Preparation of a high-performance synthetic pitch from aromatic hydrocarbons containing N/Cl

The preparation of a synthetic pitch from aromatic monomers could easily regulate structure orientation at the molecu-lar level,which would be useful in fabrication.An isotropic synthetic pitch was prepared by a chlorine-and/or nitrogen-induced sub-stitution polymerization reaction method using aromatic hydrocarbon precursors containing Cl and N,which for this study were chloromethyl naphthalene and quinoline.This method was verified by investigating the structural changes under different synthesis conditions,and the synthesis mechanism induced by aromatics containing Cl was also probed.The result shows that the pyridinic N in quinoline contains a lone pair of electrons,and is an effective active site to induce the polymerization reaction by coupling with aromatic hydrocarbons containing Cl.The reaction between such free radicals causes strong homopolymerization and oligomeriza-tion.A higher reaction temperature and longer reaction time significantly increased the degree of polymerization and thus increased the softening point of the pitch.A linear molecular structure was formed by the Cl substitution reaction,which produced a highly spinnable pitch with a softening point of 258.6℃,and carbon fibers with a tensile strength of 1163.82 MPa were obtained.This study provides a relatively simple and safe method for the preparation of high-quality spinnable pitch.

Conversion of Lignin into Porous Carbons for High-Performance Supercapacitors via Spray Drying and KOH Activation: Structure-Properties Relationship and Reaction Mechanism

Lignin-derived porous carbons have emerged as promising electrode materials for supercapacitors.However,the challenge remains in designing and controlling their structure to achieve ideal electrochemical performance due to the complex molecular structure of lignin and its intricate chemical reactions during the activation process.In this study,three porous carbons were synthesized from lignin by spray drying and chemical activation with vary-ing KOH ratios.The specific surface area and structural order of the prepared porous carbon continued to increase with the increase of the KOH ratio.Thermogravimetric-mass spectrometry(TG-MS)was employed to track the molecular fragments generated during the pyrolysis of KOH-activated lignin,and the mechanism of the thermochemical conversion was investigated.During the thermochemical conversion of lignin,KOH facili-tated the removal of H2 and CO,leading to the formation of not only more micropores and mesopores,but also more ordered carbon structures.The pore structure exhibited a greater impact than the carbon structure on the electrochemical performance of porous carbon.The optimized porous carbon exhibited a capacitance of 256 F g-1 at a current density of 0.2 A g-1,making it an ideal electrode material for high-performance supercapacitors.

Free radicals trigger the closure of open pores in lignin-derived hard carbons toward improved sodium-storage capacity

The chemical activation of various precursors is effective for creating additional closed pores in hard carbons for sodium storage.However,the formation mechanism of closed pores under the influence of pore-forming agents is not well understood.Herein,an effective chemical activation followed by a high-temperature self-healing strategy is employed to generate interconnected closed pores in lignin-derived hard carbon(HCs).By systematic experimental design combined with electron paramagnetic res-onance spectroscopy,it can be found that the content of free radicals in the carbon matrix influences the closure of open pores at high temperatures.Excessively high activation temperature(>700 C)leads to a low free radical concentration,making it difficult to achieve self-healing of open pores at high tempera-tures.By activation at 700°C,a balance between pore making and self-healing is achieved in the final hard carbon.A large number of free radicals triggers rapid growth and aggregation of carbon microcrys-tals,blocking pre-formed open micropores and creating additional interconnected closed pores in as-obtained hard carbons.As a result,the optimized carbon anode(LK-700-1300)delivers a high reversible capacity of 330.8 mA h g^(-1) at 0.03 A g^(-1),which is an increase of 86 mA h g^(-1) compared to the pristine lignin-derived carbon anode(L-700-1300),and exhibits a good rate performance(202.1 mA h g^(-1) at 1 A g^(-1)).This work provides a universal and effective guidance for tuning closed pores of hard carbons from otherprecursors.

Defect Engineering of Carbons for Energy Conversion and Storage Applications

Sustainable energy conversion and storage technologies are a vital prerequisite for neutral future carbon.To this end,carbon materials with attractive features,such as tunable pore architecture,good electrical conductivity,outstanding physicochemical stability,abundant resource,and low cost,have used as promising electrode materials for energy conversion and storage.Defect engineering could modulate the structures of carbon materials,thereby affecting their electronic properties.The presence of defects on carbons may lead to asymmetric charge distribution,change in geometrical configuration,and distortion of the electronic structure that may result in unexpected electrochemical performances.In this review,recent advances in defects of carbons used for energy conversion and storage were examined in terms of types,regulation strategies,and fine characterization means of defects.The applications of such carbons in supercapacitors,rechargeable batteries,and electrocatalysis were also discussed.The perspectives toward the development of defect engineering carbons were proposed.In all,novel insights related to improvement in high-performance carbon materials for future energy conversion and storage applications were provided.

Synthesis of MgO-doped ordered mesoporous carbons by Mg^(2+)-tannin coordination for efficient isomerization of glucose to fructose

In-situ MgO-doped ordered mesoporous carbon(OMC@MgO)was fabricated by formaldehyde-free self-assembly method,in which biomass-derived tannin was used as carbon precursor replacing fossil-based phenolics,Mg^(2+)as both cross-linker and precursor of catalytic sites.Up to~20 wt% MgO could be doped in the carbon skeleton with good dispersion retaining well-ordered mesoporous structures,while more MgO content(35 wt%)led to the failing in the formation of ordered mesoporous structure.The OMC@MgO possessed a high specific surface area(298.8 m^(2) g^(-1)),uniform pore size distribution(4.8 nm)and small crystallite size of MgO(1.73 nm)due to the confinement effect of ordered mesoporous structure.Using OMC@MgO as the heterogeneous catalyst,a maximum fructose yield of 32.4% with a selectivity up to 81.1%was achieved from glucose in water(90℃,60 min),which is much higher than that obtained using the MgO doped active carbon via conventional post-impregnation method(26.5%yield with 58.3% selectivity).Higher reaction temperature(>90℃)resulted in decrease of selectivity due to the formation of humins.The designed OMC@MgO displayed tolerant to high initial glucose concentrations(10 wt%)and could remain good recyclability without significant loss of activity for three cycles.

Molecular Simulation of Methane Adsorption in Different Micro Porous Activated Carbons at Different Temperatures

We employed the previously developed micro porous activated carbon models of different pore sizes ranges of 9-11?,10-12?,and 13-16?that were constructed by molecular simulation method based on a random packing of platelets of carbon sheets,functionalized with oxygen containing groups,to study the adsorption behavior of methane molecules.In studying methane adsorption behavior,we used Grand Canonical Monte Carlo and Molecular Dynamics methods at different temperatures of 273.15,298.15 and303.15 K.Adsorption isotherms,isosteric heats of adsorption,adsorption energy distributions and porosity changes of the models during adsorption process were analyzed and discussed.Furthermore,radial distribution Functions,relative distribution and diffusion coefficients of methane molecules in activated carbon models at different temperatures were studied.After the analysis,the main results indicated that large micro pores activated carbons were favorable for storing methane at lower temperatures and small micro pores were the most favorable for adsorbing methane molecules at higher temperatures.Interestingly,the developed model structures showed high capacities to store methane molecule at ambient temperatures and low pressure.

煤矿充填固碳理论基础与技术构想

在国家“双碳”目标背景下,如何减少煤炭行业的碳排放、实现碳封存已成为亟待解决的难题。煤炭行业作为高碳化石能源生产者和主体碳排放源提供者,在生产和消费过程中引发的大宗固废堆存、大型采空区形成和大量CO_(2)排放是制约煤炭可持续开发利用与绿色健康发展的瓶颈所在。为协同解决二氧化碳封存与矿山固废消纳问题,将大宗固废处置、固废高值化利用、CO_(2)封存、采空区利用有机结合,提出了二氧化碳充填的理念,从碳汇能力评估角度界定了二氧化碳充填的3种类型。具体开展工作包括:①分析了CO_(2)充填料浆输运过程和矿化反应过程涉及到的基础理论,给出了各个过程的数学方程以及碳封存量计算公式,指出了温度、湿度等因素对矿化反应机理、碳封存量和充填体强度的影响规律。②总结了现阶段CO_(2)矿化的工艺方法、主要碱性工业固废的CO_(2)封存能力和CO_(2)矿化强化措施。在此基础上提出了基于直接湿法矿化和间接矿化的2种CO_(2)充填材料制备工艺,满足矿井充填的流动性、凝固特性和强度要求。③针对CO_(2)充填过程中的CO_(2)物理封存问题,提出了窄条带式胶结充填和综采架后胶结充填2种技术路径,前者通过在弱充填条带中构筑多贯通孔隙的充填体CO_(2)物理封存,后者借助充填支架和链式自行充填挡板在长壁工作面采空区中间断构筑充填带,控制顶板垮落,形成CO_(2)物理化学封存空间。④为了评估CO_(2)充填的碳平衡效果,依据全生命周期法界定了CO_(2)充填中碳足迹及碳消纳的计算边界。然后,梳理了CO_(2)充填过程中的碳足迹及碳消纳,分别考虑了CO_(2)的来源、用量、损耗、转化等因素。给出了包括原料运输、充填料浆制备、井下注入与充填等过程中的碳足迹及碳消纳计算方法。研究成果有望降低CO_(2)封存的能耗及成本,对煤炭绿色开采及其可持续开发利用具有深远的意义。

水土保持碳汇内涵与测算方法

水土保持深刻改变着地表覆被和结构、土地利用方式和陆地生态系统结构等,是增强陆地碳汇能力的重要途径。以水土保持林草、工程和耕作措施为切入点,按照“机理阐述—模型构建—分类测算”的总体思路,阐明水土保持碳汇内涵,明确了水土保持碳汇途径,构建水土保持碳汇测算方法,估算全国水土保持碳汇量。结果表明:水土保持具有垂向碳增汇、横向保土固碳(减少侵蚀土壤横向输移导致的碳流失)与减蚀减碳(避免碳排放)的多重功能。2021年,全国现存水土保持措施垂向碳增汇总量为1.54亿t,对陆域碳汇的贡献约43.5%~56.5%,其中林草措施植被和土壤碳汇量超过95%。水土保持保土固碳作用显著,2021年全国水土保持措施保土固碳总量为3 040.86万t,且具有明显的累积效应和长效作用。总体来说,2021年水土保持碳增汇(不包括水土保持林草措施植被碳汇量和土壤碳汇量)和减碳量为5 115万~6 230万t CO_(2),约占到全国现有陆地生态系统碳中和总量的4%~6%,这一部分尚未纳入国家碳汇核算体系,其应是实现“双碳”目标的重要环节。

Highly reactive and reusable heterogeneous activated carbons-based palladium catalysts for Suzuki-Miyaura reaction

Suzuki-Miyaura reaction of aryl halides with phenylboronic acid using a heterogeneous palladium catalyst based on activated carbons(AC) was systematically investigated in this work. Two different reaction modes(batch procedure and continuous-flow procedure) were used to study the variations of reaction processing. The heterogeneous catalysts presented excellent reactivity and recyclability for iodobenzene and bromobenzene substrates in batch mode, which can be attributed to stabilization of Pd nanoparticles by the thiol and amino groups on the AC supports. However, significant dehalogenation in the reaction mixture and Pd leaching from the heterogeneous catalysts were observed in continuous-flow mode.This unique phenomenon in continuous-flow mode resulted in a dramatic decline in reaction selectivity and durability of heterogeneous catalysts comparing with that of batch mode. In addition, the heterogeneous Pd catalysts with thiol-and amino-modified AC supports exhibited different reactivity and durability in batch and continuous-flow mode owing to the difference of interaction between Pd species and AC supports.

Reactive ball-milling synthesis of Co-Fe bimetallic catalyst for efficient hydrogenation of carbon dioxide to value-added hydrocarbons

Catalytic hydrogenation of CO_(2) using renewable hydrogen not only reduces greenhouse gas emissions,but also provides industrial chemicals.Herein,a Co-Fe bimetallic catalyst was developed by a facile reactive ball-milling method for highly active and selective hydrogenation of CO_(2) to value-added hydrocarbons.When reacted at 320℃,1.0 MPa and 9600 mL h^(-1) g_(cat)^(-1),the selectivity to light olefin(C_(2)^(=)-C_(4)^(=)) and C_(5)+ species achieves 57.3% and 22.3%,respectively,at a CO_(2) co nversion of 31.4%,which is superior to previous Fe-based catalysts.The CO_(2) activation can be promoted by the CoFe phase formed by reactive ball milling of the Fe-Co_(3)O_(4) mixture,and the in-situ Co_(2)C and Fe_(5)C_(2) formed during hydrogenation are beneficial for the C-C coupling reaction.The initial C-C coupling is related to the combination of CO species with the surface carbon of Fe/Co carbides,and the sustained C-C coupling is maintained by self-recovery of defective carbides.This new strategy contributes to the development of efficient catalysts for the hydrogenation of CO_(2) to value-added hydrocarbons.

Fixed-Bed Column Adsorption Modeling of MnO4- Ions from Acidic Aqueous Solutions on Activated Carbons Prepared with the Biomass

Activated carbons calcined at 400˚C and 600˚C (AC-400 and AC-600), prepared using palm nuts, collected in the town of Franceville in Gabon, were used to study the dynamic adsorption of MnO4- ions in acidic media on fixed bed column and on the kinetic modeling of experimental data of breakthrough curves of MnO4- ions obtained. Results on the adsorption of MnO4- ions in fixed-bed dynamics obtained on AC-400 and AC-600 adsorbents beds indicated that the AC-400 bed appears to be the most efficient in removing MnO4- ions in acidic media. Indeed, the adsorbed amounts, the adsorbed capacities at saturation and the elimination percentage of MnO4- ions obtained with AC-400 (31.24 mg;52.06 mg·g-1 and 41.65% respectively) were higher compared to those obtained with AC-600 (9.87 mg;16.45 mg·g-1 and 17.79% respectively). The breakthrough curves kinetic modeling revealed that the Thomas model and the pseudo-first-order kinetic model were the most suitable models to describe the adsorption of MnO4- ions on adsorbents studied in our experimental conditions. The results of the intraparticle diffusion model showed that intraparticle diffusion was involved in the adsorption mechanism of MnO4- ions on investigated adsorbents and was not the limiting step and the only process controlling MnO4- ions adsorption. In contrast to AC-400, the intraparticle diffusion on AC-600 bed plays an important role in the adsorption mechanism of MnO4- ions.

煤矿负碳高效充填开采理论与技术构想

矿山安全高效绿色低碳开采是永恒的主题,近零冲击地压、近零生态损害以及低碳、零碳、负碳的绿色开采将成为保障我国能源安全供应与绿色低碳发展的新要求。充填开采是实现这一要求的必然途径。然而,现有充填开采原理与技术装备体系难以突破高产高效、低碳开采的技术瓶颈,对充填材料及充填模式进行变革已势在必行。针对“千米深井资源开发和千万吨产能矿井充填(两个一千)”与“近零生态损害和近零冲击地压(两个近零)”的煤炭绿色低碳开采战略目标,提出了负碳高效充填开采技术全新构想,系统阐述了负碳高效充填开采的定义与科学内涵,提出和建立了由CO_(2)、矸石与快速胶结物混合而成的负碳高孔隙充填材料结构CGIF(CO_(2)Gangue Inorganic Framework)拓扑构型与强度理论以及CGIF混合物充填体固碳理论、快速黏凝胶结材料反应动力学理论、矿区充填开采防治冲击地压等负碳高效充填理论构想;提出了矸石快速高效胶结高孔隙充填材料制备技术、快速黏凝胶结材料绿色高效制备技术、CGIF充填体负碳高效充填开采技术、多面并采高效充填开采技术与工艺、全周期立体高效充填开采防冲技术等关键技术体系。在此基础上,明确了煤矿负碳高效充填开采“基础研究—技术攻关—工程示范”的“三阶段”发展规划,构建了煤矿负碳高效充填开采理论与技术体系构想;评估了煤矿负碳高效充填CO_(2)封存能力,可望实现煤炭负碳开采、低碳利用的煤炭开发利用全过程自身实现碳中和的新格局。

中国式现代化目标下构建新型能源体系之路径思考

倡导人与自然和谐共生的中国式现代化,对中国能源领域的高质量可持续发展提出了新要求、新部署,“加快规划建设新型能源体系”势在必行。为了助推中国式现代化目标下新型能源体系的构建,分析了其提出的战略背景,明确了其重要意义,阐述了其内涵特征,提出了其路径建议。研究结果表明:①新型能源体系是社会主义现代化强国建设的关键抓手,是实现碳达峰碳中和目标以及推进生态文明建设的重要支撑,是国家能源安全和国家竞争力的有力保障;②新型能源体系以促进人与自然和谐共生为根本宗旨,以保证能源安全和经济社会发展稳定为基本前提,具有理念更新、能源结构更新、技术创新、治理创新、产业革新、电力革新等内涵特征;③新型能源体系的构建路径包括加快培育绿色低碳文化、加快推动能源结构转型、加快推动产业结构升级、加快攻关关键核心技术、加快构建体制机制保障等。结论认为,立足我国能源资源禀赋,坚持“先立后破”的方式构建清洁低碳、安全高效的新型能源体系,提高能源自给率,特别是油气自给率,确保能源转型平稳有序、能源保障安全可靠,可以为当前复杂国际形势下的国家能源安全提供强有力的保障。

中国粮食主产省区农业碳排放特征及影响因素

[目的]分析粮食主产省区农业碳排放特征及影响因素,为促进碳减排、农业可持续发展提供参考。[方法]基于农用投入物质、农作物种植、畜禽业养殖、秸秆焚烧4类农业碳排放源测算2010—2020年粮食主产区的农业碳排放并采用TAPIO脱钩模型和LMDI模型分析粮食主产区农业碳排放特征及影响因素。[结果]2010—2020年粮食主产区碳排放呈现先增长后下降的趋势,2010年的860.78 Mt增长至2020年的871.64 Mt,增加了10.86 Mt,增幅1.26%。2017年达到峰值927.68 Mt;农用投入物质为主要碳排放源。碳排放强度呈下降趋势,省域最高碳排强度可达3.99 t/万元。农业碳排放与经济增长的关系上,低排高产区为理想状态,目前,除河北省为低排高产区域,其余研究省域多数处于高排、低产区域。粮食主产区农业碳排放与农业经济的关系不断改善,2020年已有7省处于强脱钩状态。农业生产效率、地区产业结构、农村人口、农业产业结构是抑制碳排的主要因素。[结论]实现粮食主产区碳减排,促进农业可持续发展应从提升农业生产效率、控制畜禽出栏量和存栏量等多方面协同推进。

海洋CO_(2)地质封存研究进展与发展趋势

CO_(2)捕集、利用和封存是中国实现“双碳”目标的核心技术,也是全球研究的热点。CO_(2)地质封存是其中的关键环节,特别是海洋CO_(2)地质封存是今后的重点发展方向。以国内外海洋CO_(2)地质封存的发展历程为基础,结合典型CO_(2)海洋封存示范项目案例,系统梳理了国内外海洋CO_(2)地质封存理论研究进展,分析了CO_(2)在井筒流动、相变与传热、CO_(2)流体运移与储层物性参数展布规律、海洋地质封存机制及封存潜力、地质封存盖层完整性及安全性评估等方面的研究现状。认识到中国目前对海底地质结构中CO_(2)注入过程的多相态转化、溶解、捕获传质特征及动力学特性认识尚浅,对海洋封存机制及不同封存机制之间的相互作用机理尚不明确,未来应开展海洋CO_(2)动态地质封存空间重构机制研究,解决地质封存相态转化及流体动态迁移机理等关键科学问题,揭示海洋CO_(2)地质封存机制的相互作用机理,形成适用于中国海洋地质封存CO_(2)高效注入和增效封存方法。

大地幔楔的两个深部碳循环圈:差异及宜居效应

本文总结评述了西太平洋板块深俯冲及在东亚地幔过渡带滞留和与之相关的晚白垩世和新生代东亚板内玄武岩共同构成的大地幔楔板内深部碳循环圈存在的证据;探讨了大地幔楔板内碳循环圈与岛弧系统碳循环圈在地幔碳酸盐化交代介质、碳酸盐种属、氧化还原反应及碳酸盐化地幔部分熔融发生机制等方面的差异和对显生宙大气氧含量保持稳定及温室效应周期性变化的影响;并指出了定量估计深俯冲碳酸盐歧化反应还原成金刚石而留在地幔过渡带和通过板内玄武质火山返还大气的碳各自所占有比例应是未来需研究的重要课题。

BIM技术在建筑碳排放计算领域研究进展

结合国内外相关文献,对BIM技术在建筑碳排放计算领域的研究进展进行综述。通过对研究进程的归纳,以及对建筑碳排放计算政策、计算方法、BIM技术适用性等影响因素的分析,总结BIM技术在建筑碳排放计算领域的研究现状。基于当前研究成果,将BIM技术在建筑碳排放计算领域的研究内容划分为理论方法、工具平台、应用价值三个层面。理论方法主要关注计算边界和计算方法的确定、BIM模型的数据提取方式以及BIM模型的参数扩展内容;工具平台主要探讨BIM建模工具、人工处理及算法程序、BIM软件插件、BIM平台系统的具体应用;应用价值主要体现基于BIM技术的建筑碳排放计算在建筑设计、物化、运营等各阶段的成果效益。三个层面虽已取得许多研究成果但也存在问题和难点。未来的研究可以在数字技术融合和信息管理完善两个方面深入发展。

低碳矿区综合能源系统经济运行优化研究

针对煤矿开采过程中碳排放量高以及乏风、瓦斯、矿井涌水等伴生能源得不到及时有效利用的问题,提出一种低碳经济运行的矿区综合能源系统(coal mine integrated energy system, CMIES)。首先,为使矿区伴生能源得到充分利用,搭建了一个包含燃气轮机、乏风氧化发电单元、水源热泵等设备的CMIES模型。其次,为降低矿区碳排放量,在CMIES中加入光伏、风电、电转气与氢燃料电池等设备。同时,引入阶梯式碳交易机制与绿色证书交易机制(green certificate trading, GCT),通过“双机制”模型来约束系统碳排放、激励新能源设备出力。最后,调用CPLEX商业求解器,以购能成本、新能源设备运行成本、碳排放成本最小为目标函数进行求解。结果表明:优化后的CMIES碳排放量显著降低,运行成本大幅减少。

“双碳”目标下火电厂CO_(2)计量技术研究现状与展望

中国电力行业CO_(2)排放量是CO_(2)排放的主要来源,其中火电厂CO_(2)排放量在电力行业中占比最大。在“双碳”目标下,CO_(2)计量技术可以实现对火电厂中CO_(2)排放量的直观判断,为火电厂CO_(2)减排提供重要支撑,促进火电厂参与碳交易,带动区域经济发展。结合国内外政策,讨论了目前通用CO_(2)计量方法的实施进展,总结归纳了以碳核算为主、碳监测为辅的火电厂CO_(2)计量方法存在的问题,并对火电厂CO_(2)计量技术应用的重难点进行了分析。最后,对火电厂CO_(2)计量技术的发展及应用进行了展望。

同行“双碳”政策感知对企业创新绩效的影响研究

科技创新是实现“双碳”目标的关键支撑,如何充分调动企业科技创新的主观能动性则成为亟需解决的问题。本文运用文本计量方法测算上市公司的同行“双碳”政策感知,定量分析同行“双碳”政策感知对企业创新绩效的影响,并对这种溢出效应机制进行探索。研究发现:同行的“双碳”政策感知能够显著提高企业的研发强度、专利申请量和专利获取量;该创新促进效应的重要渠道是“双碳”政策感知在行业与企业间的传递;外部环境、企业性质和行业特征是该创新促进效应的重要调节变量。本文研究结果验证了凝聚绿色低碳转型的行业共识,可以充分调动企业科技创新的主观能动性,并指出激励政策和给予特殊行业补贴的策略至关重要。