideration of the origins of the 3 lithofacies, two shale oil enrichment models are classified, i.e., the deep lacustrine high-TOC bedded argillaceous shale (Model-I) and the semi-deep lacustrine moderate-high-TOC laminated diamictite shale (Model-II). In the Model-I, the shale is characterized by high hydrocarbon generation ability, high total oil content, abundant horizontal bedding fractures, and vertical and high angle fractures locally; the complex fracture network formed by horizontal bedding fractures and vertical fractures improve the storage capacity and permeability of the shale reservoir, increase the enrichment space for movable oil. In the Model-II, the shale is characterized by good hydrocarbon generation ability and fairly high total oil content, and as the brittle laminae contain large intergranular pores, the shale has a higher movable oil content. Based on the two models, shale oil sweet-spot areas of 2880 km2 in the southern Songliao Basin are favorable for further exploration. Aimed at the difficulties in reservoir fracturing of the lacustrine shale with a high content of clay minerals, the composite fracturing technology with supercritical carbon dioxide was used in the shale oil reservoir for the first time, realizing large-scale volume fracturing in shale with a high content of clay minerals and strong heterogeneity, marking a breakthrough of oil exploration in continental shale with a high content of clay minerals in China.

Taking the inter-salt organic-rich shales in the third member of Paleogene Shahejie Formation (Es3) of Dongpu sag in Bohai Bay Basin as an example, the origin of overpressure, development characteristics, formation and evolution mechanism, formation stages and geological significance on shale oil and gas of overpressure fractures in the inter-salt shale reservoir were investigated by means of thin section identification, scanning electron microscopy observation, analysis of fluid inclusions, logging data analysis, and formation pressure inversion. The results show that overpressure is universal in the salt-lake basin of Dongpu sag, and under-compaction caused by the sealing of salt-gypsum layer, pressurization due to hydrocarbon generation, transformation and dehydration of clay minerals, and fault sealing are the 4 main factors leading to the occurrence of overpressure. The overpressure fractures are small in scale, with an average length of 356.2 μm and an average underground opening of 11.6 μm. But they are densely developed, with an average surface density of 0.76 cm/cm2. Moreover, they are often accompanied by oil and gas charging, and thus high in effectiveness. Overpressure fractures were mainly formed during two periods of large-scale oil and gas charging, approximately 25–30 Ma ago and 0–5 Ma ago. Inter-salt overpressure fractures play dual roles as the storage space and migration paths of shale oil and gas. They contribute 22.3% to the porosity of shale reservoir and 51.4% to the permeability. They can connect fracture systems of multiple scales, greatly improving the quality of shale reservoir. During the development of shale oil and gas, inter-salt overpressure fractures can affect the extension and morphology of hydraulic fractures, giving rise to complex and highly permeable volumetric fracture networks, improving hydraulic fracturing effect and enhancing shale oil and gas productivity.

Nonmetal doping is a convenient method to adjust the visible light photocatalytic activity of graphitic carbon nitride (g-C3N4). Herein, highly active sulfur-doped porous g-C3N4 (C3N4-S) was successfully prepared by one-step calcination using thiourea and melamine as the precursors. C3N4-S exhibited excellent photocatalytic performance for the degradation of Rhodamine B (RhB) under visible light irradiation. C3N4-S not only promoted the separation of photogenerated electron-hole pairs, but also enhanced electron transfer, resulting in a great improvement in the photocatalytic efficiency. Based on capture experiments and DMPO spin-trapping ESR spectra, the superoxide radical (˙O2-) was proved to be the predominant active species and the possible photocatalytic mechanism of C3N4-S was proposed. The photocatalytic mechanism of RhB degradation over C3N4-S was further explored using high-resolution mass spectra (HRMS).

In this study, molybdenum disulfide (MoS2) was used as an adsorbent to quickly and efficiently remove Rhodamine B (RhB) from wastewater. Ultrathin layered MoS2 nanoflowers with rich active sites were prepared via a hydrothermal method. The ultrathin layered MoS2 nanoflowers exhibited remarkable adsorption capacity for RhB dyes, which reached 365 mg g−1 within 20 min, due to the large specific BET surface area, the large amount of active sites and the intensive electrostatic attraction between the negative charges of MoS2 nanoflowers and the RhB cationic molecules. The large BET surface area (71.7 m2 g−1) could provide a high number of active sites and storage centers for the RhB molecules. The adsorption behaviors were well fitted with the pseudo-second-order adsorption model and the Langmuir isotherm model. The reusability tests demonstrated that the MoS2 nanoflowers could be reused 6 times and could retain more than 85% of their adsorption capacity. The results exhibited that the MoS2 structure had significant adsorption capacity and could be used as an adsorbent in wastewater treatment.

Nonmetal doping is a convenient method to adjust the visible light photocatalytic activity of graphitic carbon nitride (g-C3N4). Herein, highly active sulfur-doped porous g-C3N4 (C3N4-S) was successfully prepared by one-step calcination using thiourea and melamine as the precursors. C3N4-S exhibited excellent photocatalytic performance for the degradation of Rhodamine B (RhB) under visible light irradiation. C3N4-S not only promoted the separation of photogenerated electron-hole pairs, but also enhanced electron transfer, resulting in a great improvement in the photocatalytic efficiency. Based on capture experiments and DMPO spin-trapping ESR spectra, the superoxide radical (˙O2-) was proved to be the predominant active species and the possible photocatalytic mechanism of C3N4-S was proposed. The photocatalytic mechanism of RhB degradation over C3N4-S was further explored using high-resolution mass spectra (HRMS).

Pt/RGO electrocatalyst was successfully prepared by the deposition of platinum nanoparticles on the surface of reduced graphene oxide with a rapid and environment-friendly microwave-assisted polyol method. The electrochemical activity of as-synthesized Pt/RGO for methanol electrooxidation was investigated in detail. As can be seen from certain values including diffusion coefficient, current density of forward oxidation peak and ratio of the current density of forward peak to reverse peak, the electrooxidation performance of Pt/RGO was superior to that of Pt/C and Pt/graphite catalysts. For example, the current density of forward oxidation peak obtained with Pt/RGO catalyst for methanol oxidation was 18.5 mA/cm(2), which was higher than that obtained with Pt/C catalyst (9.65 mA/cm(2)).

A new Co-containing metal-organic framework (Co-MOF), [Co(BDC)(bib)]n (bib = 1,4-bis-imidazolebenzene; H2BDC = 1,4-benzenedicarboxylic), has been synthesized under hydrothermal conditions. Its structural characterization was carried out by means of elemental analysis, infrared spectroscopy, thermogravimetric analysis, UV–Vis and single X-ray diffraction. The Co-MOF exhibits 2-fold interpenetrated sql topology, which is further stacked through hydrogen-bond interactions leading to the formation of a 3D supramolecular architecture. The CV results of [Co(BDC)(bib)]n modified electrode show a pair of redox peaks at ca. 0.13 V in 0.5 M NaOH solution and also display good electrocatalytic activity for oxidation of hydrogen peroxide in alkaline medium.

e21605 Background: To observe the clinical efficacy and survival of UMIPIC combined with low-dose chemotherapy in patients with lung cancer. Methods: 840 patients with lung cancer underwent UMIPIC treatment from January 2011 to December 2015 were selected as the study subjects, 341 cases combined with low-dose chemotherapy in group A and 499 cases not combined with chemotherapy in group B. All patients were diagnosed with lung cancer and signed a consent form for treatment. The patients were treated according to the UMIPIC treatment guidelines. This study was mainly to observe the adverse reactions, clinical efficacy, survival time and survival rate of lung cancer patients after receiving UMIPIC combined with or without low dose chemotherapy. Results: The common adverse reactions in group A were fever 38.12%, followed by pain 9.38%, hemoglobin 7.94%, white blood cells 5.01%, nausea 2.35%, liver function damage 1.19%, vomiting 1.17%, and kidney function damage 0.30%; Common adverse reactions in group B were fever 38.68%, followed by pain 13.23%, hemoglobin reduction 12.87%, white blood cell reduction 5.29%, nausea 2.00%, vomiting 2.00%, liver function damage 1.92%. The hemoglobin reduction in group A was significantly lower than that in group B (P < 0.05), and there was no difference in the other adverse reactions (P > 0.05). Clinical efficacy of the two groups revealed that the benefit rate of group A was 95.45% higher than that of group B 93.47% (P > 0.05). After follow-up, it was found that the average survival time and median survival time of patients in group A were 20.744 and 13.270 months, respectively, which were significantly higher than those of group B at 19.514 and 10.070 months (P < 0.05). The survival rates of the two groups of patients, The 1-year, 2-year, and 5-year survival rates of group A patients are 52.48%, 23.60%, and 16.95%, and the 1-year, 2-year, and 5-year survival rates of group B patients are 42.96% and 17.07 % And 10.26%, the one-year survival rate of group A was significantly higher than that of group B (P < 0.05). Conclusions: UMIPIC combined with low-dose chemotherapy has a good clinical effect in treating lung cancer without increasing the incidence of adverse reactions, and a significant effect on extending survival time and improving survival rate of lung cancer patients.

e16130 Background: To observe the effect of adjuvant on the clinical efficacy and survival period of patients with liver cancer treated by UMIPIC (Ultra-minimum Incision personalized intratumoral chemoimmunotherapy). Methods: 156 liver cancer patients who were treated with UMIPIC with hapten or without hapten from January 2011 to December 2015 were selected for the study objects, including 124 cases with hapten as studying group and 32 cases without hapten as comparing group. All patients signed the treatment consent, treated according to the treatment guidelines of UMIPIC, followed up for the efficacy and the survival period of all patients more than 3 months, and observed whether there was effect on the clinical efficacy, adverse reactions, survival period and survival rate of patients with liver cancer patients treated with UMIPIC. Results: The common side effects of hapten group were fever 45.16%, pain 27.42%, hemoglobin reduction 14.78%, leucopenia 11.97%, thrombocytopenia 10.26%, liver function damage 5.26%, nausea 4.03%, renal dysfunction 2.61%. No rash, neurotoxicity and hair loss were found; The common adverse reactions in the non hapten group were fever 40.63%, pain 25.00%, hemoglobin reduction 17.24%, leucopenia 13.79%, thrombocytopenia 10.34%, nausea 6.25%. No other adverse reactions were found; there was no difference between the two groups (P > 0.05). The benefit rate of hapten group was 89.06% lower than that of non hapten group (94.74%) (P > 0.05). According to the follow-up results, the mean and median survival time of hapten group was 26.421 and 9.930 months, significantly higher than that of non hapten (16.473 and 7.230 months) (P < 0.05).The 1-year, 2-year, 3-year and 5-year survival rates of adjuvant group respectively were 45.69%, 33.33%, 25.68% and 20.83%,The 1-year, 2-year, 3-year and 5-year survival rates in the adjuvant free group respectively were 27.50%, 20.59%, 14.81% and 14.29%, The 1-year survival rate of hapten group was significantly higher than that of non hapten group (P < 0.05). Conclusions: There is no significant difference in the adverse reactions and clinical efficacy of UMIPIC in the treatment of liver cancer patients with and without hapten. Adding hapten can significantly prolong the survival time and improve the survival rate of patients with liver cancer patients treated with UMIPIC.

e16532 Background: To observe the effect of chronic disease condition on the therapeutic effect and survival period of cancer patients treated with UMIPIC. Methods: 2594 cancer patients in our hospital from January 2011 to December 2015 who received UMIPIC for the study objects. 576 cases with chronic diseases, 2018 without chronic disease, 840 with lung cancer, 712 with esophageal cancer, 254 with liver cancer, 108 with pancreatic cancer, 93 with gastric cancer, 587 with other cancers. They signed the consent for treatment, evaluated the efficacy, followed up to the clinical effect, adverse reactions, survival data of patients. Results: The side effects of the chronic disease patients with cancer after UMIPIC therapy is fever at 26.56%, pain at 15.10%, the second was hemoglobin reduction 16.48%, leucopenia 5.27%, liver function damage 2.67%, thrombocytopenia 2.45%, nausea 2.26%, vomiting 1.39%, neurotoxicity and hair loss of less than 0.20%, while cancer patients without chronic disease after UMIPIC therapy, side effect is fever at 32.37%, pain at14.87%, hemoglobin reduction 13.26%, leucopenia 6.09%, nausea 2.73%, thrombocytopenia 2.6% 3%, liver function damage 1.77%, vomiting 1.73%, kidney function damage 0.89%, neurotoxicity and hair loss were lower than 0.20%; there is only fever difference in the two groups (P < 0.05).There was no significant difference in other adverse reactions. This may be due to the immunity of normal patients was stronger than that of chronic patients. It was found that the clinical benefit rate of 90.91% in patients with chronic diseases was significantly lower than 93.44% in patients without chronic diseases (P = 0.021); after follow-up, we found that the mean survival time of patients with chronic diseases was 22.149 months, median survival time was 10.300 months, while median survival time of patients without chronic diseases was 22.940 months, median survival time was 11.200 months, and the survival rates of patients without chronic diseases for 1, 2, 3 and 5-year were 48.94%, 29.97%, 25.19%, and 25.18% respectively, it is significantly higher than those of patients with chronic diseases (43.19%, 22.33%, 18.37% and 16.04%) (P

Laminated sandstone is abundant in tight reservoirs filled with the hydrocarbon fluid that flows through the lamina induced fractures (LFs). To study the fracture permeability evolution during the rupture phase in the triaxial compression process of laminated sandstone, we tested 12 column samples with different lamina angles in a particular experimental apparatus during the triaxial compression process. This study proposed a permeability model for the lamina induced fractures, which is composed of a variable of radius strain and three critical parameters, including the lamina angle, the initial rupture radius strain, and the rupture stress difference. The model was built based on the Palmer and Mansoori's fracture permeability model (the P-M model), the modified Tien and Kuo's LF failure criteria (the T-K criteria), and the redefined rock compressibility (the change rate of porosity with the radius strain). In this research, the simulation agreed well with the test results. The permeability evolution lines were characterized by two phases: a rapidly increase phase and a following stable phase. The samples with the medium lamina angles were usually characterized by a more rapidly increasing phase and a higher stable fracture permeability, indicating a preferential hydraulic fracturing target for the tight oil exploration. Furthermore, to satisfy the flow principle of the lamina induced fractures, it is proposed that horizontal wells of the laminated tight sandstone reservoir should be designed in a polyline or oblique trajectory which should be intersected with the formation lamina to create a proper perforating direction.

Layered metal sulfides (LMS) are promising in the electrochemical hydrogen evolution reaction (HER). Unfortunately, LMS shows poor electrical conductivity, only the exposed edges are active for hydrogen evolution reaction. In this work, a MoS2/SnS2 heterojunction with an open 3D flower-like structure is prepared via a simple hydrothermal method. The MoS2/SnS2 heterojunction displays a high HER activity, obtaining a current density of 10 mA cm−2 at an overpotential of 288 mV and a Tafel slope of 50 mV dec-1. In addition, the MoS2/SnS2 heterojunction shows high durability for HER. Structure and composition analysis, together with electrochemical measurements show that the MoS2/SnS2 heterojunction could effectively induce the interface-coupling effect and adjust the electronic structure, optimize the kinetics process, in turn, enhance the HER performances.

We report a novel Co-doped porous Ni5P4 nanoflower as an efficient hydrogen evolution electrocatalyst with high activity and electrochemical stability. In 0.5 M H2SO4, Co-doped (6.6at.%) Ni5P4 has an overpotential of 310 mV at the current density of 10 mA cm−2, while Ni5P4 and Co-doped (3.3 at.%) Ni5P4 have the overpotential of 410 and 370 mV, respectively. In addition, the current density lost value of Co-doped (6.6 at.%) Ni5P4 after 18 h of reaction is negligible, and therefore has good stability. Co-doped (6.6 at.%) Ni5P4 exhibits excellent hydrogen evolution activity, which can be attributed to a stable surface and a highly conductive structure.

Porous flower-like Ni5P4 was successfully synthesized and characterized by XRD, SEM, TEM and XPS. The flower-like Ni5P4 modified glassy carbon electrode (Ni5P4 GCE) has significant electrocatalytic activities for glucose oxidation in 0.1 M sodium hydroxide solution. The experimental results show that the flower-like Ni5P4 has a linear detection range for glucose from 0.002 to 5.3 mM, the detection limit is 0.7 μM (S/N = 3). In addition, this Ni5P4 GCE can be successfully utilized to measure glucose content in human serum, therefore it is expected to be used to determine glucose in actual samples.

Although extensive studies have been conducted on unconventional shale oil resources in recent years, little work has been performed on the resource potential of lacustrine shales. The Es3L (lower sub-member of the third member of the Eocene Shahejie Formation) shale of the Bonan Sag, a set of thick lacustrine-deposited sediments, offers a good example for furthering the understanding of these rocks. Geochemical and mineralogical investigations were carried out on a large sample set from the 220 m thick sequence of well Luo69. In total 200 core samples were analyzed for total organic carbon (TOC) and Rock-Eval pyrolysis, and 421 core samples were analyzed for mineral compositions. The Es3L shales have a very high TOC content, with Type I lacustrine oil prone kerogen in the early oil generation stage. Rock-Eval Tmax suppression is evident in the lower part of the Es3L member associated with a rise in PI (production index). With respect to fracability or brittleness, the content of brittle minerals in the Es3L shale is generally higher than that of marine shales in the USA, with higher calcite mineral (averaging 51.82 wt.%) and lower clay content (averaging 18.86 wt.%). Interparticle pores (in minerals grains or clay aggregates), intraparticle pores (intercrystalline dolomite and pyrite framboid) and four types of fractures (tectonic fractures, abnormal pressure fractures, clay shrinkage fractures and inter-laminar fractures) are developed in the Es3L shale. Organic matter pores are not present in the studied samples probably due to lower maturity. Tectonic fracture may play an important role in hydrocarbon migration and accumulation. The results of this study suggest that the Es3L shale in the Bonan sag has very good shale oil potential, especially in the lower section.

A magnetic recyclable nano-triphenylphosphine (nano-TPP) ligand was synthesized by simply loading a dopamine-triphenylphosphine derivative onto the surface of super paramagnetic iron oxide nanoparticle (SPION). Via the cooperation between surface neighbor TPP units, nano-TPPs can bond to Rh atoms forming magnetic recyclable nano-TPPRh complexes to catalyze the hydroformylation reaction and can be reused for 20 times with the compensation of Rh salt.

Gypsum-salt rocks and coccolith calcareous shale are widely deposited in the lower part of the Paleogene Shahejie Formation in the Dongying Sag, Shandong Province. The gypsum-salt rock is believed to be formed during the earlier deposition in salt lake, while the overlying coccolith shale in saline lake with relatively low salinity. By comparing the lake environment and lacustrine microbial communities between ancient and recent lakes, cyanobacteria are regarded as the main representative of productivity during the formation of gypsum-salt strata series, with the annual productivity of 1500–2000 gC m−2 yr−1. Based on the research of ultramicrofossils in the calcareous shale, coccolith is considered as the main contributor to the productivity during the formation of calcareous shale. On the basis of statistic data of sedimentary rates, shale laminations, and coccolith fossils in each lamination, the quantitative value of productivity is calculated, with the annual productivity of 2250–3810 gC m−2 yr−1 (averagely 3120 gC m−2 yr−1). Statistic data of large amount of pyrite framboids indicate that the lower water column was persistently in sulfidic or anoxic conditions during the deposition of gypsum-salt strata series, but it changed to be dysoxic when the coccolith calcareous shale was deposited. Both of these water conditions are favorable for the preservation of organic matter. It is estimated that the organic carbon burial efficiency of the Lower Paleogene salt lakes and saline lakes of Dongying Depression is about 10%–15%, which is calculated and analyzed using the multi-parameter geobiological model.

Samples of argillaceous source rocks were taken at different depth in Dongying Sag and pretreated with different methods. Contrastive analysis to those samples by using N2 adsorption, pyrolysis, X-ray diffraction detection has been made, so as to discuss the validity and credibility of the detection method for specific surface area (SSA), and work for the study on shale gas preservation characteristics. The source rocks were treated with hydrogen peroxide and chloroform. It is found that the average TOC content in the source rock samples treated with hydrogen peroxide decreased than that of the original sample by 61.3% on average for the removal of organic matter in particle state and surface adsorption state, whereas decreased by 20.9% in the samples treated with chloroform for the dissolved organic matter (organic matter in intergranular pores and physical adsorbed) removal, accordingly, the average BET specific surface area increased by 77.5% in the samples treated with hydrogen peroxide than that of the original sample, whereas increased by 22.0% in the samples treated with chloroform, which shows that the organic matter on the specific surface of source rocks can be effectively removed and BET specific surface area extended both with chloroform and hydrogen peroxide treatment. Nonetheless, further analysis shows that the samples treated with chloroform contain the same mineral compositions as the original samples, while the samples treated with hydrogen peroxide have considerably different mineral compositions from the original samples, thus breaking up the original rock structure and the mineral content of the source rocks. Based on the study and analysis above, it is the best choice to select the chloroform treatment to the bulk rock samples for detecting the BET specific surface area, which is possible not only to effectively remove organic matter but also keep the original mineral structure of the rock, thus obtaining true in situ external specific surface area of source rocks, and providing reliable parameters for the study of shale gas occurrence state.

A tetranuclear copper(II) complex, Cu4(NAA)8(CH3CN)2 (1) (HNAA = α-naphthylacetic acid), has been prepared and structurally characterized by IR, elemental analysis, TGA, and single-crystal X-ray diffraction. Complex 1 features a tetranuclear cluster based on two bridged binuclear units, which is further interlinked into a higher dimensional supramolecular framework by intermolecular weak interactions. The weak antiferromagnetic behavior in 1 can be observed.

Layered nanocomposite of methylene blue (MB)-intercalated vanadium oxide was obtained through a simple hydrothermal synthesis method using MB, V2O5, and NaI as starting materials. The intercalation reaction was proven to be successful using X-ray diffraction pattern. The MB-V2O5 nanocomposite was characterized using a scanning electron micrograph, infrared spectra, thermogravimetric analysis, UV spectra, and electrochemical measurements. The intercalated MB cations showed a fine diffusion-controlled electrochemical redox process and facilitated the immobilized horseradish peroxidase's (HRP) good catalytic reduction upon H2O2. The as-prepared MB-V2O5/HRP biosensor showed a linear response to H2O2 over a range from 2.0 × 10(-6) to 9.5 × 10(-5) M with a detection limit of 9.7 × 10(-7) M (S/N ratio = 3).

By hydrothermal reactions of a newly designed ligand, 2-(p-tert-butylphenyl)-1H-imidazole-4,5-dicarboxylic acid (H3BuPhIDC) with Cd(II) or Zn(II), three metal-organic frameworks, [Cd(μ3-HBuPhIDC)(H2O)]·2H2O (1), [Cd(μ3-HBuPhIDC)(4,4′-bipy)0.5] (4,4′-bipy = 4,4′-bipyridine) (2), and [Zn2(μ3-HBuPhIDC)2(CH3OH)2] (3), have been obtained and characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction. In 1, small countless diamond grids form a mesh structure and then are bridged through μ3-HBuPhIDC2− linkers building a 3-D framework. Compared with 1, 4,4′-bipy participates in the construction of a 3-D structure of 2. Polymer 3 shows an interesting 3-D open architecture, which contains infinite 1-D octagonal channels built by left- and right-handed helical chains. Thermal and solid-state photoluminescence properties of the polymers have been investigated.

Cationic iron (III) tetrakis-5, 10, 15, 20-(N-methyl-4-pyridyl) porphyrin (FeIIITMPyP) was intercalated into layered semiconductor KNb3O8 by ion-exchange method. The target product was characterized by XRD, Fourier transform infrared, UV–vis, and TGA. FeIIITMPyP forms an inclined monolayer between Nb3O8 − nanosheets and endues the nanocomposite with excellent electrochemical catalytic activities. The target nanocomposite modified glass carbon electrode shows good electrocatalytic activities for the oxidation of ascorbic acid (AA); the catalytic mechanism was proposed. Differential pulse voltammetric technique was used for detection of AA in neutral aqueous solution; a detection limit of 4.2 × 10−5 M was obtained, and the modified electrode showed good reproducibility in electrochemical detection.

A new Cu metal–organic framework (Cu-MOF), [Cu(adp)(BIB)(H2O)]n (BIB = 1,4-bisimidazolebenzene; H2adp = adipic acid), is synthesised under hydrothermal conditions. Single-crystal X-ray analysis reveals a three-dimensional supramolecular architecture with channels originating from two-dimensional layers extended by hydrogen bonds. The cyclic voltammogram of a [Cu(adp)(BIB)(H2O)]n-modified electrode shows a pair of redox peaks at ca. 0.43 V in 0.1 M NaOH solution corresponding to CuIII(OH)-MOF/CuII(H2O)-MOF couple. The Cu-MOF-modified electrode shows high electrocatalytic activity towards H2O2 oxidation with a linear range from 0.1 μM to 2.75 μM and a detection limit of 0.068 μM. Thus, Cu-MOF is a promising material for H2O2 detection. Keywords: Metal–organic framework, Electrochemical behaviour, Hydrogen peroxide, Electrocatalysis

Based on the micro-fluorescence observation of polished sections of source rocks, two types of micro-layers with different wetting properties formed in thermal evolution, i.e., oil-wetting and water-wetting micro-layers, are distinguished. The wetting property is found closely related to the abundance of organic matter and its occurrences with inorganic minerals. The alternating distribution and intercrossing of two types of micro-layers formed many separated spaces with different wettabilities. The strong capillary forces in these separated spaces with different wettibilities obstruct the cross flows of pore fluids and result in nearly independent and closed fluid systems. As a consequence, these spatially superposed spaces in source rocks bear the overburden pressure and then abnormally high pressures have developed in the whole source rock unit. Therefore, the abundance and occurrences of organic matter are the main inner factors influencing the formation of abnormally high pressures, whereas the formation, distribution and development of micro-layers with different wettabilities during the evolution of source rock determine the intensity and spatial distribution of abnormally high pressures.

Cationic iron (III) tetrakis-5, 10, 15, 20-(N-methyl-4-pyridyl)porphyrin (FeIIITMPyP) was intercalated into layered semiconductor KNb3O8 for the first time by ion-exchange method. FeIIITMPyP forms an inclined monolayer between Nb3O8− nanosheets and endues the nanocomposite with a pair of characteristic redox peaks of FeIIITMPyP. The FeIIITMPyP–Nb3O8− nanocomposite modified glass carbon electrode shows high electrochemical catalysis toward reduction of hydrogen peroxide with a linear range at low concentration and a detection limit of 1.75 μM, the promising utilization of the nanocomposite as a material for biosensor was proposed.

Two zinc(II) and cadmium(II) metal-organic frameworks with mixed ligands, {[Zn2(biim-4)2(TDC)2]·2.5H2O}n (1) and {[Cd2(biim-4)2(TDC)2·2H2O]}n (2) [biim-4 = 1,1′-(1,4-butanediyl)bis(imidazole); H2TDC = thiophene-2,5-dicarboxylic acid], were hydrothermally synthesized. Both of them are characterized by elemental analysis, IR spectroscopy, and single crystal X-ray diffraction. In 1, the four-connected ZnII nodes are connected by four linear ligands extending into a 3D network, which further integrates a fivefold interpenetrating diamond 3D topological network and the free water molecules distribute in void space, whereas in 2, the CdII ions are in a distorted octahedral arrangement linked by TDC2– and biim-4 ligands to construct a 3D framework. In topology analysis, C11 and C14 are simplified as 3-connected nodes and the 3D framework displays a (3,5)-connected net. Furthermore, the thermal and photoluminescent properties of 1 and 2 were also studied.

A novel coordination polymer, [Cd2(PMP)2Cl4] n (PMP = 1-phenyl-3-methyl-2-pyrazoline-5-one), was prepared by the reaction of cadmium chloride hemidihydrate and PMP, and characterized by elemental analysis, IR spectrum, TGA/DTA and electrochemical analysis. Single crystal X-ray diffraction revealed that the title complex is orthorhombic, space group Pna2(1), with a = 16.5398(14), b = 18.238(2), c = 3.8367(7) A, V = 1157.4(3) A3, Z = 2. Each cadmium atom is hexa-coordinate and surrounded by an OCl5 environment, adopting a distorted octahedral geometry, in which three Cl− ions act as μ3-linker and two as μ2-linker. The Cd(II), Cl− and PMP form an infinite 1D chain with complicated chair-like features through μ2- and μ3-Cl bridges. The electrochemical behavior of the complex was investigated in DMF by cyclic voltammetry. The antibacterial activity of the complex, PMP and cadmium chloride hemidihydrate was tested against Escherichia coli, Staphylococcus aureus and Bacillus subtilis by the agar diffusion method.

A new Schiff base, N,N′-bis(4-methoxy-benzylidene)-1,4-bis(3-aminopropyl)piperazine (BMBA), has been synthesized by the reaction of 1,4-bis(3-aminopropyl)piperazine and 4-methoxy-benzaldehyde in methanol solution. The title compound was characterized by elemental analysis, IR spectrum, 1H NMR, 13C NMR and X-ray single crystal diffraction analyses. The compound crystallizes in the monoclinic system with space group C2/c and a = 24.071(5), b = 9.4035(19), c = 11.263(2) A, β = 96.787(2)°, V = 2531.6(9) A3, D c = 1.193 g/cm3, M r = 454.60, Z = 4, F (000) = 984, μ = 0.079 mm−1, R 1 = 0.0693, and ωR 2 = 0.2269. In the crystal structure, molecules of BMBA and water of crystallization are linked through intermolecular O2W–H2′···N2 hydrogen bond, forming a 1D hydrogen bonding network that generates planar “ribbons” running parallel to the c-axis. Furthermore, the antibacterial activity of title compound was investigated preliminary by agar diffusion method, and it exhibited certain inhibited effect against Escherichia coli, Staphylococcus aureus and Bacillus subtilis. A new Schiff base, N,N′-bis(4-methoxy-benzylidene)-1,4-bis(3-aminopropyl)piperazine, has been synthesized by the reaction of 1,4-bis(3-aminopropyl)piperazine and 4-methoxy-benzaldehyde in methanol solution, and characterized by elemental analysis, IR spectrum, 1H NMR, 13C NMR and X-ray single crystal diffraction analyses. Furthermore, the antibacterial activity was investigated by agar diffusion method, and the results indicated that the Schiff base was active relatively against Escherichia coli, Staphylococcus aureus and Bacillus subtilis.

A new intercalation compound of layered perovskite (K4Nb6O17·3H2O) with cationic Co-porphyrin 5,10,15,20-tetrakis(N-methylpyridinium-4-yl) porphyrinato cobalt(III), CoTMPyP, was successfully synthesized by a guest-exchange method using PrNH3+–Nb6O17 as an intermediate. The resulting nanocomposite CoTMPyP–Nb6O17 has been characterized by X-ray diffraction, elemental analysis, scanning electron microscopy and UV–vis absorption spectra. The glassy carbon (GC) electrode modified with CoTMPyP–Nb6O17 film exhibited two well-defined redox waves at −0.77 and −0.56 V, corresponding to the CoII/ITMPyP and CoIII/IITMPyP couple (vs. SCE, in pH 12.0 phosphate buffer solution). The catalytic performance of the novel catalyst CoTMPyP–Nb6O17 for the epoxidation of cyclohexene was investigated using molecular oxygen as oxidant and isobutylaldehyde as co-reductant. The intercalated cobalt porphyrin appears to be a promising catalyst owing to its good catalytic activity and selectivity. CoTMPyP–Nb6O17 could be reused and showed no appreciable decrease in activity after six reaction cycles.

Cationic iron porphyrin 5,10,15,20-tetrakis(N-methylpyridinium-4-yl) porphyrinato iron(III), FeTMPyP, has been intercalated into layered niobate (K4Nb6O17) through a guest–guest exchange method by using propylammonium niobate ( PrNH 3 + – Nb 6 O 17 ) as a precursor. The microstructure and morphology characterizations for the resulting material FeTMPyP–Nb6O17 have been investigated by means of XRD, FTIR and SEM. The UV–vis spectra results suggest that the incorporation of FeTMPyP in the bidimensional nanostructure produces a red-shift in the Soret absorption band of the cationic metalloporphyrin. By simple dropcoating method, FeTMPyP–Nb6O17 was used as a modifier on the glassy carbon electrode (GCE). The cyclic voltammetry (CV) curves exhibit nearly symmetric anodic and cathodic peaks, corresponding to the Fe(III)/Fe(II) couple. Furthermore, the anodic and cathodic peak currents are linearly dependent on the square root of scan rate, implying a fine diffusion-controlled electrode process.

Polypyrrole/layered niobate (PPy–Nb6O17) nanocomposite has been synthesized by the intercalation of pyrrole monomer into the layer structure of organo-modified niobate followed by the subsequent in situ polymerization of pyrrole in the interlayer spaces. The microstructure and morphology characterizations for the resulting material have been investigated by means of XRD, FTIR, and SEM. On the basis of the experimental results, the mechanism for the formation of PPy chains within the confined galleries of the inorganic host material is presented. The cyclic voltammogram of the PPy–Nb6O17 nanocomposite thin film exhibits a fine diffusion-controlled electrode process, which hints the possibility of being utilized as an electrode modifying material.

One of major drawbacks of magnesium alloy is its low corrosion resistance, which can be improved by using an aluminized coating. In this paper, 7075 Al/Mg-12Gd-3Y-0·5Zr/7075 Al laminated composites were produced by a hot roll bonding method. The rolling temperature was determined based on the flow stresses of Mg-12Gd-3Y-0·5Zr magnesium alloy and 7075 Al alloy at elevated temperature. The bonding strength of the laminate composites and their mechanism were studied. The effects of the reduction ratio (single pass), the rolling temperature, and the subsequent annealing on the bonding strength were also investigated. It was observed that the bonding strength increased rapidly with the reduction ratio and slightly with the rolling temperature. The bonding strength increases with the annealing time until the annealing time reaches 2 h and then decreases. The mechanical bond plays a major role in the bonding strength.

A new polynitrile, N,N,N′,N′-tetra(2-cyanoethyl)-1,4-bis(3-aminopropyl)piperazine, was synthesized by the nucleophilic addition reaction of 1,4-bis(3-aminopropyl)piperazine and acrylonitrile for the first time. The title compound was characterized by elemental analysis, IR spectrum, and its crystal structure determined by X-ray single-crystal diffraction. The compound crystallizes in the monoclinic system with space group P2 1/c and a = 8.6195(12), b = 9.300(14), c = 16.221(2) A, β = 97.824(2)°, V = 1288.2(3) A3, D c = 1.064 g cm−3, M r = 412.59, Z = 2, F(000) = 448, μ = 0.067 mm−1. The TG–DTA analysis revealed that the title compound possesses relatively good thermal stability under 220 °C. A new polynitrile, N,N,N′,N′-tetra(2-cyanoethyl)-1,4-bis(3-aminopropyl)piperazine, was synthesized and characterized by elemental analysis, IR spectrum, TG–DTA, and X-ray single-crystal diffraction.