Pilot Trial on the Efficacy and Safety of a Natural Mineral Water Rich in Hydrogen Carbonate on Functional Dyspepsia and Heartburn

Background: Dyspepsia and heartburn are among the most frequent complaints of the upper gastrointestinal tract impacting quality of life. The present study aimed to investigate the impact of drinking a natural mineral water (medicinal product category “Heilwasser” in Germany) high in hydrogen carbonate (Staatl. Fachingen STILL) on functional dyspeptic complaints and heartburn. Methods: 56 men and women with self-reported heartburn were enrolled to this one-arm pilot study. They had to drink 1.5 L of a hydrogen carbonate rich mineral water each day over a course of six weeks. Participants reported the number and duration of heartburn episodes in a daily dairy. The Reflux Disease Questionnaire (RDQ), Quality of Life in Reflux and Dyspepsia questionnaire (QOLRAD) and the Gastrointestinal Quality of Life Index (GILQI) were used to assess the therapeutic course of the treatment and the Short Form Health Survey (SF-12) to assess general quality of life. Mean ± standard deviation were calculated and pre- and post-treatment changes were compared using the Wilcoxon test. Results: The consumption of a hydrogen carbonate rich mineral water decreased the number of heartburn episodes per week significantly by 4.8 ± 8.2 at the end of the study (p < 0.001). The duration of episodes was also significantly reduced by 25.7 minutes after six weeks of intervention (p < 0.001). Accordingly, the subjectively perceived severity of heartburn, regurgitation and dyspeptic complaints as well as the GERD dimension as assessed by Reflux Disease Questionnaire improved significantly. There was a significant improvement in the disease-specific quality of life as measured by the Gastrointestinal Quality of Life Index (p < 0.001) and by the Quality Of Life in Reflux and Dyspepsia (p < 0.001) questionnaires and the general health-related quality of life as assessed by SF-12 (p < 0.007). Conclusions: The present pilot study provides evidence that supplementation with natural mineral water rich in hydrogen carbonate may improve heartburn and dyspeptic symptoms, which finally resulted in an improvement of the subjectively perceived quality of life. Drinking mineral water rich in hydrogen carbonate may be an alternative remedy for the treatment of dyspeptic symptoms and heartburn. Trial Registration: Eudra CT No 2013-001256-36.

An efficient and stable Cu/SiO_2 catalyst for the syntheses of ethylene glycol and methanol via chemoselective hydrogenation of ethylene carbonate

The efficient synthesis of methanol and ethylene glycol via the chemoselective hydrogenation of ethylene carbonate（EC） is important for the sustainable utilization of CO_2 to produce commodity chemicals and fuels. In this work, a series of β-cyclodextrin-modified Cu/SiO_2 catalysts were prepared by ammonia evaporation method for the selective hydrogenation of EC to co-produce methanol and ethylene glycol. The structure and physicochemical properties of the catalysts were characterized in detail by N_2 physisorption, XRD, N_2O titration, H_2-TPR, TEM, and XPS/XAES. Compared with the unmodified 25 Cu/SiO_2 catalyst, the involvement of β-cyclodextrin in 5β-25 Cu/SiO_2 could remarkably increase the catalytic activity—excellent activity of 1178 mgEC g_（cat）^（–1） h^（–1） with 98.8%ethylene glycol selectivity, and 71.6% methanol selectivity could be achieved at 453 K. The remarkably improved recyclability was primarily attributed to the remaining proportion of Cu~＋/（Cu^0＋Cu~＋）. Furthermore, the DFT calculation results demonstrated that metallic Cu^0 dissociated adsorbed H_2, while Cu~＋ activated the carbonyl group of EC and stabilized the intermediates. This study is a facile and efficient method to prepare highly dispersed Cu catalysts—this is also an effective and stable heterogeneous catalyst system for the sustainable synthesis of ethylene glycol and methanol via indirect chemical utilization of CO_2.

Pt nanoparticles entrapped in ordered mesoporous carbons:An efficient catalyst for the liquid-phase hydrogenation of nitrobenzene and its derivatives

Pt nanoparticles entrapped in ordered mesoporous CMK-3 carbons with p6mm symmetry were prepared using a facile impregnation method, and the resulting materials were characterized using X-ray diffraction spectroscopy, N2 adsorption-desorption, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The Pt nanoparticles were highly dispersed in the CMK-3 with 43.7% dispersion. The Pt/CMK-3 catalyst was an effective catalyst for the liquid-phase hydrogenation of nitrobenzene and its derivatives under the experimental conditions studied here. The Pt/CMK-3 catalyst was more active than commercial Pt/C catalyst in most cases. A highest turnover frequency of 43.8 s-1 was measured when the Pt/CMK-3 catalyst was applied for the hydrogenation of 2-methyl-nitrobenzene in ethanol under optimal conditions. It is worthy of note that the Pt/CMK-3 catalyst could be recycled easily, and could be reused at least fourteen times without any loss in activity or selectivity for the hydrogenation of nitrobenzene in ethanol.

Catalytic Performance of Carbon Materials Supported Pd Nanoparticles in Selective Hydrogenation of Acetylene

Pd/C catalysts were prepared by deposited Pd nanoparticles （NPs） on different carbon supports including activated carbon （AC）, graphite oxide （GO）, and reduced graphite oxide （rGO） using sol-immobilization method. Through transmission electron microscopy, powder X-ray di raction, and X-ray photoelectron spectroscopy, the role of the carbon supports for the catalytic performances of Pd/C catalysts was examined in selective hydrogenation of acetylene. The results indicate that Pd/AC exhibited higher activity and selectivity than Pd/GO and Pd/rGO in the gas phase selective hydrogenation of acetylene. Thermal and chemical treatment of AC supports also have some effect on the catalytic performance of Pd/AC catalysts. The differences in the activity and selectivity of various Pd/C catalysts were partly attributed to the metal-support interaction.

Effect of In_(2)O_(3)particle size on CO_(2) hydrogenation to lower olefins over bifunctional catalysts

A reaction-coupling strategy is often employed for CO_(2)hydrogenation to produce fuels and chemicals using oxide/zeolite bifunctional catalysts.Because the oxide components are responsible for CO_(2)activation,understanding the structural effects of these oxides is crucial,however,these effects still remain unclear.In this study,we combined In_(2)O_(3),with varying particle sizes,and SAPO‐34 as bifunctional catalysts for CO_(2)hydrogenation.The CO_(2)conversion and selectivity of the lower olefins increased as the average In_(2)O_(3)crystallite size decreased from 29 to 19 nm;this trend mainly due to the increasing number of oxygen vacancies responsible for CO_(2) and H_(2) activation.However,In_(2)O_(3)particles smaller than 19 nm are more prone to sintering than those with other sizes.The results suggest that 19 nm is the optimal size of In_(2)O_(3)for CO_(2)hydrogenation to lower olefins and that the oxide particle size is crucial for designing catalysts with high activity,high selectivity,and high stability.

CO_2 hydrogenation to methanol over Cu/Zn/Al/Zr catalysts prepared by liquid reduction

Cu/Zn/Al/Zr catalysts containing Cu in three valence states(Cu2+,Cu+and Cu0)were prepared usinga liquid reduction method and subsequently calcined at different temperatures.The effects of thecalcination temperature on the catalyst structure,interactions among components,reducibility anddispersion of Cu species,surface properties and exposed Cu surface area were systematically investigated.These materials were also applied to the synthesis of methanol via the hydrogenation ofCO2.The results show that a large exposed Cu surface area promotes catalytic CO2conversion andthat there is a close correlation between the Cu+/Cu0ratio and the selectivity for methanol.A calcinationtemperature of573K was found to produce a Cu/Zn/Al/Zr catalyst exhibiting the maximumactivity during the synthesis of methanol.

Direct carbon dioxide hydrogenation to produce bulk chemicals and liquid fuels via heterogeneous catalysis

The hydrogenation of carbon dioxide(CO_(2))to produce chemicals and transportation liquid fuels in huge demand via heterogeneous thermochemical catalysis achieved using renewable energy has received increasing attention,and substantial advances have been made in this research field in recent years.In this study,we summarize our progress in the rational design and construction of highly efficient catalysts for CO_(2) hydrogenation to methanol,lower olefins,aromatics,and gasolineand jet fuel-range hydrocarbons.The structure‐performance relationship,nature of the active sites,and mechanism of the reactions occurring over these catalysts are explored by combining computational and experimental evidence.The results of this study will promote further fundamental studies and industrial applications of heterogeneous catalysts for CO_(2) hydrogenation to produce bulk chemicals and liquid fuels.

Comparative Study of Hydrogen and Carbon Isotopic Composition of Gases Generated from the Pyrolysis of a Peat under Saltwater and Freshwater Conditions

To understand the influence of the diagenetic water medium on the isotopic compositions of thermogenic coalbed gas, both hydrous and anhydrous closed-system pyrolyses were performed at temperatures of 250°C to 650°C on an herbaceous marsh peat. Compared to the results of anhydrous pyrolysis, the hydrocarbon gases generated from hydrous pyrolyses have very different hydrogen isotopic compositions. However, the carbon isotopic compositions of the hydrocarbon gases became only slightly heavier in hydrous pyrolysis, compared to that from anhydrous pyrolysis. With the progress of thermal evolution from peat to a more advanced thermal maturity of vitrinite reflectance values（Ro） of 5.5% during the pyrolysis, the difference in the average δD value increased from 52‰ to 64‰ between the hydrous pyrolysis with saltwater and anhydrous pyrolysis and increased from 18‰ to 29‰ between the hydrous pyrolysis with freshwater and anhydrous pyrolysis, respectively. The difference in the average δ^（13）C value was only 1‰–2‰ between the hydrous and anhydrous pyrolysis. The relationships between the δD values of the generated hydrocarbon gases and Ro values as well as among δD values of the hydrocarbon gas species are established. The close relationships among these parameters suggest that the water medium had a significant effect on the hydrogen isotopic composition and a minimal effect on the carbon isotopic composition of the hydrocarbon gases. The results of these pyrolyses may provide information for the understanding of the genesis of coalbed gas from herbaceous marsh material with the participation of different diagenetic water media.

Water Role and Its Influence on Hydrogen Isotopic Composition of Natural Gas during Gas Generation

In order to discuss the role and influence of water during the generation of natural gas,the participation mechanism of water during the evolution of organic matter and its influences were summarized.In addition,we carried out an anhydrous cracking experiment of oil extracted from the Feixianguan Formation source rock in a closed system,which led to the establishment of the kinetic models for describing carbon and hydrogen isotopic fractionation during gas generation from organic matter.The models were calibrated and then applied to the northeastern Sichuan Basin.By combining a series of gas generation experiments from octadecane pyrolysis without water or with distilled water in varying mass proportions,several results were proved:(1) the hydrogen isotopic composition of natural gas becomes lighter with the participation of formation water;(2) we can quantitatively study the hydrogen isotopic fractionation with the kinetic model for describing carbon isotopic fractionation; (3) more abundant and reliable geological information can be obtained through the combined application of carbon and hydrogen isotopic indices.

Influence of Microwave Power on the Properties of Hydrogenated Diamond-Like Carbon Films Prepared by ECR Plasma Enhanced DC Magnetron Sputtering

Electron cyclotron resonance （ECR） plasma was applied to enhance the direct current magnetron sputtering to prepare hydrogenated diamond-like carbon （H-DLC） films. For different microwave powers, both argon and hydrogen gas are introduced separately as the ECR working gas to investigate the influence of microwave power on the microstructure and electrical property of the H-DLC films deposited on P-type silicon substrates. A series of characterization methods including the Raman spectrum and atomic force microscopy are used. Results show that, within a certain range, the increase in microwave power affects the properties of the thin films, namely the sp3 ratio, the hardness, the nanoparticle size and the resistivity all increase while the roughness decreases with the increase in microwave power. The maximum of resistivity amounts to 1.1×10^9 Ω.cm. At the same time it is found that the influence of microwave power on the properties of H-DLC films is more pronounced when argon gas is applied as the ECR working gas, compared to hydrogen gas.

A new kinetic model for direct CO2 hydrogenation to higher hydrocarbons on a precipitated iron catalyst:Effect of catalyst particle size

The kinetic of the direct COhydrogenation to higher hydrocarbons via Fischer–Tropsch synthesis（FTS）and reverse water-gas shift reaction（RWGS） mechanisms over a series of precipitated Fe/Cu/K catalysts with various particle sizes was studied in a well mixed, continuous spinning basket reactor. The iron catalysts promoted with copper and potassium were prepared via precipitation technique in various alcohol/water mixtures to achieve a series of catalyst particle sizes between 38 and 14 nm. A new kinetic model for direct COhydrogenation was developed with combination of kinetic model for FTS reaction and RWGS equilibrium condition. For estimate of structure sensitivity of indirect COhydrogenation to higher hydrocarbons, the kinetic parameters of developed model are evaluated for a series of iron catalysts with various particle sizes. For kinetic study a wide range of syngas conversions have been obtained by varying experimental conditions. The results show that the new developed model fits favorably with experimental data. The values of activation energies for indirect COhydrogenation reaction are fall within the narrow range of 23–16 kJ/mol.

Effect of alkali metals on the performance of CoCu/TiO_2 catalysts for CO_2 hydrogenation to long-chain hydrocarbons

CoCu/TiO_2 catalysts promoted using alkali metals（Li, Na, K, Rb, and Cs） were prepared by the homogeneous deposition-precipitation method followed by the incipient wetness impregnation method. The influences of the alkali metals on the physicochemical properties of the CoCu/TiO_2 catalysts and the catalytic performance for CO_2 hydrogenation to long-chain hydrocarbons（C_（5＋））were investigated in this work. According to the characterization of the catalysts based on X-ray photoelectron spectroscopy, X-ray diffraction, CO_2 temperature-programmed desorption（TPD）, and H_2-TPD, the introduction of alkali metals could increase the CO_2 adsorption and decrease the H_2 chemisorption, which could suppress the formation of CH_4, enhance the production of C_（5＋）, and decrease the hydrogenation activity. Among all the promoters, the Na-modified CoCu/TiO_2 catalyst provided the maximum C_（5＋） yield of 5.4%, with a CO_2 conversion of 18.4% and C_（5＋） selectivity of42.1%, because it showed the strongest basicity and a slight decrease in the amount of H_2 desorption;it also exhibited excellent catalytic stability of more than 200 h.

Selective hydrogenation of biomass-derived 5-hydroxymethylfurfural using palladium catalyst supported on mesoporous graphitic carbon nitride

Selective hydrogenation of biomass-derived 5-hydroxymethylfurfural（HMF） to 2,5-dihydroxymethyltetrahydrofuran（DHMTHF） with 96% selectivity and a complete HMF conversion is obtained over palladium catalyst supported on mesoporous graphitic carbon nitride（Pd/mpg-C_3N_4） under pressured hydrogen atmosphere in aqueous media. The excellent catalytic performance of Pd/mpg-C_3N_4 is attributed to hydrogen bonding-related competitive interactions between reactant HMF and “intermediate” 2,5-dihydroxymethylfuran（DHMF） with the support mpg-C_3N_4, which leads to a deep hydrogenation of DHMF to DHMTHF.

Ball-milling MoS_2/carbon black hybrid material for catalyzing hydrogen evolution reaction in acidic medium

Replacing platinum for catalyzing hydrogen evolution reaction （HER） in acidic medium remains great chal- lenges. Herein, we prepared few-layered MoS2 by ball milling as an efficient catalyst for HER in acidic medium, The activity of as-prepared MoS2 had a strong dependence on the ball milling time, Furthermore, Ketjen Black EC 300J was added into the ball-milled MoS2 followed by a second ball milling, and the resultant MoS2/carbon black hybrid material showed a much higher HER activity than MoS2 and carbon black alone. The enhanced activity of the MoS2/carbon black hybrid material was attributed to the increased abundance of catalytic edge sites of MoS） and excellent electrical coupling to the underlving carbon network.

Stability and Electronic Properties of Hydrogenated Zigzag Carbon Nanotube Focused on Stone-Wales Defect

We present a first-principles study of the chemisorption of hydrogen on a Stone-Wales （SW） defective carbon nanotube （10,0）. The investigated configurations include four configurations covering single defects and double defects. One hydrogen dimer adsorption is energetically favored on bonds shared by carbon heptagon-heptagon for configurations with the defect parallel to the tube axis compared with the carbon pentagon-hexagon sites for ones with a slanted defect. This different behavior is also demonstrated for hydrogen dimer chain adsorption, the favored site for the former ones is through the defect, which is the nearest neighbor site to defect for the latter ones. It is found that the energy band gaps of hydrogenated configurations may be enlarged or decreased by altering the adsorption site or defect position. The semiconductor-to-metal transition may occur for configurations with the defect or defects parallel to the tube axis due to low electronic localization. Our results highlight the interest of the interaction of multi-factor system by providing a detailed bond and position picture of a hydrogenated defective carbon nanotube （10,0）.

MAGNETIC ACOUSTIC EMISSION CHARACTERISTICS OF HYDROGEN ATTACKED LOW CARBON STEEL

Hydrogen attack occurred in low carbon steel and steel 25CrMo which had been exposed in hydrogen under 18MPa at 450 and 500℃ for 240,480 and 720 h.The methane bubbles and microcracks grow along grain boundaries.The degree of hydrogen attack increases with increasing exposure time and temperature.Magnetic acoustic emission(MAE) was used to detect the degree of hydrogen attack.The results show that the characteristics of MAE for samples of low carbon steel and steel 15CrMo with hydrogen attack have changed obviously comparing to the samples without hydrogen attack,and the MAE signals was sensitive to the degree of hydrogen attack at the last stage of hydrogen attack.The magnetic detection way,as a new method of nonrestrictive testing of hydrogen attack,can be used to detect the hydrogen attack in practice.

A nano-engineered graphene/carbon nitride hybrid for photocatalytic hydrogen evolution

A metal-free photocatalytic hydrogen evolution system was successfully fabricated using heteroatom doped graphene materials as electron-transfer co-catalysts and carbon nitride as a semiconductor. The catalytic role of graphene is significantly dependent on the heteroatom dopant of the graphene, such as O, S, B, N doped/undoped graphene co-catalysts, and N-graphene shows the best catalytic hydrogen evolution rate.

Theoretical Investigation for Two-state Reactivity of CO_2 Hydrogenation Catalyzed by Ru in Gas Phase

Gas-phase CO_2 catalyzed activation hydrogenation by Ru atoms was studied with density functional theory. Based on the structure optimization of different potential energy surfaces,there are two crossing points between singlet and triplet potential energy surfaces and there is a crossing point between quintet and triplet potential energy surfaces in the whole catalytic cycle. Spin transition probabilities in the vicinity of the intersections have been calculated by the Landau-Zener model theory. There are three minimum energy crossing points（MECPs） with strong spin-orbital coupling effect and higher spin transition probability,and all spin inversion occurred in s orbital and different d orbitals of ruthenium,indicating this is a typical two-state reactivity（TSR） reaction. Finally,the lowest energy reaction path is ensured.

Experimental Design Technique on Removal of Hydrogen Sulfide using CaO-eggshells Dispersed onto Palm Kernel Shell Activated Carbon：Experiment,Optimization,Equilibrium and Kinetic Studies

This study presents the use of chicken eggshells waste utilizing palm kernel shell based activated carbon（PKSAC） through the modification of their surface to enhance the adsorption capacity of H2S. Response surface methodology technique was used to optimize the process conditions and they were found to be： 500 mg/L for H2S initial concentration, 540 min for contact time and 1 g for adsorbent mass. The impacts of three arrangement factors（calcination temperature of impregnated activated carbon（IAC）, the calcium solution concentration and contact time of calcination） on the H2S removal efficiency and impregnated AC yield were investigated. Both responses IAC yield（IACY, %） and removal efficiency（RE, %） were maximized to optimize the IAC preparation conditions. The optimum preparation conditions for IACY and RE were found as follows： calcination temperature of IAC of 880 ℃, calcium solution concentration of 49.3% and calcination contact time of 57.6 min, which resulted in 35.8% of IACY and 98.2% RE. In addition, the equilibrium and kinetics of the process were investigated. The adsorbent was characterized using TGA, XRD, FTIR, SEM/EDX, and BET. The maximum monolayer adsorption capacity was found to be 543.47 mg/g. The results recommended that the composite of PKSAC and Ca O could be a useful material for H2S containing wastewater treatment.

Recent advances in carbon dioxide selective hydrogenation and biomass valorization via single-atom catalysts

The utilization of fossil fuels has brought unprecedented prosperity and development to human society,but also caused environmental pollution and global warming triggered by excess greenhouse gases emission.For one thing,the excess emission of carbon dioxide(CO_(2)),which has a negative impact on global temperature and ocean acidity,needs to be controlled.For another,the depletion of fossil fuels will eventually force people to seek alternative carbon sources to maintain a sustainable economy.Thus,using renewable energy to convert CO_(2) and biomass into value-added chemicals and fuels is a promising method to overcome urgent problems.The hy-drogenation of CO_(2) is very important to mitigate the greenhouse effect caused by CO_(2),while biomass conversion can produce alternative renewable biofuels and green chemicals.As a kind of promising catalyst,heterogeneous single-atom catalyst(SAC)has received extensive attention in the past decades.SACs combine the advantages of homogeneous catalysts with uniform active sites and heterogeneous catalysts that are easily separable.In this review,we will give a comprehensive overview of the latest progress in CO_(2) selective hydrogenation and biomass conversion via SACs.