Improving photosensitization for photochemical CO2-to-CO conversion

Inspired by nature, improving photosensitization represents a vital direction for the development of artificial photosynthesis. The sensitization ability of photosensitizers (PSs) reflects in their electron-transfer ability, which highly depends on their excited-state lifetime and redox potential. Herein, for the first time, we put forward a facile strategy to improve sensitizing ability via finely tuning the excited state of Ru(II)-PSs (Ru-1–Ru-4) for efficient CO₂ reduction. Remarkably, [Ru(Phen)₂(3-pyrenylPhen)]²⁺ (Ru-3) exhibits the best sensitizing ability among Ru-1–Ru-4, over 17 times higher than that of typical Ru(Phen)₃²⁺. It can efficiently sensitize a dinuclear cobalt catalyst for CO₂-to-CO conversion with a maximum turnover number of 66 480. Systematic investigations demonstrate that its long-lived excited state and suitable redox driving force greatly contributed to this superior sensitizing ability. This work provides a new insight into dramatically boosting photocatalytic CO₂ reduction via improving photosensitization.     

中国农田非CO2温室气体减排的研究现状与建议

温室气体减排对控制全球气候变暖具有重要意义。2014年我国农田非CO₂温室气体(主要指CH₄和N₂O)排放占全国温室气体排放总量的4.3%,预计2030年我国实现碳达峰后,化石能源逐步被清洁能源替代,农田CH₄和N₂O排放占全国温室气体排放的比重也将随之增大,其减排的紧迫性和重要性将日渐凸显。然而,现有农田碳减排技术由于缺乏立法教育宣传和成果激励机制等,并未得到充分转化应用与推广示范,使得减排成果难以落地坐实,不利于我国农业碳减排目标的顺利实现。文章总结了我国农田CH₄和N₂O减排工作的研究进展,指出了当前我国农田CH₄和N₂O减排所面临的问题,并在今后长效监测平台运维、新方法技术突破、大众减排意识提升及成果推广示范加强4个方面提出了技术和政策上的建议。     

Exposed facet-controlled N2 electroreduction on distinct Pt3Fe nanostructures of nanocubes,nanorods and nanowires

Understanding the correlation between exposed surfaces and performances of controlled nanocatalysts can aid effective strategies to enhance electrocatalysis, but this is as yet unexplored for the nitrogen reduction reaction (NRR). Here, we first report controlled synthesis of well-defined Pt₃Fe nanocrystals with tunable morphologies (nanocube, nanorod and nanowire) as ideal model electrocatalysts for investigating the NRR on different exposed facets. The detailed electrocatalytic studies reveal that the Pt₃Fe nanocrystals exhibit shape-dependent NRR electrocatalysis. The optimized Pt₃Fe nanowires bounded with high-index facets exhibit excellent selectivity (no N₂H₄ is detected), high activity with NH₃ yield of 18.3 μg h⁻¹ mg⁻¹_cat (0.52 μg h⁻¹ cm⁻²_ECSA; ECSA: electrochemical active surface area) and Faraday efficiency of 7.3% at −0.05 V versus reversible hydrogen electrode, outperforming the {200} facet-enclosed Pt₃Fe nanocubes and {111} facet-enclosed Pt₃Fe nanorods. They also show good stability with negligible activity change after five cycles. Density functional theory calculations reveal that, with high-indexed facet engineering, the Fe-3d band is an efficient d-d coupling correlation center for boosting the Pt 5d-electronic exchange and transfer activities towards the NRR.     

Linking deep CO2 outgassing to cratonic destruction

Outgassing of carbon dioxide from the Earth''s interior regulates the surface climate through deep time. Here we examine the role of cratonic destruction in mantle CO₂ outgassing via collating and presenting new data for Paleozoic kimberlites, Mesozoic basaltic rocks and their mantle xenoliths from the eastern North China Craton (NCC), which underwent extensive destruction in the early Cretaceous. High Ca/Al and low Ti/Eu and δ²⁶Mg are widely observed in lamprophyres and mantle xenoliths, which demonstrates that the cratonic lithospheric mantle (CLM) was pervasively metasomatized by recycled carbonates. Raman analysis of bubble-bearing melt inclusions shows that redox melting of the C-rich CLM produced carbonated silicate melts with high CO₂ content. The enormous quantities of CO₂ in these magmas, together with substantial CO₂ degassing from the carbonated melt–CLM reaction and crustal heating, indicate that destruction of the eastern NCC resulted in rapid and extensive mantle CO₂ emission, which partly contributed to the early Cretaceous greenhouse climate episode.     

中国CO2排放强度下降的结构分解——基于1997年-2007年的投入产出分析

本文以中国1997年和2007年的投入产出表为基础,核算了CO₂排放强度的变化。结果表明,中国1997年CO_排放总量为381788.56万t,强度为5.04t/万元。2007年CO₂排放总量为775346.15万t,强度为4.23t/万元。10年间,CO₂排放强度降低近20%。在此基础上进一步构建结构分解分析模型,将促使CO₂排放强度降低的因素分解为4种效应,即能源效率因素、能源结构因素、产业结构效应和经济增长方式效应。计量结果表明,部门单位产出能源消费强度变化和部门能源消费结构变化是造成CO₂排放强度下降的因素,其中以前者的影响最为显著。而产业结构变化和经济增长方式变化是促使CO₂排放强度上升的因素,并且前者的影响更为显著。因此,未来要实现2020年CO₂排放强度比2005年下降40%～45%的目标,必须调整产业结构,改变经济增长方式,以充分挖掘经济增长结构和方式转变的节能减排潜力。     

基于系统动力学的2000-2050年上海市化石能源CO2排放情景模拟

基于系统动力学方法和联合国政府间气候变化专门委员会(IPCC)排放因子法,对上海市 2000—2019 年的化石能源 CO₂排放进行定量核算,构建上海市化石能源 CO₂排放系统动力学模型,并模拟基础排放、低排放、高排放 3 种情景下的未来 CO₂排放变化。研究发现：(1)根据 2000—2019 年统计数据,上海市化石能源的 CO₂排放从 2003 年开始攀升,到 2010 年开始趋于平稳增长,其中增长最快的阶段为 2004—2007 年,增长了 32.7%;(2)上海市生产总值(GDP)年增长,2050 年低排放情景较基础情景下降 25%,高排放情景较基础情景上升 33%;(3)2020—2050 年低排放情景的能源消费量呈下降趋势,基础情景与高排放情景的能源消费量呈先增后降趋势,分别在 2029 年、2037 年达到峰值,但能源强度从高到低为低排放情景、基础情景、高排放情景,主要是由于 GDP 增长问题导致;(4)基础情景与低排放情景的 CO₂排放在 2030 年达到峰值,...     

Correlating the electronic structures of metallic/semiconducting MoTe2 interface to its atomic structures

Contact interface properties are important in determining the performances of devices that are based on atomically thin two-dimensional (2D) materials, especially for those with short channels. Understanding the contact interface is therefore important to design better devices. Herein, we use scanning transmission electron microscopy, electron energy loss spectroscopy, and first-principles calculations to reveal the electronic structures within the metallic (1T^′)-semiconducting (2H) MoTe₂ coplanar phase boundary across a wide spectral range and correlate its properties to atomic structures. We find that the 2H-MoTe₂ excitonic peaks cross the phase boundary into the 1T^′ phase within a range of approximately 150 nm. The 1T^′-MoTe₂ crystal field can penetrate the boundary and extend into the 2H phase by approximately two unit-cells. The plasmonic oscillations exhibit strong angle dependence, that is a red-shift of π+σ (approximately 0.3–1.2 eV) occurs within 4 nm at 1T^′/2H-MoTe₂ boundaries with large tilt angles, but there is no shift at zero-tilted boundaries. These atomic-scale measurements reveal the structure–property relationships of the 1T^′/2H-MoTe₂ boundary, providing useful information for phase boundary engineering and device development based on 2D materials.     

Anthropogenic emission is the main contributor to the rise of atmospheric methane during 1993–2017

Atmospheric methane (CH₄) concentrations have shown a puzzling resumption in growth since 2007 following a period of stabilization from 2000 to 2006. Multiple hypotheses have been proposed to explain the temporal variations in CH₄ growth, and attribute the rise of atmospheric CH₄ either to increases in emissions from fossil fuel activities, agriculture and natural wetlands, or to a decrease in the atmospheric chemical sink. Here, we use a comprehensive ensemble of CH₄ source estimates and isotopic δ¹³C-CH₄ source signature data to show that the resumption of CH₄ growth is most likely due to increased anthropogenic emissions. Our emission scenarios that have the fewest biases with respect to isotopic composition suggest that the agriculture, landfill and waste sectors were responsible for 53 ± 13% of the renewed growth over the period 2007–2017 compared to 2000–2006; industrial fossil fuel sources explained an additional 34 ± 24%, and wetland sources contributed the least at 13 ± 9%. The hypothesis that a large increase in emissions from natural wetlands drove the decrease in atmospheric δ¹³C-CH₄ values cannot be reconciled with current process-based wetland CH₄ models. This finding suggests the need for increased wetland measurements to better understand the contemporary and future role of wetlands in the rise of atmospheric methane and climate feedback. Our findings highlight the predominant role of anthropogenic activities in driving the growth of atmospheric CH₄ concentrations.     

Three Gorges Dam: friend or foe of riverine greenhouse gases?

Dams are often regarded as greenhouse gas (GHG) emitters. However, our study indicated that the world''s largest dam, the Three Gorges Dam (TGD), has caused significant drops in annual average emissions of CO₂, CH₄ and N₂O over 4300 km along the Yangtze River, accompanied by remarkable reductions in the annual export of CO₂ (79%), CH₄ (50%) and N₂O (9%) to the sea. Since the commencement of its operation in 2003, the TGD has altered the carbonate equilibrium in the reservoir area, enhanced methanogenesis in the upstream, and restrained methanogenesis and denitrification via modifying anoxic habitats through long-distance scouring in the downstream. These findings suggest that ‘large-dam effects’ are far beyond our previous understanding spatiotemporally, which highlights the fundamental importance of whole-system budgeting of GHGs under the profound impacts of huge dams.     

Identification of the activity source of CO2 electroreduction by strategic catalytic site distribution in stable supramolecular structure system

Identification of the real catalytic site in CO₂ reduction reaction (CO₂RR) is critical for the rational design of catalysts and the understanding of reactive mechanisms. In this study, the catalytic activity of pyridine-containing materials was for the first time structurally demonstrated in CO₂RR by crystalline supramolecular coordination compounds model system. The system consists of three stable supramolecular coordination compounds (Ni-TPYP, Ni-TPYP-1 and Ni-TPP) with different numbers (4, 2 and 0) of active pyridine groups (i.e. uncoordinated pyridine nitrogen atoms). The electrocatalytic test results show that with the decrease of the number of active pyridine groups, the CO₂RR performance is gradually reduced, mainly showing the reduction of highest FE_CO (99.8%, 83.7% and 25.6%, respectively). The crystallographic, experimental and theoretical evidences prove that the CO₂RR activity is more likely derived from uncoordinated pyridine nitrogen than the electrocatalytic inert metal nickel in porphyrin center. This work serves as an important case study for the identification of electrocatalytic activity of pyridine-containing materials in CO₂RR by simple supramolecular model system.     

Selective electrochemical production of hydrogen peroxide at zigzag edges of exfoliated molybdenum telluride nanoflakes

The two-electron reduction of molecular oxygen represents an effective strategy to enable the green, mild and on-demand synthesis of hydrogen peroxide. Its practical viability, however, hinges on the development of advanced electrocatalysts, preferably composed of non-precious elements, to selectively expedite this reaction, particularly in acidic medium. Our study here introduces 2H-MoTe₂ for the first time as the efficient non-precious-metal-based electrocatalyst for the electrochemical production of hydrogen peroxide in acids. We show that exfoliated 2H-MoTe₂ nanoflakes have high activity (onset overpotential ∼140 mV and large mass activity of 27 A g⁻¹ at 0.4 V versus reversible hydrogen electrode), great selectivity (H₂O₂ percentage up to 93%) and decent stability in 0.5 M H₂SO₄. Theoretical simulations evidence that the high activity and selectivity of 2H-MoTe₂ arise from the proper binding energies of HOO^* and O^* at its zigzag edges that jointly favor the two-electron reduction instead of the four-electron reduction of molecular oxygen.     

城乡家庭直接能源消费和CO2排放变化的分析与比较

中国正处在城市化的快速发展阶段,家庭能源消费和CO2排放不断增长.本文以1991年-2010年为样本期,对城乡家庭直接能源消费和CO2排放的变化特征和原因进行分析,并对二者的差异进行比较.分析表明,城镇和农村户均直接能源消费和CO2排放以及总量变化,都呈现出以1998年为拐点的先下降后上升特征.原因在于1998年之前,直接能源消费强度下降与家庭规模缩小的节能减排效应大于消费水平提高的增能增排效应,而1998年之后,后者超过了前者.城镇和农村家庭直接能源消费结构变化促使户均直接能源消费CO2排放增加,原因在于电力的CO2排放不断增加.城镇的户均直接能源消费和CO2排放一直高于农村,但差距正在缩小,原因在于城镇直接能源消费强度下降、直接能源消费结构优化、家庭规模缩小所产生的节能减排效应逐步增大,抵消了人均消费水平提高所产生的增能增排效应.     

以二氧化碳规模化利用技术为核心的碳减排方案

碳资源是人类社会发展进入工业时代的基石。人类大量使用含碳资源产生的二氧化碳(CO_2)不应给人类社会带来威胁,更不应是碳资源利用的终结者,而是人类实现可持续发展必须善加利用的资源。文章在国内CO_2利用技术研发取得了可喜进展的基础上,提出了几种未来可能适合于中国的以CO_2规模化利用技术为核心的碳减排方案,包括化石能源耦合CO_2的转化利用技术、零碳能源耦合CO_2的转化利用技术以及温和条件下CO_2直接转化利用技术等。基于我国能源消费结构、短中期化石能源的主导地位以及可再生能源日新月异的发展,化石能源的易获取性和低成本使得其耦合CO_2的转化利用技术方案近年来飞速发展,并可能将在近期带来巨大碳减排潜力和经济效益;零碳能源发电技术的突飞猛进有利于核能/可再生能源发电耦合CO_2生产燃料化学品技术的发展,成为中期最具竞争力的CO_2大规模利用技术;远期来说太阳能驱动的CO_2温和转化可以实现真正意义上的生态碳循环,是远期最有前景的CO_2还原技术。     

Efficient potential-tuning strategy through p-type doping for designing cathodes with ultrahigh energy density

Designing new cathodes with high capacity and moderate potential is the key to breaking the energy density ceiling imposed by current intercalation chemistry on rechargeable batteries. The carbonaceous materials provide high capacities but their low potentials limit their application to anodes. Here, we show that Fermi level tuning by p-type doping can be an effective way of dramatically raising electrode potential. We demonstrate that Li(Na)BCF₂/Li(Na)B₂C₂F₂ exhibit such change in Fermi level, enabling them to accommodate Li⁺(Na⁺) with capacities of 290–400 (250–320) mAh g⁻¹ at potentials of 3.4–3.7 (2.7–2.9) V, delivering ultrahigh energy densities of 1000–1500 Wh kg⁻¹. This work presents a new strategy in tuning electrode potential through electronic band structure engineering.     

Anisotropic alignments of hierarchical Li2SiO3/TiO2 @nano-C anode//LiMnPO4@nano-C cathode architectures for full-cell lithium-ion battery

We report on low-cost fabrication and high-energy density of full-cell lithium-ion battery (LIB) models. Super-hierarchical electrode architectures of Li₂SiO₃/TiO₂@nano-carbon anode (LSO.TO@nano-C) and high-voltage olivine LiMnPO₄@nano-carbon cathode (LMPO@nano-C) are designed for half- and full-system LIB-CR2032 coin cell models. On the basis of primary architecture-power-driven LIB geometrics, the structure keys including three-dimensional (3D) modeling superhierarchy, multiscale micro/nano architectures and anisotropic surface heterogeneity affect the buildup design of anode/cathode LIB electrodes. Such hierarchical electrode surface topologies enable continuous in-/out-flow rates and fast transport pathways of Li⁺-ions during charge/discharge cycles. The stacked layer configurations of pouch LIB-types lead to excellent charge/discharge rate, and energy density of 237.6 Wh kg⁻¹. As the most promising LIB-configurations, the high specific energy density of hierarchical pouch battery systems may improve energy storage for long-driving range of electric vehicles. Indeed, the anisotropic alignments of hierarchical electrode architectures in the large-scale LIBs provide proof of excellent capacity storage and outstanding durability and cyclability. The full-system LIB-CR2032 coin cell models maintain high specific capacity of ∼89.8% within a long-term life period of 2000 cycles, and average Coulombic efficiency of 99.8% at 1C rate for future configuration of LIB manufacturing and commercialization challenges.     

海口市旅游业直接能源需求与CO_2排放的定量测算

旅游业利用能源,并由此产生CO2排放是旅游业环境影响的重要方面。由于独特的地理位置和优越的海洋旅游资源,旅游业对海口市的经济的贡献较大,是国民经济的支柱产业。动态来看,随着产业规模的不断扩大,旅游业能耗与排放无论是存量还是增量都呈明显的增势。海口市旅游业能源消耗及CO2排放关乎海南生态之岛、绿色之岛、和谐之岛建设的大计。由于国情及旅游业发展实际等因素,国内现有的旅游业能耗与排放的测算中涉及的各种交通工具、酒店及旅游活动的单位能耗与排放强度等核心参数几乎都使用的是国外5年甚至10年前的经验数据。本文采用自下而上法,结合大量的实地调研,采用符合我国及海口市实际的能耗与排放强度关键参数,较为准确地测算了海口市2011年旅游业直接能源消耗与CO2排放量。结果表明,2011年海口市旅游业直接能耗为28.11PJ,占当年全市总能耗的22.67%;旅游业直接CO2排放总量为2.12Mt。旅游业正在或已经成为海口市重点用能产业。为应对气候变化和节能减排,应设法延长游客在海口的停留天数、减少进出往返的飞行次数;加快建立旅游酒店行业能源统计与审计制度,积极引入合同能源管理;在充分研究论证的基础上,考虑开征旅游环境税或生态补偿基金等。     

大气14CO2观测：碳排放评估的新方法

我国作为碳排放大国,面临着碳达峰、碳中和（以下简称“双碳”）目标任务和国际碳减排压力。因此,准确的碳排放数据对于评估“双碳”目标和国际履约非常重要。联合国政府间气候变化专门委员会（IPCC）报告推荐将二氧化碳（CO₂）观测与大气反演结合来“自上而下”地校验“自下而上”的碳排放清单,并指出加入大气¹⁴CO₂观测可以更准确地校验碳排放清单。放射性碳同位素（ ¹⁴C）是化石源CO₂最准确的示踪剂,已被国际社会广泛推荐用于碳排放评估。文章基于大气¹⁴CO₂观测的国际发展趋势和国内的紧迫状况,建议加大支持力度,建立大气¹⁴CO₂观测网络;开展培训,统一相关标准,积极参与国际交流;尽快开展¹⁴CO₂观测与大气反演相结合的研究。以此使我国的碳排放研究水平与国际接轨,并提高碳排放数据的可靠性,进而服务国家的“双碳”目标和气候外交谈判。     

Large dipole moment induced efficient bismuth chromate photocatalysts for wide-spectrum driven water oxidation and complete mineralization of pollutants

Herein, a wide-spectrum (∼678 nm) responsive Bi₈(CrO₄)O₁₁ photocatalyst with a theoretical solar spectrum efficiency of 42.0% was successfully constructed. Bi₈(CrO₄)O₁₁ showed highly efficient and stable photocatalytic water oxidation activity with a notable apparent quantum efficiency of 2.87% (420 nm), superior to many reported wide-spectrum driven photocatalysts. Most remarkably, its strong oxidation ability also enables the simultaneous degradation and complete mineralization for phenol, and its excellent performance is about 23.0 and 2.9 times higher than CdS and P25-TiO₂, respectively. Its high activity is ascribed to the giant internal electric field induced by its large crystal dipole, which accelerates the rapid separation of photogenerated electron–hole pairs. Briefly, the discovery of wide-spectrum bismuth chromate and the mechanism of exponentially enhanced photocatalytic performance by increasing the crystal dipole throw light on improving solar energy conversion.     

中国人口发展对家庭生活基本能耗及碳排放的影响分析

人口发展是影响家庭生活基本能耗及碳排放的重要因素,而生活用能作为终端能源消费对总能源的消费结构、供求关系和节能减排具有重要影响。本文基于STIRPAT模型,运用中国1997-2010年30个省份的动态及静态面板数据模型,分析了城镇化进程中不同地区人口发展与家庭生活基本能耗及碳排放的关系。结果表明,人均消费水平成为导致家庭生活基本能耗和碳排放升高主要的影响因子,而提高电力使用百分比和城镇化率抑制其增长。老龄化率及家庭规模在城镇化过程中对家庭生活基本能耗及碳排放的影响有着不同的作用。     

Recent advances in the synthesis of hierarchically mesoporous TiO2 materials for energy and environmental applications

Because of their low cost, natural abundance, environmental benignity, plentiful polymorphs, good chemical stability and excellent optical properties, TiO₂ materials are of great importance in the areas of physics, chemistry and material science. Much effort has been devoted to the synthesis of TiO₂ nanomaterials for various applications. Among them, mesoporous TiO₂ materials, especially with hierarchically porous structures, show great potential owing to their extraordinarily high surface areas, large pore volumes, tunable pore structures and morphologies, and nanoscale effects. This review aims to provide an overview of the synthesis and applications of hierarchically mesoporous TiO₂ materials. In the first section, the general synthetic strategies for hierarchically mesoporous TiO₂ materials are reviewed. After that, we summarize the architectures of hierarchically mesoporous TiO₂ materials, including nanofibers, nanosheets, microparticles, films, spheres, core-shell and multi-level structures. At the same time, the corresponding mechanisms and the key factors for the controllable synthesis are highlighted. Following this, the applications of hierarchically mesoporous TiO₂ materials in terms of energy storage and environmental protection, including photocatalytic degradation of pollutants, photocatalytic fuel generation, photoelectrochemical water splitting, catalyst support, lithium-ion batteries and sodium-ion batteries, are discussed. Finally, we outline the challenges and future directions of research and development in this area.