MOF‐derived 1D/3D N‐doped porous carbon for spatially confined electrochemical CO_(2) reduction to adjustable syngas

Electrochemical reduction of CO_(2) to syngas(CO and H_(2))offers an efficient way to mitigate carbon emissions and store intermittent renewable energy in chemicals.Herein,the hierarchical one‐dimensional/three‐dimensional nitrogen‐doped porous carbon(1D/3D NPC)is prepared by carbonizing the composite of Zn‐MOF‐74 crystals in situ grown on a commercial melamine sponge(MS),for electrochemical CO_(2) reduction reaction(CO_(2)RR).The 1D/3D NPC exhibits a high CO/H_(2) ratio(5.06)and CO yield(31 mmol g^(−1)h^(−1))at−0.55 V,which are 13.7 times and 21.4 times those of 1D porous carbon(derived from Zn‐MOF‐74)and N‐doped carbon(carbonized by MS),respectively.This is attributed to the unique spatial environment of 1D/3D NPC,which increases the adsorption capacity of CO_(2) and promotes electron transfer from the 3D N‐doped carbon framework to 1D carbon,improving the reaction kinetics of CO_(2)RR.Experimental results and charge density difference plots indicate that the active site of CO_(2)RR is the positively charged carbon atom adjacent to graphitic N on 1D carbon and the active site of HER is the pyridinic N on 1D carbon.The presence of pyridinic N and pyrrolic N reduces the number of electron transfer,decreasing the reaction kinetics and the activity of CO_(2)RR.The CO/H_(2) ratio is related to the distribution of N species and the specific surface area,which are determined by the degree of spatial confinement effect.The CO/H_(2) ratios can be regulated by adjusting the carbonization temperature to adjust the degree of spatial confinement effect.Given the low cost of feedstock and easy strategy,1D/3D NPC catalysts have great potential for industrial application.

A progress review of black carbon deposition on Arctic snow and ice and its impact on climate change

The rapid warming of the Arctic,accompanied by glacier and sea ice melt,has significant consequences for the Earth’s climate,ecosystems,and economy.Black carbon(BC)deposition on snow and ice can trigger a significant reduction in snow albedo and accelerate melting of snow and ice in the Arctic.By reviewing the published literatures over the past decades,this work provides an overview of the progress in both the measurement and modeling of BC deposition and its impact on Arctic climate change.In summary,the maximum value of BC deposition appears in the western Russian Arctic(26 ng·g^(–1)),and the minimum value appears in Greenland(3 ng·g^(–1)).BC records in the Arctic ice core already peaked in 1920s and 1970s,and shows a regional difference between Greenland and Canadian Arctic.The different temporal variations of Arctic BC ice core records in different regions are closely related to the large variability of BC emissions and transportation processes across the Arctic region.Model simulations usually underestimate the concentration of BC in snow and ice by 2–3 times,and cannot accurately reflect the seasonal and regional changes in BC deposition.Wet deposition is the main removal mechanism of BC in the Arctic,and observations show different seasonal variations in BC wet deposition in Ny-Ålesund and Barrow.This discrepancy may result from varying contributions of anthropogenic and biomass burning(BB)emissions,given the strong influence by BC from BB emissions at Barrow.Arctic BC deposition significantly influences regional climate change in the Arctic,increasing fire activities in the Arctic have made BB source of Arctic BC more crucial.On average,BC in Arctic snow and ice causes an increase of+0.17 W·m^(–2)in radiative forcing and 8 Gt·a^(–1)in runoff in Greenland.As stressed in the latest Arctic Monitoring and Assessment Programme report,reliable source information and long-term and high-resolution observations on Arctic BC deposition will be crucial for a more comprehensive understanding and a better mitigation strategy of Arctic BC.In the future,it is necessary to collect more observations on BC deposition and the corresponding physical processes(e.g.,snow/ice melting,surface energy balance)in the Arctic to provide reliable data for understanding and clarifying the mechanism of the climatic impacts of BC deposition on Arctic snow and ice.

Syngas Production by Methane Reforming with Carbon Dioxide on Noble Metal Catalysts

A series of noble metal catalysts （Ru, Rh, Ir, Pt, and Pd） supported on alumina-stabilized magnesia （Spinel） were used to produce syngas by methane reforming with carbon dioxide. The synthesized catalysts were characterized using BET, TPR, TPO, TPH, and H2S chemisorption techniques. The activity results showed high activity and stability for the Ru and Rh catalysts. The TPO and TPH analyses indicated that the main reason for lower activity and stability of the Pd catalyst was the formation of the less reactive deposited carbon and sintering of the catalyst.

Carbon Dioxide Reforming of Methane to Syngas by Thermal Plasma

Experiments were conducted on syngas preparation from dry reforming of methane by carbon dioxide with a DC arc plasma at atmospheric pressure. In all experiments, nitrogen gas was used as the working gas for thermal plasma to generate a high-temperature jet into a horizontal tube reactor. A mixture of methane and carbon dioxide was fed vertically into the jet. In order to obtain a higher conversion rate of methane and carbon dioxide, chemical energy efficiency and fuel production efficiency, parametric screening studies were conducted, in which the volume ratio of carbon dioxide to methane in fed gases and the total flux of fed gases were taken into account. Results showed that carbon dioxide reforming of methane to syngas by thermal plasma exhibited a larger processing capacity, higher conversion of methane and carbon dioxide and higher chemical energy efficiency and fuel production efficiency. In addition, thermodynamic simulation for the reforming process was conducted. Experimental data agreed well with the thermodynamic results, indicating that high thermal efficiency can be achieved with the thermal plasma reforming process.

Effects of Syngas Particulate Fly Ash Deposition on the Mechanical Properties of Thermal Barrier Coatings on Simulated Film-Cooled Turbine Vane Components

Research is being conducted to study the effects of particulate deposition from contaminants in coal synthesis gas (syngas) on the mechanical properties of thermal barrier coatings (TBC) employed on integrated gasification combined cycle (IGCC) turbine hot section airfoils. West Virginia University (WVU) had been working with US Department of Energy, National Energy Technology Laboratory (NETL) to simulate deposition on the pressure side of an IGCC turbine first stage vane. To model the deposition, coal fly ash was injected into the flow of a combustor facility and deposited onto TBC coated, angled film-cooled test articles in a high pressure (approximately 4 atm) and a high temperature (1560 K) environment. To investigate the interaction between the deposition and the TBC, a load-based multiple-partial unloading micro-indentation technique was used to quantitatively evaluate the mechanical properties of materials. The indentation results showed the Young’s Modulus of the ceramic top coat was higher in areas with deposition formation due to the penetration of the fly ash. This corresponds with the reduction of strain tolerance of the 7% yttria-stabilized zirconia (7YSZ) coatings.

Investigation of Deuterium Isotope Effects in the Carbon Dioxide Reforming of Methaneto Syngas over Rhodium Catalysts

Deuterium isotope effects in the CO2-reforming of methane to syngas were firstinvestigated over SiO2-supported rhodium catalysts. Normal deuterium isotop effect was morenoticeable on the methane conversion reaction than on the CO formation reaction, while there wasno such effect on the CO2 conversion reaction. It can be concluded that the dissociation of the C-Hbond in methane is a key mp and some CO is formed by the reverse water-gas shift reaction.

Organic carbon deposition flux on the North Chukchi Sea shelf based on ^(210)Pb radioactivity dating

Deposition of organic carbon forms the final net effect of the ocean carbon sink at a certain time scale. Organic carbon deposition on the Arctic shelves plays a particularly important role in the global carbon cycle because of the broad shelf area and rich nutrient concentration. To determine the organic carbon deposition flux at the northern margin of the Chukchi Sea shelf, the 210pb dating method was used to analyze the age and deposition rate of sediment samples from station R17 of the third Chinese National Arctic Research Expedition. The results showed that the deposition rate was 0.6 mm＇aI, the apparent deposition mass flux was 0.72 kg.m2a1, and the organic carbon deposition flux was 517 mmol C.m2.al. It was estimated that at least 16% of the export organic carbon flux out of the euphoric zone was transferred and chronically buried into the sediment, a value which was much higher than the average ratio （-10%） for low- to mid-latitude regions, indicating a highly effective carbon sink at the northern mar- gin of the Chukchi Sea shelf. With the decrease of sea ice coverage caused by warming in the Arctic Ocean, it could be inferred that the Arctic shelves will play an increasingly important role in the global carbon cycle.

Effects of specific surface area of metallic nickel particles on carbon deposition kinetics

Carbon deposition on nickel powders in methane involves three stages in different reaction temperature ranges. Temperature programing oxidation test and Raman spectrum results indicated the formation of complex and ordered carbon structures at high deposition temperatures. The values of I（D）/I（G） of the deposited carbon reached 1.86, 1.30, and 1.22 in the first, second, and third stages, respectively. The structure of carbon in the second stage was similar to that in the third stage. Carbon deposited in the first stage rarely contained homogeneous pyrolytic deposit layers. A kinetic model was developed to analyze the carbon deposition behavior in the first stage. The rate-determining step of the first stage is supposed to be interfacial reaction. Based on the investigation of carbon deposition kinetics on nickel powders from different resources, carbon deposition rate is suggested to have a linear relation with the square of specific surface area of nickel particles.

Manipulating photogenerated electron flow in nickel single‐atom catalysts for photocatalytic CO_(2) reduction into tunable syngas

The key to designing photocatalysts is to orient the migration of photogenerated electrons to the target active sites rather than dissipate at inert sites.Herein,we demonstrate that the doping of phosphorus(P)significantly enriches photogenerated electrons at Ni active sites and enhances the performance for CO_(2) reduction into syngas.During photocatalytic CO_(2) reduction,Ni single‐atom‐anchored P‐modulated carbon nitride showed an impressive syngas yield rate of 85μmol gcat^(−1)h^(−1) and continuously adjustable CO/H_(2) ratios ranging from 5:1 to 1:2,which exceeded those of most of the reported carbon nitride‐based single‐atom catalysts.Mechanistic studies reveal that P doping improves the conductivity of catalysts,which promotes photogenerated electron transfer to the Ni active sites rather than dissipate randomly at low‐activity nonmetallic sites,facilitating the CO_(2)‐to‐syngas photoreduction process.

Topography,structure,and formation kinetic mechanism of carbon deposited onto nickel in the temperature range from 400 to 850°C

The carbon deposition behavior on nickel particles was observed within the temperature range from 400 to 800°C in a pure methane atmosphere. The topography, properties, and molecular structure of the deposited carbon were investigated using field-emission scanning electron microscopy (FESEM), temperature-programmed oxidation (TPO) technology, X-ray diffraction (XRD), and Raman spectroscopy. The deposited carbon is present in the form of a film at 400-450°C, as fibers at 500-600°C, and as particles at 650-800°C. In addition, the structure of the deposited carbon becomes more ordered at higher temperatures because both the TPO peak temperature of deposited carbon and the Raman shift of the G band increase with the increase in experimental temperature, whereas the intensity ratio between the D bands and the G band decreases. An interesting observation is that the carbon deposition rate is suppressed in the medium-temperature range (M-T range) and the corresponding kinetic mechanism changes. Correspondingly, the FWHM of the G and D1 bands in the Raman spectrum reaches a maximum and the intensities of the D2, D3, and D4 bands decrease to low limits in the M-T range. These results indicate that carbon structure parameters exhibit two different tendencies with respect to varying temperature. Both of the two group parameters change dramatically as a peak function with increasing reaction temperature within the M-T range.

Influence of Supports on Catalytic Performance and Carbon Deposition of Palladium Catalyst for Methane Partial Oxidation

The catalytic performance of methane partial oxidation was investigated on Pd/CeO2-ZrO2 and Pd/α-Al2O3 catalysts.The catalysts were characterized by XRD,Raman spectra,and TG-DTA techniques.The results show that CeO2-ZrO2 support is more advantageous for the catalytic activity and stability of catalysts compared to α-Al2O3.TG-DTA and Raman spectra results indicated that carbon deposited on the catalysts was in the form of graphite,which is the main reason for the deactivation of catalysts after a 24-hour reaction.Moreover,CeO2-ZrO2 had positive effect on inhibiting carbon deposition.

Characterization of Carbon Deposits Formed During Plasma Pyrolysis of Xinjiang Candle Coal

Carbon deposits were formed on the reactor wall during plasma pyrolysis of the Xinjiang candle coal in our V-style plasma pyrolysis pilot-plant. The carbon deposits were studied using a scanning electronic microscope （SEM） and the X-ray diffraction （XRD） method. It was found that carbon deposits located at different parts in the reactor exhibited different microscopic patterns. The formation mechanism of the carbon deposits was deduced. The downward increase in the graphitization degree of the carbon deposits was found and interpreted.

Kinetics of Carbon Deposition on Hexaaluminate LaNiAl_(11)O_(19) Catalyst During CO_2 Reforming of Methane

In this paper, the properties of carbon deposited on hexaaluminateLaNiAl_(11)O_(19) catalyst were characterized by X-ray photoelectron spectroscopy (XPS), and in themeantime, the amount of carbon deposited on the catalyst, after both CH_4 decomposition and CO_2reforming of CH_4, was determined by means of thermogravimetric analysis (TGA), respectively. Therates of carbon deposited on the catalyst were also investigated and the apparent kinetic equationof CO_2 reforming of CH_4: ν_c = kp^(0.72)(CH_4)·p^(-0.55)(CO_2), was established by analyzing therelation between the rates of deposited carbon and the pressure ratio of CH_4 and CO_2.

Three dimensional microstructures of carbon deposition on Ni-YSZ anodes under polarization

In the present study,two Ni/YSZ anodes with different volume ratios of Ni and YSZ,30:70 and 45:55 vol%,are operated in dry methane under open circuit and polarized conditions.Three-dimensional(3D)Ni/YSZ microstructures after carbon deposition are reconstructed by the focused ion beam-scanning electron microscopy(FIB-SEM)with the help of machine learning segmentation.From the reconstructed mircostructures,volume fraction,connectivity,three phase boundary(TPB)density,and tortuosity are quantified.In addition,local carbon microstructures are quantitatively reconstructed,and the effect of polarization on carbon morphology is investigated.It is demonstrated that Ni surface in the vicinity of active TPB near the electrolyte is free from carbon formation,while remaining Ni surface at some distances from TPB exhibits severe carbon deposition.In average,total amount of carbon deposition is larger near the electrolyte.These observations imply complex interplay between the electrochemical steam generation and methane cracking on Ni surface which take place very locally near the active TPB.

Minimizing carbon deposition in plasma-induced methane coupling with structured hydrogenation catalysts

The effect of temperature and hydrogen addition on undesired carbonaceous deposit formation during methane coupling was studied in DBD-plasma catalytic-wall reactors with Pd/Al2 O3, using electrical power to drive the reaction.Experiments with thin catalyst layers allowed comparison of the performance of empty reactors and catalytic wall reactors without significantly influencing the plasma properties.The product distribution varies strongly in the temperature window between 25 and 200℃Minimal formation of deposits is found at an optimal temperature around 75℃ in the catalytic-wall reactors.The selectivity to deposits was c.a.10% with only 9 mg of catalyst loading instead of 45% in the blank reactor,while decreasing methane conversion only mildly.Co-feeding H2 to an empty reactor causes a similar decrease in selectivity to deposits,but in this case methane conversion also decreased significantly.Suppression of deposits formation in the catalytic-wall reactor at 75℃ is due to catalytic hydrogenation of mainly acetylene to ethylene.In the empty reactor,H2 co-feed decreases conversion but does not change the product distribution.The catalytic-wall reactors can be regenerated with H2-plasma at room temperature,which produces more added-value hydrocarbons.

Study on Highly Active Catalysts and a Once-Through Process for Methanol Synthesis from Syngas

Highly active CNT-promoted co-precipitated Cu-ZnO-Al_2O_3 catalysts,symbolized as Cu_iZn_jAl_k-x%CNTs, were prepared, and their catalytic activity for once-throughmethanol synthesis from syngas was investigated. The results illustrated that, under the reactionconditions (at 493 K, 5.0 MPa, the volume ratio of H_2/CO/CO_2/N_2= 62/30/5/3, GHSV= 4000 h^(-1),the observed single-pass CO-conversion and methanol-STY over a Cu_6Zn_3Al_1-12.5%CNTs catalystreached 64% and 1210 mg/(h-g), which was about 68% and 66% higher than those (38% and 730 mg/(h·g))over the corresponding CNT-free catalyst, Cu-6Zn_3Al_1, respectively. The characteristic studies ofthe catalysts revealed that appropriate incorporation of a minor amount of the CNTs into theCu_iZn_jAl_k brought about little change in the apparent activation energy of the methanol synthesisreaction, however, led to a considerable increase in the catalyst's active Cu surface area andpronouncedly enhanced the stationary-state concentration of active hydrogen-adspecies on the surfaceof the functioning catalyst, which would be favorable to increasing the rate of the COhydro-genation reactions. Moreover, the operation temperature for methanol synthesis over theCNT-promoted catalysts can be 10-20 degrees lower than that over the corresponding CNT-free contrastsystem, which would contribute considerably to an increase in equilibrium CO-conversion andCH_3OH-yield.

Simultaneous syngas production with different H_2/CO ratio in a multi-tubular methane steam and dry reformer by utilizing of CLC

For syngas production, the combustion of fossil fuels produces large amounts of CO2 as a greenhouse gas annually which intensifies global warming. In this study, chemical looping combustion （CLC） has been utilized for the elimination of CO2 emission to atmosphere during simultaneous syngas production with different H2/CO ratio in steam reforming of methane （SR） and dry reforming of methane （DR） in a CLC-SR-DR configuration. In CLC-SR-DR with 184 reformer tubes （similar to an industrial scale steam reformer in Zagros Petrochemical Company, Assaluyeh, Iran）, DR reaction occurs over Rh-based catalysts in 31 tubes. Also, SR reaction is happened over Ni-based catalysts in 153 tubes. CLC via employment of Mn-based oxygen carriers supplies heat for DR and SR reactions and produces CO2 and H2O as raw materials simultaneously. A steady state heterogeneous catalytic reaction model is applied to analyze the performance and applicability of the proposed CLC-SR-DR configuration. Simulation results show that combustion efficiency reached 1 at the outlet of fuel reactor （FR）. Therefore, pure CO2 and H2O can be recycled to DR and SR sides, respectively. Also, CH4 conversion reached 0.2803 and 0.7275 at the outlet of SR and DR sides, respectively. Simulation results indicate that, 3223 kmol.h-l syngas with a H2/CO ratio equal to 9.826 was produced in SR side of CLC-SR-DR. After that, 1844 kmol.h-1 syngas with a H2/CO ratio equal to 0.986 was achieved in DR side of CLC-SR-DR. Results illustrate that by increasing the number of DR tubes to 50 tubes and considering 184 fixed total tubes in CLC-SR-DR, CH4 conversions in SR and DR sides decreased 2.69% and 3.31%, respectively. However, this subject caused total syngas production in SR and DR sides （in all of 184 tubes） enhance to 5427 kmol-h-1. Finally, thermal and molar behaviors of the proposed configuration demonstrate that CLC-SR-DR is applicable for simultaneous syngas production with high and low Hx/CO ratios in an environmental friendly process.

Geochronology and geodynamic setting of the carbonate-hosted Pb-Zn deposits in world-class Sichuan-Yunnan-Guizhou triangle,South China

Unraveling the precise mineralization age is vital to understand the geodynamic setting and ore-forming mechanism of the sediment-hosted Pb-Zn deposit;this has long been a challenge.The Sichuan-Yunnan-Guizhou(SYG)triangle in the southwestern margin of the Yangtze Block is a globally recognized carbonate-hosted Pb-Zn metallogenic province and also an essential part of the South China low-temperature metallogenic domain.This region has>30 million tons(Mt)Zn and Pb resources and shows the enrichment of dispersed metals,such as Ga,Ge,Cd,Se,and Tl.During the past 2 decades,abundant data on mineralization ages of Pb-Zn deposits within the SYG triangle have been documented based on various radioisotopic dating methods,resulting in significant progress in understanding the geodynamic background and ore formation of Pb-Zn deposits hosted in sedimentary rocks at SYG triangle.This paper provides a comprehensive summary of the geochronological results and Pb-Sr isotopic data regarding Pb-Zn deposits in the SYG triangle,which identified two distinct Pb-Zn mineralization periods influencing the dynamic processes associated with the expansion and closure of the Paleo-Tethys Ocean in the western margin of the Yangtze Block.The predominant phase of Pb-Zn mineralization at SYG triangle spanned from the Middle Triassic to Early Jurassic(226-191 Ma),which was intensely correlated with the large-scale basin fluid transport triggered by the closure of the Paleo-Tethys Ocean and Indosinian orogeny.The secondary Pb-Zn mineralization phase occurred during the Late Devonian to Late Carboniferous and was controlled by extensional structures associated with the expansion of the Paleo-Tethys Ocean.Further investigation is necessary to clarify the occurrence and potential factors involved in the Pb-Zn mineralization events during the Late Devonian to Late Carboniferous.

Numerical study on soot removal in partial oxidation of methane to syngas reactors

The serious carbon deposition existing in catalytic partial oxidation of methane(CPOM) to syngas process is one of the key problems that impede its industrialization. In this study, 3-dimensional unsteady numerical simulations of the soot formation and oxidation in oxidation section in a heat coupling reactor were carried out by computational fluid dynamics(CFD) approach incorporating the Moss-Brookes model for soot formation. The model has been validated and proven to be in good agreement with experiment results. Effects of nozzle type,nozzle convergence angle, channel spacing, number of channels, radius/height ratio, oxygen/carbon ratio, preheat temperature and additional introduction of steam on the soot formation were simulated. Results show that the soot formation in oxidation section of the heat coupling reactor depends on both nozzle structures and operation conditions, and the soot concentration can be greatly reduced by optimization with the maximum mass fraction of soot inside the oxidation reactor from 2.28% to 0.0501%, and so that the soot mass fraction at the exit reduces from0.74% to 0.03%.

Investigation and Mitigation of Carbon Deposition over Copper Catalyst during Electrochemical CO_(2)Reduction

Copper(Cu)is considered to be the most effective catalyst for electrochemical conversion of carbon dioxide(CO_(2))into value-added hydrocarbons,but its stability still faces considerable challenge.Here,we report the poisoning effect of carbon deposition during CO_(2)reduction on the active sites of Cu electrodea critical deactivation factor that is often overlooked.We find that,*C,an intermediate toward methane formation,could desorb on the electrode surface to form carbon species.We reveal a strong correlation between the formation of methane and the carbon deposition,and the reaction conditions favoring methane production result in more carbon deposition.The deposited carbon blocks the active sites and consequently causes rapid deterioration of the catalytic performance.We further demonstrate that the carbon deposition can be mitigated by increasing the roughness of the electrode and increasing the pH of the electrolyte.This work offers a new guidance for designing more stable catalysts for CO_(2)reduction.