Steam reforming of acetic acid over Ni/biochar of low metal-loading:Involvement of biochar in tailoring reaction intermediates renders superior catalytic performance

Biochar is a reactive carrier as it may be partially gasified with steam in steam reforming,which could influence the formation of reaction intermediates and modify catalytic behaviors.Herein,the Ni/biochar as well as two comparative catalysts,Ni/Al_(2)O_(3) and Ni/SiO_(2),with low nickel loading(2%(mass))was conducted to probe involvement of the varied carriers in the steam reforming.The results indicated that the Ni/biochar performed excellent catalytic activity than Ni/SiO_(2) and Ni/Al_(2)O_(3),as the biochar carrier facilitated quick conversion of the eOH from dissociation of steam to gasify the oxygen-rich carbonaceous intermediates like C]O and CeOeC,resulting in low coverage while high exposure of nickel species for maintaining the superior catalytic performance.In converse,strong adsorption of aliphatic intermediates over Ni/Al_(2)O_(3) and Ni/SiO_(2) induced serious coking with polymeric coke as the main type(21.5%and 32.1%,respectively),which was significantly higher than that over Ni/biochar(3.9%).The coke over Ni/biochar was mainly aromatic or catalytic type with nanotube morphology and high crystallinity.The high resistivity of Ni/biochar towards coking was due to the balance between formation of coke and gasification of coke and partially biochar with steam,which created developed mesopores in spent Ni/biochar while the coke blocked pores in Ni/Al_(2)O_(3) and Ni/SiO_(2) catalysts.

Importance of oxygen-containing functionalities and pore structures of biochar in catalyzing pyrolysis of homologous poplar

Biochar and bio-oil are produced simultaneously in one pyrolysis process,and they inevitably contact and may interact,influencing the composition of bio-oil and modifying the structure of biochar.In this sense,biochar is an inherent catalyst for pyrolysis.In this study,in order to investigate the influence of functionalities and pore structures of biochar on its capability for catalyzing the conversion of homologous volatiles in bio-oil,three char catalysts(600C,800C,and 800AC)produced via pyrolysis of poplar wood at 600 or 800℃or activated at 800℃,were used for catalyzing pyrolysis of homologous poplar wood at 600℃,respectively.The results indicated that the 600C catalyst was more active than 800C and 800AC for catalyzing cracking of volatiles to form more gas(yield increase by 40.2%)and aromatization of volatiles to form more light or heavy phenolics,due to its abundant oxygen-containing functionalities acting as active sites.The developed pores of the 800AC showed no such catalytic effect but could trap some volatiles and allow their further conversion via sufficient aromatization.Nevertheless,the interaction with the volatiles consumed oxygen on 600C(decrease by 50%),enhancing the aromatic degree and increasing thermal stability.The dominance of deposition of carbonaceous material of a very aromatic nature over 800C and 800AC resulted in net weight gain and blocked micropores but formed additional macropores.The in situ diffuse reflectance infrared Fourier transform spectroscopy characterization of the catalytic pyrolysis indicated superior activity of 600C for removal of -OH,while conversion of the intermediates bearing C=O was enhanced over all the char catalysts.

A universal charge-compensating strategy for high-energy-density pseudocapacitors

For pseudocapacitive electrode materials(PseEMs),despite much progress having been made in achieving both high power density and high energy density,a general strategy to guide the enhancement of intrinsic capacitive properties of PseEMs remains lacking.Here,we demonstrate a universal chargecompensating strategy to improve the charge-storage capability of PseEMs intrinsically:ⅰ) in the electrolyte with anion as charge carriers(such as OH-),reducing the multivalent cations of PseEMs into lower valences could create more reversible low-to-high valence redox cou ples to promote the intercalation of the anions;ⅱ) in the electrolytes with cation as charge carriers(such as H^(+),Li^(+),Na^(+)),oxidizing the multivalent cations of PseEMs into higher valences could introduce more reversible high-to-low valence redox couples to promote the intercalation of the cations.And we demonstrated that the improved intrinsic charge-storage capability for PseEMs originates from the increased Faradaic charge storage sites.

Cu-LaCoO_3催化剂选择氢解生物质基糠醇制备1,5-和1,2-戊二醇（英文）

高效转化可再生生物质资源制备人类社会必需的燃料和化学品是当前关注和研究的热点之一.生物质基糠醇来源于玉米芯、甘蔗渣、秸秆等农林副产物,价廉易得,是选择氢解合成高附加值1,2-和1,5-戊二醇的理想原料.目前生物质基呋喃衍生物氢解制备二元醇的研究主要集中在Pt,Ru,Rh和Ir等贵金属催化剂,对无Cr非贵金属催化剂的研究甚少.基于纳米Cu催化剂较高的C-O键氢解活性和较低的C-C键裂解活性,以及碱性载体对反应物和反应中间体的稳定作用,我们在前期Cu-Mg_3AlO_(4.5)和Cu-Al_2O_3催化剂催化糠醇氢解研究基础上,以具有一定碱性的ABO_3结构的钙钛矿型化合物为载体负载活性Cu开展糠醇氢解研究,深入研究催化剂结构、组成和活性金属价态等对催化剂活性和选择性影响,并研究了催化剂循环使用稳定性.首先我们采用柠檬酸一步络合法制备了一系列具有一定钙钛矿结构的不同Cu负载量(0-20 wt%)的Cu-LaCoO_3催化剂以及LaCoO_3负载的5 wt%Pt,Ru,Rh和Pd催化剂并考察了它们的糠醇选择氢解制备戊二醇性能.研究发现,在相同活性金属负载量(5 wt%)时,Cu-LaCoO_3催化剂具有较优异的呋喃环C-O键氢解活性,而贵金属催化剂倾向于催化呋喃环C=C键加氢饱和.考察不同Cu负载量的Cu-LaCoO_3催化剂催化糠醇氢解性能发现,随着Cu负载量的增加,糠醇转化率先升高后降低,在10 wt%Cu负载量时达最高(94.6%),戊二醇总选择性也随Cu负载量的增加先升高后降低,在5 wt%Cu负载量时最高(52.2%),总体以10 wt%Cu负载量催化剂表现出最优异的性能.接着我们考察了反应动力学条件如温度、压力和反应时间以及还原处理条件对10 wt%Cu-LaCoO_3催化性能的影响.研究发现适当的高温(～433 K)和高压(6 MPa H_2)有利于Cu-LaCoO_3催化糠醇氢解制戊二醇,而低浓度氢气(5 vol%)还原有利于1,5-戊二醇的生成,高氢气浓度(纯氢)还原有利于呋喃环加氢饱和的四氢糠醇生成.10 wt%Cu负载量的催化剂经5%H_2-95%N_2处理后,在413 K和6 MPa H_2条件下可取得100%的糠醇转化率以及55.5%的戊二醇总选择性(其中1,5-戊二醇和1,2-戊二醇的选择性之比接近3:1).进一步考察了10 wt%Cu-LaCoO_3催化剂的循环使用稳定性,研究发现无论是在高初始转化率(～93.7%)还是低初始转化率(～30.5%)条件下,经多次循环使用后糠醇转化率先升高后基本保持不变,而戊二醇总选择性呈下降趋势,四氢糠醇的选择性逐渐上升.结合XRD,XPS,BET,H_2-TPR,CO_2-TPD,NH3-TPD和HRTEM等多种表征技术对Cu-LaCoO_3催化剂的结构及在糠醇氢解反应中的活性位进行了表征,发现高分散的活性物种、合适的碱性以及部分还原的活性组分均有利于提高催化剂的活性与1,5-戊二醇的化学选择性,高分散的Cu^0与部分还原的Co_3O_4(很可能是CoO)之间的协同催化对于取得较优异的糠醇氢解性能,尤其是较高的1,5-/1,2-戊二醇比例至关重要.

Biomass pyrolysis: A review of the process development and challenges from initial researches up to the commercialisation stage

Lignocellulosic biomass can be convert to a condensable liquid named bio-oil,a solid product named as char and a mixture of gaseous products comprising CO2,CO,H2,CH4,etc.In recent years,much effort has been made on the investigation of conversion of biomass through pyrolysis.However,commercialisation of the biomass pyrolysis technology is still challenging due to various issues such as the deleterious properties of bio-oil including the low heating value and the high instability at elevated temperatures.To overcome such issues,many processes,reactors and catalysts have been developed for pyrolysis and catalytic pyrolysis of biomass.A state to the art of pyrolysis or catalytic pyrolysis of biomass need to be summarised to have an overall evaluation of the technologies,in order to provide a useful reference for the further development of pyrolysis technology.This study reviews the various pyrolysis process,especially focus on the effects of essential parameters,the process design,the reactors and the catalysts on the pyrolysis process.In addition,progress in commercialisation of pyrolysis technology was also reviewed and the remaining issues in the process of commercialisation were discussed.

Ultra-stable CsPbBr3 Perovskite Nanosheets for X-Ray Imaging Screen

Wet chemistry methods,including hot-injection and precipitation methods,have emerged as major synthetic routes for high-quality perovskite nanocrystals in backlit display and scintillation applications.However,low chemical yield hinders their upscale production for practical use.Meanwhile,the labile nature of halide-based perovskite poses a major challenge for long-term storage of perovskite nanocrystals.Herein,we report a green synthesis at room temperature for gram-scale production of CsPbBr3 nanosheets with minimum use of solvent,saving over 95% of the solvent for the unity mass nanocrystal production.The perovskite colloid exhibits record stability upon long-term storage for up to 8 months,preserving a photoluminescence quantum yield of 63% in solid state.Importantly,the colloidal nanosheets show self-assembly behavior upon slow solidification,generating a crack-free thin film in a large area.The uniform film was then demonstrated as an efficient scintillation screen for X-ray imaging.Our findings bring a scalable tool for synthesis of high-quality perovskite nanocrystals,which may inspire the industrial optoelectronic application of large-area perovskite film.

Steam reforming of acetic acid over Ni-Ba/Al2O3 catalysts:Impacts of barium addition on coking behaviors and formation of reaction intermediates

The influence of barium addition to a Ni/Al2O3 catalyst on the reaction intermediates formed,the activity,resistance of the catalyst to coking,and properties of the coke formed after acetic acid steam reforming were investigated in this study.The results showed the drastic effects of barium addition on the physicochemical properties and performances of the catalyst.The solid-phase reaction between alumina and BaO formed BaAl2O4,which re-constructed the alumina structure,resulting in a decrease in the specific surface area and an increase in the resistance of metallic Ni to sintering.The addition of barium was also beneficial for enhancing the catalytic activity,resulting from the changed catalytic reaction network.The in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study of the acetic acid steam reforming indicated that barium could effectively suppress the accumulation of the reaction intermediates of carbonyl,formate,and C=C functional groups on the catalyst surface,attributed to its relatively high ability to cause the gasification of these species.In addition,coking was considerably more significant over the Ba-Ni/Al2O3 catalyst.Moreover,the Ba-Ni/Al2O3 catalyst was more stable than the Ni/Al2O3catalyst,owing to the distinct forms of coke formed (carbon nanotube form over the Ba-Ni/Al2O3 catalyst,and the amorphous form over the Ni/Al2O3 catalyst).

Mitochondrial malic enzyme 2 promotes breast cancer metastasis via stabilizing HIF-1α under hypoxia

Objective: α-ketoglutarate(α-KG) is the substrate to hydroxylate collagen and hypoxia-inducible factor-1α(HIF-1α), which are important for cancer metastasis. Previous studies have shown that the upregulation of collagen prolyl 4-hydroxylase in breast cancer cells stabilizes the expression of HIF-1α by depleting α-KG levels. We hypothesized that mitochondrial malic enzyme 2(ME2) might also affect HIF-1α expression via modulating α-KG levels in breast cancer cells.Methods: We evaluated ME2 protein expression in 100 breast cancer patients using immunohistochemistry and correlated with clinicopathological indicators. The effect of ME2 knockout on cancer metastasis was evaluated using an orthotopic breast cancer model. The effect of ME2 knockout or knockdown on the levels of α-KG and HIF-1α proteins in breast cancer cell lines was determined both in vitro and in vivo.Results: ME2 was found to be upregulated in the human breast cancerous tissues compared with the matched precancerous tissues(P<0.001). The elevated expression of ME2 was associated with a poor prognosis(P=0.019).ME2 upregulation was also related to lymph node metastasis(P=0.016), pathological staging(P=0.033), and vascular cancer embolus(P=0.014). Also, ME2 knockout significantly inhibited lung metastasis in vivo. In the tumors formed by ME2 knockout cells, the levels of α-KG were significantly increased and collagen hydroxylation level did not change significantly but HIF-1α protein expression was significantly decreased, compared to the control samples. In cell culture, cells with ME2 knockout or knockdown demonstrated significantly higher α-KG levels but significantly lower HIF-1α protein expression than control cells under hypoxia. Exogenous malate and α-KG exerted similar effect on HIF-1α in breast cancer cells to ME2 knockout or knockdown. Additionally,treatment with malate significantly decreased 4 T1 breast cancer lung metastasis. ME2 expression was associated with HIF-1α levels in human breast cancer samples(P=0.008).Conclusions: Our results provide evidence that upregulation of ME2 is associated with a poor prognosis of breast cancer patients and propose a mechanistic understanding of a link between ME2 and breast cancer metastasis.

Detection of nasopharyngeal carcinoma using surface-enhanced laser desorption and ionization mass spectrometry profiles of the serum proteome

Background and Objective: Early diagnosis of nasopharyngeal carcinoma (NPC) is difficult due to the insufficient specificity of the conventional examination method. This study was to investigate potential and consistent biomarkers for NPC, particularly for early detection of NPC. Methods: A proteomic pattern was identified in a training set (134 NPC patients and 73 control individuals) using the surface-enhanced laser desorption and ionization-mass spectrometry (SELDI-MS), and used to screen the test set (44 NPC patients and 25 control individuals) to determine the screening accuracy. To confirm the accuracy, it was used to test another group of 52 NPC patients and 32 healthy individuals at 6 months later. Results: Eight proteomic biomarkers with top-scored peak mass/charge ratios (m/z) of 8605 Da, 5320 Da, 5355 Da, 5380 Da, 5336 Da, 2791 Da, 7154 Da, and 9366 Da were selected as the potential biomarkers of NPC with a sensitivity of 90.9% (40/44) and a specificity of 92.0% (23/25). The performance was better than the current diagnostic method by using the Epstein-Barr virus (EBV) capsid antigen IgA antibodies (VCA/IgA). Similar sensitivity (88.5%) and specificity (90.6%) were achieved in another group of 84 samples. Conclusion: SELDI-MS profiling might be a potential tool to identify patients with NPC, particularly at early clinical stages.

Roles of furfural during the thermal treatment of bio-oil at low temperatures

The reactive O-containing species in bio-oil could induce the polymerization of bio-oil during its thermal treatment, which affects the relevant utilization of bio-oil significantly. Furans, as the highly reactive Ocontaining species in bio-oil, play important roles during the thermal treatment of bio-oil. In this study,furfural was chosen as the representative of the furans in bio-oil to investigate its roles during the thermal treatment of bio-oil. The raw bio-oil with and without the addition of extra furfural(10 wt% of bio-oil) and pure furfural were pyrolyzed in a fixed-bed reactor at 200–500 ℃. The results show that the interactions among furfural and bio-oil components can take place prior to the evaporation of furfural(<140 ℃) to form the intermediates, then these intermediates could be further polymerized to form large molecular compounds, and coke can be formed via the interactions at temperatures ≥ 300 ℃. At temperatures ≤ 300 ℃, furfural mainly interacts with anhydrosugars. As the temperature further increases, the aromatics are involved in the interactions to form coke. The increased percentage of the coke formed via the interactions is in a linear relation with the conversion of furfural during the pyrolysis at 300–500 ℃(no coke formed at 200 ℃). Meanwhile, more non-aromatic light components(≤ C6) and less aromatics in the tars could be formed due to the interactions.

Cross-polymerization between the model furans and phenolics in bio-oil with acid or alkaline catalysts

Polymerization is a major challenge for the upgrading of bio-oil to biofuels,but is preferable for the production of carbon material from biooil.Understanding the mechanism for polymerization is of importance for tailoring property of carbon material.This study investigated the characteristics for the polymerisation of furfural,vanillin,their cross-polymerization and the impacts of catalysts on their polymerization.The results indicated that the organic acids like acetic acid and formic acid could catalyze the polymerisation of furfural,while H_(2)SO_(4)or NaOH as catalyst could drastically enhance the degree of polymerization of furfural.Vanillin showed a higher tendency towards polymerization than furfural and H_(2)SO_(4)or NaOH significantly facilitated the polymerization of vanillin via shifting the pasty product to solid polymer.The crosspolymerization between furfural and vanillin occurred even in the absence of catalyst,while the presence of H_(2)SO_(4)or NaOH catalyst resulted in the formation of more solid polymer via cross-polymerization.The polymerisation reactions were accompanied with the consumption of–C¼O via aldol addition/condensation reactions.In addition,the morphology and thermal stability of the polymers formed were affected by both the type of the catalysts employed,which can in turn enhance the cross-polymerization between furfural and vanillin.

TILA-TACE – an approach for effective local control of hepatocellular carcinoma

INTRODUCTION HCC is the sixth common cancer but the third leading cause of cancer-related death(1).More than50%of all HCC patients worldwide are from China alone.The incidence rate of HCC is nearly equal to the mortality rate(1),indicating a highly unmet medical need.Most HCC patients at first diagnosis are already at the BCLC(Barcelona Clinic Liver Cancer Staging Classification)stage B or C,not suitable for curative therapy including surgery,ablation,and liver transplantation.

Direct conversion of furfural to levulinic acid/ester in dimethoxymethane:Understanding the mechanism for polymerization

This study investigated the conversion of furfural to 5-hydroxymethylfurfural(HMF)and further to levulinic acid/ester in dimethoxymethane under acidic conditions,with the particular focus on understanding the mechanism for polymer formation.The results showed that furfural could react with dimethoxymethane via electrophilic substitution reaction to form HMF or the ether/acetal of HMF,which were further converted to levulinic acid and methyl levulinate.The polymerization of furfural and the cross-polymerization between dimethoxymethane and the levulinic acid/ester produced were the main side reactions leading to the decreased yields of levulinic acid/ester.Comparing to the other solvent,methanol as the co-solvent helped to alleviate but not totally inhibited the occurrences of the polymerization,as the polymerization reactions via aldol condensation did not eliminate the C=O functionalities.As a consequence,the polymerization reactions continued to proceed.Other co-solvent used such as guaiacol,dimethyl sulfoxide and acetone interfered with the transformation of furfural to HMF or aided the polymerization reactions.The polymer produced from the reactions between furfural and DMM was different from that produced from levulinic acid/ester.The former had a higher crystallinity,while the latter was more aliphatic.The DRIFTS and TG-MS studies showed that the polymer had the carboxylic group,methyl group and the aliphatic structure in the skeleton.The removal of these functionalities was accompanied by the aromatization of the polymer.The condensation of DMM with levulinic acid/ester was the key reason for the diminished production of levulinic acid/ester.

Ni–Co bimetallic coordination effect for long lifetime rechargeable Zn–air battery

The development of bifunctional oxygen electrocatalysts with high efficiency, high stability, and low cost is of great significance to the industrialization of rechargeable Zn–air batteries. A widely accepted view is that the oxygen reduction reaction(ORR) and the oxygen evolution reaction(OER) follow different catalytic mechanisms, and accordingly they need different active sites for catalysis. Transition metal elements have admirable electronic acceptance ability for coordinating with reactants, and this can weaken the bond energy between reactants, thus promoting the ORR or OER reactions. Herein, the ORR and OER activities of different transition metal supported nitrogen-doped carbon nanotubes were systematically studied and compared. The optimal catalyst for synchronous ORR and OER was obtained by pyrolyzing melamine, cobalt nitrate, and nickel nitrate on carbon nanotubes, called cobalt–nickel supported nitrogenmixed carbon nanotubes(CoNi–NCNT), which were equipped with two types of high-performance active sites—the Co/Ni–N–C structure for the ORR and Co Ni alloy particles for the OER—simultaneously. Remarkably, the optimized Co Ni–NCNT exhibited a satisfactory bifunctional catalytic activity for both the ORR and OER. The value of the oxygen electrode activity parameter,△E, of CoNi–NCNT was 0.81 V, which surpasses that of catalysts Pt/C and Ir/C, and most of the non-precious metal-based bifunctional electrocatalysts reported in previous literatures. Furthermore, a specially assembled rechargeable Zn–air cell with Co Ni–NCNT loaded carbon paper as an air cathode was used to evaluate the practicability. As a result, a superior specific capacity of 744.3 mAh/gZn, a peak power density of 88 mW/cm2, and an excellent rechargeable cycling stability were observed, and these endow the Co Ni–NCNT with promising prospects for practical application.

Beyond catalytic materials:Controlling local gas/liquid environment in the catalyst layer for CO_(2)electrolysis

Electrochemical reduction of CO_(2)to value-added chemicals using renewable electricity provides a promising strategy to achieve sustainable fuel production and carbon neutrality.Along with the development of electrocatalysts,fow cells with gas-diffusion electrodes(GDEs)have been used to reach commercially viable current densities for CO_(2)electrolysis,while the local environment and CO_(2)mass transport in the electrodes remain to be elucidated.In this review article,we highlight some insights into the microenvironment in the catalyst layer for CO_(2)electrolysis,including typical mass transport models for CO_(2)reduction in H-type cells and GDE fow cells,the effect of a hydrophobic microenvironment on CO_(2)mass transport and catalytic performance,and the formation of a gas/liquid balance and solid–liquid–gas interfaces for CO_(2)electrolysis.The insights and discussions in this article can provide important guidelines on the design of catalysts,electrodes,and electrolyzers for CO_(2)electrolysis,as well as other gas-involving electrocatalytic reactions.

Regulating adsorption ability toward polysulfides in a porous carbon/Cu_(3)P hybrid for an ultrastable high-temperature lithium-sulfur battery

Lithium-sulfur batteries(LSBs)can work at high temperatures,but they suffer from poor cycle life stability due to the“shuttle effect”of polysulfides.In this study,pollen-derived porous carbon/cuprous phosphide(PC/Cu_(3)P)hybrids were rationally synthesized using a one-step carbonization method using pollen as the source material,acting as the sulfur host for LSBs.In the hybrid,polar Cu_(3)P can markedly inhibit the“shuttle effect”by regulating the adsorption ability toward polysulfides,as confirmed by theoretical calculations and experimental tests.As an example,the camellia pollen porous carbon(CPC)/Cu_(3)P/S electrode shows a high capacity of 1205.6 mAh g^(−1) at 0.1 C,an ultralow capacity decay rate of 0.038%per cycle after 1000 cycles at 1 C,and a rather high initial Coulombic efficiency of 98.5%.The CPC/Cu_(3)P LSBs can work well at high temperatures,having a high capacity of 545.9 mAh g^(−1) at 1 C even at 150℃.The strategy of the PC/Cu_(3)P hybrid proposed in this study is expected to be an ideal cathode for ultrastable high-temperature LSBs.We believe that this strategy is universal and worthy of in-depth development for the next generation energy storage devices.

Competition between acidic sites and hydrogenation sites in Cu/ZrO_(2) catalysts with different crystal phases for conversion of biomass-derived organics

Oxides with different crystal phases can have important effects on the configuration of surface atoms,which can further affect the distribution of hydrogenation sites and acidic sites as well as the competitions of these varied types of catalytic sites.This could be potentially used to tailor the distribution of the products.In this study,zirconium oxides with different crystal phases supported copper catalysts were prepared for the hydrogenation of the biomass-derived furfural,vanillin,etc.The results showed that both calcination temperature and Cu species affected the shift of zirconia from tetragonal phase to the monoclinic phase.Monoclinic zirconia supported copper catalyst can effectively catalyze the hydrogenation of furfural to furfuryl alcohol via hydrogenation route due to its low amount of Brønsted acidic sites,although the surface area and the exposed metallic Cu surface area were much lower than the tetragonal zirconia supported copper catalyst.Zirconia with tetragonal or tetragonal/monoclinic phases supported copper catalysts contain abundant acidic sites and especially the Br?nsted acidic sites,which catalyzed mainly the conversion of furfural via the acid-catalyzed routes such as the acetalization,rather than the hydrogenation.The acidic sites over the Cu/ZrO_(2)catalyst played more predominant roles than the hydrogenation sites in determining the conversion of the organics like furfural and vanillin.

Mg-Al-hydrotalcite with alkaline sites protects Ni/KIT-6 from formation of amorphous coke in glycerol steam reforming via tailoring reaction intermediates

During steam reforming,the performance of a catalyst and amount/property of coke are closely related to reaction intermediates reaching surface of a catalyst.Herein,modification of reaction intermediates by placing Mg-Al-hydrotalcite above Ni/KIT-6 catalyst in steam reforming of glycerol was conducted at 300 to 600°C.The results revealed that the catalytic activity of Ni/KIT-6 in the lower bed was enhanced with either Mg1-Al5-hydrotalcite(containing more acidic sites)or Mg5-Al1-hydrotalcite(containing more alkaline sites)as upper-layer catalyst.The in situ infrared characterization of steam reforming demonstrated that Mg-Al-hydrotalcite catalyzed the deoxygenation of glycerol,facilitating the reforming of the partially deoxygenated intermediates over Ni/KIT-6.Mg-Al-hydrotalcite as protective catalyst,however,did not protect the Ni/KIT-6 from formation of more coke.Nonetheless,this did not lead to further deactivation of Ni/KIT-6 while Mg5-Al1-hydrotalcite even substantially enhanced the catalytic stability,even though the coke was much more significant than that in the use of single Ni/KIT-6(52.7%vs.28.6%).The reason beneath this was change of the property of coke from more aliphatic to more aromatic.Mg5-Al1-hydrotalcite catalyzed dehydration of glycerol,producing dominantly reaction intermediates bearing C=C,which formed the catalytic coke of with carbon nanotube as the main form with smooth outer walls as well as higher aromaticity,C/H ratio,crystallinity,crystal carbon size,thermal stability,and resistivity toward oxidation on Ni/KIT-6 in the lower bed.In comparison,the abundance of acidic sites on Mg1-Al5-hydrotalcite catalyzed the formation of more oxygen-containing species,leading to the formation of carbon nanotubes of rough surface on Ni/KIT-6.

Sequential pyrolysis for understanding specific influence of cellulose- and lignin-derived volatiles on properties of counterpart char

Interactions of cellulose-and lignin-derived intermediates have been well documented during pyrolysis of lignocellulosic biomass.The reaction network for the interactions is rather complex,as cellulose-derived volatiles could interact/react with not only lignin-derived volatiles but also lignin-derived char and vice versa.To probe specifically the impacts of cellulose-derived volatiles on the lignin-derived char or the opposite,herein the sequential pyrolysis was performed by arranging cellulose in the upper bed with lignin in the lower bed or lignin above with cellulose below at 350 and 650℃,respectively.The results indicated that the sequential pyrolysis of cellulose→lignin or lignin→cellulose at 350℃induced increased char yield from formation of carbonaceous deposits via volatiles-char interactions.Compared with the lignin-derived volatiles,the cellulose-derived volatiles,especially aldehyde fractions,were more reactive towards the lignin-derived char at 350℃,forming oxygen-rich lignin-derived char with a higher yield,an abundance of aliphatic structures and consequently lower thermal stability.In sequential pyrolysis of lignin→cellulose,more aromatics-rich species were deposited on cellulose-derived char,but the lignin-derived volatiles were less reactive for enhancing the char yield.At 650℃,instead of polymerisation of the volatiles on the char,either the cellulose-or lignin-derived char catalyzed the cracking of the counterpart volatiles to remove the aliphatic functionalities,which made the char more aromatic and thermally more stable.

Hallmark guided identification and characterization of a novel immune-relevant signature for prognostication of recurrence in stageⅠ-Ⅲlung adenocarcinoma

The high risk of postoperative mortality in lung adenocarcinoma(LUAD)patients is principally driven by cancer recurrence and low response rates to adjuvant treatment.Here,A combined cohort containing 1,026 stageⅠ-Ⅲpatients was divided into the learning(n Z 678)and validation datasets(n Z 348).The former was used to establish a 16-mRNA risk signature for recurrence prediction with multiple statistical algorithms,which was verified in the valida-tion set.Univariate and multivariate analyses confirmed it as an independent indicator for both recurrence-free survival(RFS)and overall survival(OS).Distinct molecular characteristics between the two groups including genomic alterations,and hallmark pathways were compre-hensively analyzed.Remarkably,the classifier was tightly linked to immune infiltrations,high-lighting the critical role of immune surveillance in prolonging survival for LUAD.Moreover,the classifier was a valuable predictor for therapeutic responses in patients,and the low-risk group was more likely to yield clinical benefits from immunotherapy.A transcription factor regulato-ry proteineprotein interaction network(TF-PPI-network)was constructed via weighted gene co-expression network analysis(WGCNA)concerning the hub genes of the signature.The con-structed multidimensional nomogram dramatically increased the predictive accuracy.There-fore,our signature provides a forceful basis for individualized LUAD management with promising potential implications.