An integrated technology for the absorption and utilization of CO_(2)in alkanolamine solution for the preparation of BaCO_(3)in a high-gravity environment

In this study,an integrated technology is proposed for the absorption and utilization of CO_(2)in alkanolamine solution for the preparation of BaCO_(3)in a high-gravity environment.The effects of absorbent type,high-gravity factor,gas/liquid ratio,and initial BaCl2concentration on the absorption rate and amount of CO_(2)and the preparation of BaCO_(3)are investigated.The results reveal that the absorption rate and amount of CO_(2)follow the order of ethyl alkanolamine(MEA)>diethanol amine(DEA)>N-methyldiethanolamine(MDEA),and thus MEA is the most effective absorbent for CO_(2)absorption.The absorption rate and amount of CO_(2)under high gravity are higher than that under normal gravity.Notably,the absorption rate at 75 min under high gravity is approximately 2 times that under normal gravity.This is because the centrifugal force resulting from the high-speed rotation of the packing can greatly increase gas-liquid mass transfer and micromixing.The particle size of BaCO_(3)prepared in the rotating packed bed is in the range of 57.2—89 nm,which is much smaller than that prepared in the bubbling reactor(>100.3 nm),and it also has higher purity(99.6%)and larger specific surface area(14.119 m^(2)·g^(-1)).It is concluded that the high-gravity technology has the potential to increase the absorption and utilization of CO_(2)in alkanolamine solution for the preparation of BaCO_(3).This study provides new insights into carbon emissions reduction and carbon utilization.

A review on electrocatalytic CO_(2) conversion via C-C and C-N coupling

Electrochemical C-C and C-N coupling reactions with the conversion of abundant and inexpensive small molecules,such as CO_(2) and nitrogencontaining species,are considered a promising route for increasing the value of CO_(2) reduction products.The development of high-performance catalysts is the key to the both electrocatalytic reactions.In this review,we present a systematic summary of the reaction systems for electrocatalytic CO_(2) reduction,along with the coupling mechanisms of C-C and C-N bonds over outstanding electrocatalytic materials recently developed.The key intermediate species and reaction pathways related to the coupling as well as the catalyst-structure relationship will be also discussed,aiming to provide insights and guidance for designing efficient CO_(2) reduction systems.

The Capture and Catalytic Conversion of CO_(2) by Dendritic Mesoporous Silica-Based Nanoparticles

Dendritic mesoporous silica nanoparticles own three-dimensional center-radial channels and hierarchical pores,which endows themselves with super-high specific surface area,extremely large pore volumes,especially accessible internal spaces,and so forth.Dissimilar guest species(such as organic groups or metal nanoparticles)could be readily decorated onto the interfaces of the channels and pores,realizing the functionalization of dendritic mesoporous silica nanoparticles for targeted applications.As adsorbents and catalysts,dendritic mesoporous silica nanoparticles-based materials have experienced nonignorable development in CO_(2)capture and catalytic conversion.This comprehensive review provides a critical survey on this pregnant subject,summarizing the designed construction of novel dendritic mesoporous silica nanoparticles-based materials,the involved chemical reactions(such as CO_(2)methanation,dry reforming of CH_(4)),the value-added chemicals from CO_(2)(such as cyclic carbonates,2-oxazolidinones,quinazoline-2,4(1H,3H)-diones),and so on.The adsorptive and catalytic performances have been compared with traditional silica mesoporous materials(such as SBA-15 or MCM-41),and the corresponding reaction mechanisms have been thoroughly revealed.It is sincerely expected that the in-depth discussion could give materials scientists certain inspiration to design brand-new dendritic mesoporous silica nanoparticles-based materials with superior capabilities towards CO_(2)capture,utilization,and storage.

Enabling heterogeneous catalysis to achieve carbon neutrality: Directional catalytic conversion of CO_(2) into carboxylic acids

The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving carbon neutrality is the utilization of CO_(2) under economic and sustainable conditions.Recently,the strong need for carbon neutrality has led to a proliferation of studies on the direct conversion of CO_(2) into carboxylic acids,which can effectively alleviate CO_(2) emissions and create high-value chemicals.The purpose of this review is to present the application prospects of carboxylic acids and the basic principles of CO_(2) conversion into carboxylic acids through photo-,electric-,and thermal catalysis.Special attention is focused on the regulation strategy of the activity of abundant catalysts at the molecular level,inspiring the preparation of high-performance catalysts.In addition,theoretical calculations,advanced technologies,and numerous typical examples are introduced to elaborate on the corresponding process and influencing factors of catalytic activity.Finally,challenges and prospects are provided for the future development of this field.It is hoped that this review will contribute to a deeper understanding of the conversion of CO_(2) into carboxylic acids and inspire more innovative breakthroughs.

A review of interaction mechanisms and microscopic simulation methods for CO_(2)-water-rock system

This work systematically reviews the complex mechanisms of CO_(2)-water-rock interactions,microscopic simulations of reactive transport(dissolution,precipitation and precipitate migration)in porous media,and microscopic simulations of CO_(2)-water-rock system.The work points out the key issues in current research and provides suggestions for future research.After injection of CO_(2) into underground reservoirs,not only conventional pressure-driven flow and mass transfer processes occur,but also special physicochemical phenomena like dissolution,precipitation,and precipitate migration.The coupling of these processes causes complex changes in permeability and porosity parameters of the porous media.Pore-scale microscopic flow simulations can provide detailed information within the three-dimensional pore and throat space and explicitly observe changes in the fluid-solid interfaces of porous media during reactions.At present,the research has limitations in the decoupling of complex mechanisms,characterization of differential multi-mineral reactions,precipitation generation mechanisms and characterization(crystal nucleation and mineral detachment),simulation methods for precipitation-fluid interaction,and coupling mechanisms of multiple physicochemical processes.In future studies,it is essential to innovate experimental methods to decouple“dissolution-precipitation-precipitate migration”processes,improve the accuracy of experimental testing of minerals geochemical reaction-related parameters,build reliable characterization of various precipitation types,establish precipitation-fluid interaction simulation methods,coordinate the boundary conditions of different physicochemical processes,and,finally,achieve coupled flow simulation of“dissolution-precipitation-precipitate migration”within CO_(2)-water-rock systems.

Cu/TiO_(2) Photocatalysts for CO_(2) Reduction: Structure and Evolution of the Cocatalyst Active Form

Extensive work on a Cu-modified TiO_(2) photocatalyst for CO_(2) reduction under visible light irradiation was conducted. The structure of the copper cocatalyst was established using UV-vis diff use refl ectance spectroscopy, high-resolution transmis- sion electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy. It was found that copper exists in different states (Cu 0 , Cu^(+) , and Cu^(2+) ), the content of which depends on the TiO_(2) calcination temperature and copper loading. The optimum composition of the cocatalyst has a photocatalyst based on TiO_(2) calcined at 700℃ and modified with 5 wt% copper, the activity of which is 22 μmol/(h·g cat ) (409 nm). Analysis of the photocatalysts after the photocatalytic reaction disclosed that the copper metal on the surface of the calcined TiO_(2) was gradually converted into Cu_(2) O during the photocatalytic reaction. Meanwhile, the metallic copper on the surface of the noncalcined TiO_(2) did not undergo any trans- formation during the reaction.

An Integrated Framework for Geothermal Energy Storage with CO_(2)Sequestration and Utilization

Subsurface geothermal energy storage has greater potential than other energy storage strategies in terms of capacity scale and time duration.Carbon dioxide(CO_(2))is regarded as a potential medium for energy storage due to its superior thermal properties.Moreover,the use of CO_(2)plumes for geothermal energy storage mitigates the greenhouse effect by storing CO_(2)in geological bodies.In this work,an integrated framework is proposed for synergistic geothermal energy storage and CO_(2)sequestration and utilization.Within this framework,CO_(2)is first injected into geothermal layers for energy accumulation.The resultant high-energy CO_(2)is then introduced into a target oil reservoir for CO_(2)utilization and geothermal energy storage.As a result,CO_(2)is sequestrated in the geological oil reservoir body.The results show that,as high-energy CO_(2)is injected,the average temperature of the whole target reservoir is greatly increased.With the assistance of geothermal energy,the geological utilization efficiency of CO_(2)is higher,resulting in a 10.1%increase in oil displacement efficiency.According to a storage-potential assessment of the simulated CO_(2)site,110 years after the CO_(2)injection,the utilization efficiency of the geological body will be as high as 91.2%,and the final injection quantity of the CO_(2)in the site will be as high as 9.529×10^(8)t.After 1000 years sequestration,the supercritical phase dominates in CO_(2)sequestration,followed by the liquid phase and then the mineralized phase.In addition,CO_(2)sequestration accounting for dissolution trapping increases significantly due to the presence of residual oil.More importantly,CO_(2)exhibits excellent performance in storing geothermal energy on a large scale;for example,the total energy stored in the studied geological body can provide the yearly energy supply for over 3.5×10^(7) normal households.Application of this integrated approach holds great significance for large-scale geothermal energy storage and the achievement of carbon neutrality.

Meta-analysis of CO_(2) conversion,energy efficiency,and other performance data of plasma-catalysis reactors with the open access PIONEER database

This paper brings the comparison of performances of CO_(2)conversion by plasma and plasma-assisted catalysis based on the data collected from literature in this field,organised in an open access online database.This tool is open to all users to carry out their own analyses,but also to contributors who wish to add their data to the database in order to improve the relevance of the comparisons made,and ultimately to improve the efficiency of CO_(2)conversion by plasma-catalysis.The creation of this database and database user interface is motivated by the fact that plasma-catalysis is a fast-growing field for all CO_(2)conversion processes,be it methanation,dry reforming of methane,methanolisation,or others.As a result of this rapid increase,there is a need for a set of standard procedures to rigorously compare performances of different systems.However,this is currently not possible because the fundamental mechanisms of plasma-catalysis are still too poorly understood to define these standard procedures.Fortunately however,the accumulated data within the CO_(2)plasma-catalysis community has become large enough to warrant so-called“big data”studies more familiar in the fields of medicine and the social sciences.To enable comparisons between multiple data sets and make future research more effective,this work proposes the first database on CO_(2)conversion performances by plasma-catalysis open to the whole community.This database has been initiated in the framework of a H_(2)0_(2)0 European project and is called the“PIONEER Data Base”.The database gathers a large amount of CO_(2)conversion performance data such as conversion rate,energy efficiency,and selectivity for numerous plasma sources coupled with or without a catalyst.Each data set is associated with metadata describing the gas mixture,the plasma source,the nature of the catalyst,and the form of coupling with the plasma.Beyond the database itself,a data extraction tool with direct visualisation features or advanced filtering functionalities has been developed and is available online to the public.The simple and fast visualisation of the state of the art puts new results into context,identifies literal gaps in data,and consequently points towards promising research routes.More advanced data extraction illustrates the impact that the database can have in the understanding of plasma-catalyst coupling.Lessons learned from the review of a large amount of literature during the setup of the database lead to best practice advice to increase comparability between future CO_(2)plasma-catalytic studies.Finally,the community is strongly encouraged to contribute to the database not only to increase the visibility of their data but also the relevance of the comparisons allowed by this tool.

Effects of CH_(4)/CO_(2) multi-component gas on components and properties of tight oil during CO_(2) utilization and storage: Physical experiment and composition numerical simulation

An essential technology of carbon capture, utilization and storage-enhanced oil recovery (CCUS-EOR) for tight oil reservoirs is CO_(2) huff-puff followed by associated produced gas reinjection. In this paper, the effects of multi-component gas on the properties and components of tight oil are studied. First, the core displacement experiments using the CH_(4)/CO_(2) multi-component gas are conducted to determine the oil displacement efficiency under different CO_(2) and CH_(4) ratios. Then, a viscometer and a liquid density balance are used to investigate the change characteristics of oil viscosity and density after multi-component gas displacement with different CO_(2) and CH_(4) ratios. In addition, a laboratory scale numerical model is established to validate the experimental results. Finally, a composition model of multi-stage fractured horizontal well in tight oil reservoir considering nano-confinement effects is established to investigate the effects of multi-component gas on the components of produced dead oil and formation crude oil. The experimental results show that the oil displacement efficiency of multi-component gas displacement is greater than that of single-component gas displacement. The CH_(4) decreases the viscosity and density of light oil, while CO_(2) decreases the viscosity but increases the density. And the numerical simulation results show that CO_(2) extracts more heavy components from the liquid phase into the vapor phase, while CH_(4) extracts more light components from the liquid phase into the vapor phase during cyclic gas injection. The multi-component gas can extract both the light components and the heavy components from oil, and the balanced production of each component can be achieved by using multi-component gas huff-puff.

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。

超高选择性CO_(2)光还原为乙醇的CuNi异核双原子催化剂的精准设计

利用光催化还原技术将CO_(2)定向转化为乙醇(CO_(2)-乙醇)是解决日益严重的环境污染和能源危机的理想途径之一.然而,CO_(2)分子的高化学惰性以及C-C耦合反应的高化学能垒导致目前CO_(2)-乙醇转化反应的产率和选择性较低.因此,设计构建能够快速活化CO_(2)分子并同时促进C-C耦合的光催化材料具有重要研究意义.尽管已有研究表明,Cu+物种在促进C-C耦合方面具有一定优势,但其在催化反应过程中的不稳定性限制了其实际应用.基于上述认识,本文通过理论模拟预测发现,相比于Cu单原子,CuNi异核双原子(CuNi HDAs)不仅在CO_(2)活化及C-C耦合方面更具优势,而且能够有效锚定并固化Cu+物种.因此,本文设计了一种三步合成策略,精准地将Cu单原子锚定在(Ni,Zr)-UiO-66-NH2材料的Ni位上,合成了以CuNi HDAs为活性位点的Cu-(Ni,Zr)-UiO-66-NH2光催化材料.在可见光照射下,Cu-(Ni,Zr)-UiO-66-NH2表现出较好的催化CO_(2)-乙醇转化活性,其乙醇的产率和选择性分别达到~3218μmol·gCu^(-1)·h^(-1)和97.3%.光谱分析和密度泛函理论计算结果表明,Cu-(Ni,Zr)-UiO-66-NH2材料较好的光催化性能来源于CuNi HDAs特殊的电子结构.首先,CuNi HDAs通过CuNi-O界面化学键与吸光组分(Ni,Zr)-UiO-66-NH2相连,利用界面Cu-Ni-O键作为快速电子传输通道,CuNi HDAs能够富集到足够的光生电子用于涉及12电子的CO_(2)-乙醇转化反应,使得乙醇产率大幅提升.其次,Cu,Ni和O三种原子由于电子亲核能的差异,导致CuNi HDAs的电子分布呈现不对称性.这种不对称的电子结构能有效诱导CO_(2)分子的极化,打破其结构的对称性,从而显著降低CO_(2)分子的活化能.再次,相比于Cu单原子,CuNi HDAs对*CO中间体的吸附能力更强,这不仅增强了活性位点表面*CO中间体的覆盖度,还抑制CO的生成,为C-C耦合创造了充分条件.最后,由于Cu-Ni双活性位电子密度的差异,CuNi HDAs表面的C-C耦合反应势能较低,有利于*OCCHO中间体的快速生成,从而使乙醇产物的选择性大幅提升.综上,本文以理论计算模拟为指导,以UiO-66-NH2材料为基底,成功设计并制备了一种具有不对称电子结构的CuNi HDAs光催化材料,实现了高选择性CO_(2)光还原为乙醇.研究表明,CuNi HDAs的不对称结构在促进分子活化和降低C-C耦合反应能垒中起关键作用,同时促进了光生电子在CuNi HDAs活性位的富集.本文的研究结果为在原子尺度上设计并合成高性能的CO_(2)还原光催化剂提供了实验和理论参考.

粉煤灰矿化电厂烟气CO_(2)技术及关键科学问题

燃煤发电是我国能源安全的重要保障,但烟气中会排放大量CO_(2),同时,也会产生大量粉煤灰。利用粉煤灰矿化封存电厂烟气CO_(2),并将矿化产物进行综合利用,可达到大宗固废处置与CO_(2)长效封存的双重目的。目前,粉煤灰矿化电厂烟气CO_(2)技术仍存在矿化效率低、反应时间长、CO_(2)处理量小等不足,其对应的关键科学问题和技术瓶颈亟待解决。简要介绍了粉煤灰矿化烟气CO_(2)的基本原理,分析了不同反应条件对粉煤灰碱土金属离子浸出和CO_(2)矿化反应效率的影响机制,对比了CO_(2)直接矿化反应工艺、碱土金属预浸出工艺、CO_(2)预吸收工艺等3种流程的优缺点,提出了包含粉煤灰碱土金属离子高效浸出、CO_(2)矿化反应过程强化、粉煤灰矿化CO_(2)智能装备、矿化效果综合评价等方面的粉煤灰高效矿化烟气CO_(2)技术体系,总结了粉煤灰矿化CO_(2)产物的物理化学性质,提出了粉煤灰矿化CO_(2)产物高值化综合利用的构想。最后,凝练出了粉煤灰碱土金属离子快速浸出与CO_(2)高效矿化特性、粉煤灰矿化CO_(2)大型反应器中多相混合与反应规律、粉煤灰浆液矿化CO_(2)产物性质的调控机制等3个关键科学问题,指明了基础研究-关键技术与装备研发-工程应用全链条的攻关方向,为粉煤灰高效矿化烟气CO_(2)及产物综合利用提供了参考,对于双碳目标实现和固废综合利用具有重要意义。

多种构型超临界CO_(2)循环热力学解构分析与参数优化

新型超临界CO_(2)(S-CO_(2))循环可通过流程改良提高效率,构型复杂多样。为了直观阐明各种流程改良措施对循环效率提升的作用机制,本文将预压缩、后压缩、再压缩、间冷、再热等五种构型的S-CO_(2)循环解构为若干热功转换过程,建立各解构过程与循环效率之间的关联方程,进而开展流程参数优化。研究结果表明,预压缩、后压缩和再压缩方案均是通过增加压缩耗功,减少吸热量实现循环效率提升,其中再压缩方案效果最优,再压缩流量优化后循环效率提高5.1%;采用部分间冷方案,可有效降低压缩功耗,同时避免高品位热量贬值,间冷压力优化后循环效率提高2.2%;再热方案在不改变压缩耗功的前提下,增加透平出功,再热压力优化后循环效率提高1.9%;最后,循环联用再压缩、间冷和再热三种节能措施,可使效率提高9.3%。

夹层型页岩油储层CO_(2)驱替特征——以鄂尔多斯盆地长7页岩为例

针对鄂尔多斯盆地长7夹层型页岩油储层动用困难的问题,利用一维、二维核磁共振技术评价方法,从微观角度对页岩油注CO_(2)驱替特征进行研究。结果表明:随着驱替流量的增加,驱油效率增大,中孔与大孔驱油效率贡献也增大,绝对驱油贡献率均在60%以上;增大驱替流量可以显著提高基质渗透率较小的岩样驱油效率;岩样赋存状态以游离油为主,饱和原油后体积分数为40.51%~62.40%,驱替过程中游离油相对驱替体积分数在50%以上;随着驱替流量的增大,游离油/吸附油相对驱替体积分数减小;干样渗透率越大,渗透率随驱替流量的增长速率也越大。研究成果为页岩油有效开发提供理论依据。

弱碱性吸收剂碳捕集及CO_(2)富液生物再生性能

碳捕集转化一体化工艺能利用CO_(2)转化过程同步实现CO_(2)富液再生,有望降低碳捕集转化整体成本。为评价生物甲烷化与碳捕集耦合的可行性,首先,在填料塔中考察了以4.2 g/L NaHCO_(3)、6 g/L Na_(2)CO_(3)、微生物营养液配制的弱碱性吸收剂(pH=10)对模拟烟气中CO_(2)的吸收性能;其次,在厌氧瓶内利用生物甲烷化过程对CO_(2)富液开展5个周期的循环再生试验。结果表明,填料塔气体流量≤1.0 L/min时,随液体流量增加,所有试验组CO_(2)去除率逐渐上升并能稳定在80%以上,该填料塔液体流量宜≤0.9 L/min;不同气体流量(0.4~1.2 L/min)下填料塔体积总传质系数基本稳定在17~19 mol/(h·kPa·m^(3));CO_(2)吸收导致吸收液中NaHCO_(3)增加、Na_(2)CO_(3)减少,二者变量比值在1.2~1.9。气体流量为0.6 L/min、液体流量为0.7 L/min时,在维持80%以上CO_(2)去除率的前提下,该弱碱性吸收剂可循环使用6次,此时活性组分CO_(3)^(2-)利用率达89.5%,形成的CO_(2)富液中总无机碳量为0.127 mol/L,pH为8.82,能为生物甲烷化微生物提供适宜的生长环境。CO_(2)富液循环生物再生试验表明,每次再生后的吸收剂CO_(2)吸收量基本稳定在69.6~78.6 mmol/L,且再生期间CH 4产生过程具有良好的重复性;再生试验后,Firmicutes、Actinobacteriota等耐碱性门水平细菌得到一定富集;氢营养型产甲烷菌在再生前后古菌属中占比均接近99%,但再生试验期间弱碱性环境导致Methanobrevibacter相对丰度降低了19.5%,unclassified_f_Methanobacteriaceae增加了18.7%。初步证实了碳捕集耦合生物甲烷化工艺的可行性。

CO_(2)捕集、利用和封存在能源行业的应用:全球案例分析和启示

为了实现中国21世纪中叶达到碳中和,大规模应用CO_(2)捕获、利用和封存(CCUS)技术可以减少能源行业的温室气体排放。通过对国内外CCUS技术、项目的调研,得出了关于未来CCUS部署的3个见解,这些见解有助于能源行业实现转型。首先,碳源浓度较低导致碳捕集效率低,从而导致碳捕集的经济成本较高的问题是目前CCUS项目无法商业化的主要因素,在发展当前的碳捕集技术,提高捕集效率和降低捕集成本的同时也应大力研究空气捕集技术,尤其是在工艺设计和新型吸附材料研发方面,争取实现弯道超车;其次,CO_(2)在油气藏和咸水层的封存与利用应当作为CCUS技术研究的重点,逐步实现大规模推广,并在技术升级和体系完善的基础上推广CO_(2)增强地热、煤层气等其他耦合技术;最后,应当在当前国际上较成熟的碳政策的基础上研究适合中国的激励政策,建立有效的法律法规。论文总结了当前CCUS的关键挑战,并为未来的CCUS研究方向提供了指导方向。

利用光驱动的生物杂合系统实现CO_(2)转化生产化学品

太阳能作为清洁能源之一,为缓解化石燃料枯竭和温室气体排放等问题提供了一种高效、经济、可持续的解决方案.自然界中的植物和光合微生物通过自身的光合系统收集并转化太阳能,从而生产生物燃料和生物化学品.然而,由于自然光合系统存在光吸收范围相对较窄、光生电子在传输过程中易损耗等问题,限制了太阳能到化学品的转化效率.为了解决上述难题,科研人员模仿自然光合作用中的关键部分,探索构建人工光合系统,相关研究引起了广泛关注.本文通过将碲化镉量子点(CdTe QDs)与大肠杆菌(E.coli)相耦合,构建了一种光驱动无机-生物杂合系统(IBPHS),用于捕获太阳能并驱动CO_(2)转化合成高价值化学品.该系统主要由光催化模块和生物催化模块组成.在光催化模块中,通过生物合成CdTe QDs进行光能捕获,并将其转化为电子.通过敲除E.coli的Cd2+外排蛋白(ZNTA)编码基因,实现了E.coli胞内Cd2+过量积累.通过“时空耦合”方式,并借助共聚焦显微镜、高分辨率透射电镜和X射线能谱分析,确认了CdTe QDs在E.coli胞内的组装合成.利用紫外-可见分光光度计研究了光催化模块对光子的吸收能力.结果表明,光催化模块的吸收峰位于400-420 nm.利用瞬时光电流,评估了光催化模块的光生电子能力.实验发现,该模块可以产生0.07μA光电流,表明完成了光催化模块的构建.在生物催化模块中,将光催化模块产生的电子用于还原NAD+再生NADH.采用NADH生物传感器,分析了E.coli胞内NADH含量,结果表明,在蓝光照射下E.coli胞内NADH含量比黑暗条件下提高了5.1倍.在此基础上,通过表达NADH依赖型乳酸脱氢酶(LDH)将丙酮酸还原为乳酸,在蓝光光照下乳酸积累量达到了0.44 g/L,而黑暗条件下无乳酸积累,从而验证了生物催化模块的有效性.基于光催化模块和生物催化模块,进一步组装构建了IBPSH,用于驱动CO_(2)还原合成甲酸和丙酮酸.在蓝光照射下,IBPHS能够合成0.65 g/L甲酸和0.18 g/L丙酮酸,其CO_(2)利用速率分别达到51.98 mg/gDCW/h和21.92 mg/gDCW/h,超过了光合细菌.综上所述,本文利用光催化模块与生物催化模块相耦合的方式,组装构建了一种新型的人工光合系统,实现了光驱动CO_(2)还原合成高附加值化学品,为理性设计材料-生物杂合系统提供了借鉴,同时也为挖掘绿色生物制造潜力、开发太阳能化学制造平台提供参考.

CO_(2)加氢制甲醇Cu/CeO_(2)催化剂实验研究

考察了第二金属Ni改性对CO_(2)加氢制甲醇Cu/CeO_(2)催化剂活性的影响,并通过XRD、BET、XPS、H_(2)-TPR等手段对改性前后催化剂结构进行了表征。结果表明:金属负载量为20%时,Cu/CeO_(2)的比表面积最大;Cu与Ni质量比为3∶1时,催化剂碱度最大,氧空位含量最高,Cu-Ni协同作用最强;该催化剂在反应温度240℃、反应压力3 MPa、液时空速2400 mL/(g·h)、H_(2)与CO_(2)体积比为3∶1时催化CO_(2)加氢制甲醇效果较优,CO_(2)转化率为18.5%,甲醇时空产率为40.43 g/(kg·h)。

CO_(2)转化技术的环境和经济效益评价及未来发展趋势

2022年全球CO_(2)排放量约为360.7亿t,仅2.3亿t CO_(2)被捕获并利用,占比仅为0.64%。为了实现2060年的碳中和目标,CO_(2)排放量需降至50亿t,CO_(2)利用总量需达到12亿t,其利用占比将增至24%,提高CO_(2)利用水平迫在眉睫。碳捕集、利用与封存(CCUS)技术已经成为减少CO_(2)排放、应对全球气候问题最具潜力的技术选择之一,通过不同的技术路径将捕集的CO_(2)转化为具有高附加值的工业产品一直是学术界和工程界的研究重点和热点,但不同的转化技术对于CO_(2)减排的潜在贡献仍存在不确定性。对近年来CO_(2)转化技术的发展现状进行了系统的综述,聚焦于3种具有代表性的CO_(2)转化路径和产品,并结合工业应用案例,对不同技术路径和不同产品的环境影响和技术经济性进行了比较分析。CO_(2)的碳酸化、利用CO_(2)生产聚合物产品等路径具有较高的碳负排放潜力,对于减少总体CO_(2)排放具有重要意义。

硅纳米结构阵列:光热CO_(2)催化的新兴平台

人口的快速增长和高能源需求产业造成了严重的环境问题。太阳能等替代性的清洁能源对于缓解能源危机和温室效应至关重要。光催化是一种很有前途的方法,但它在转化率、效率和规模化方面存在局限性。光热催化则结合了光化学和光热效应,是在温和条件下有效催化化学反应的新概念。近年来,与传统的光热催化剂相比,硅纳米结构阵列在光热CO_(2)还原反应中表现出独特的催化性能优势。作为一种平台,它表现出优异的光收集能力、高比表面积以及多样化的材料复合选择。本文综述了光热催化CO_(2)转化的概念和原理,硅纳米结构阵列的功能,以及利用硅纳米结构阵列在光热催化CO_(2)转化方面的最新进展,最终将为高性能纳米结构阵列光热CO_(2)催化剂的发展方向提供指导。