Dalian National Laboratory for Clean Energy

Since the 1970s, splitting water using solar energy has been a focus of great attention as a possible means for converting solar energy to chemical energy in the form of clean and renewable hydrogen fuel. Approaches to solar water splitting include photocatalytic water splitting with homogeneous or heterogeneous photocatalysts, photoelectrochemical or photoelectrocatalytic (PEC) water splitting with a PEC cell, and electrolysis of water with photovoltaic cells coupled to electrocatalysts. Though many materials are capable of photocatalytically producing hydrogen and/or oxygen, the overall energy conversion efficiency is still low and far from practical application. This is mainly due to the fact that the three crucial steps for the water splitting reaction: solar light harvesting, charge separation and transportation, and the catalytic reduction and oxidation reactions, are not efficient enough or simultaneously. Water splitting is a thermodynamically uphill reaction, requiring transfer of multiple electrons, making it one of the most challenging reactions in chemistry. This Account describes the important roles of cocatalysts in photocatalytic and PEC water splitting reactions. For semiconductor-based photocatalytic and PEC systems, we show that loading proper cocatalysts, especially dual cocatalysts for reduction and oxidation, on semiconductors (as light harvesters) can significantly enhance the activities of photocatalytic and PEC water splitting reactions. Loading oxidation and/or reduction cocatalysts on semiconductors can facilitate oxidation and reduction reactions by providing the active sites/reaction sites while suppressing the charge recombination and reverse reactions. In a PEC water splitting system, the water oxidation and reduction reactions occur at opposite electrodes, so cocatalysts loaded on the electrode materials mainly act as active sites/reaction sites spatially separated as natural photosynthesis does. In both cases, the nature of the loaded cocatalysts and their interaction with the semiconductor through the interface/junction are important. The cocatalyst can provide trapping sites for the photogenerated charges and promote the charge separation, thus enhancing the quantum efficiency; the cocatalysts could improve the photostability of the catalysts by timely consuming of the photogenerated charges, particularly the holes; most importantly, the cocatalysts catalyze the reactions by lowering the activation energy. Our research shows that loading suitable dual cocatalysts on semiconductors can significantly increase the photocatalytic activities of hydrogen and oxygen evolution reactions, and even make the overall water splitting reaction possible. All of these findings suggest that dual cocatalysts are necessary for developing highly efficient photocatalysts for water splitting reactions.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTTitanium Dioxide-Based Nanomaterials for Photocatalytic Fuel GenerationsYi Ma†, Xiuli Wang†, Yushuai Jia†, Xiaobo Chen‡, Hongxian Han*†, and Can Li*†View Author Information† State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences and Dalian National Laboratory for Clean Energy, 457 Zhongshan Road, Dalian 116023, China‡ Department of Chemistry, College of Arts and Sciences, University of Missouri-Kansas City, 5100 Rockhill Road, Kansas City, Missouri 64110, United States*Phone: 86-411-84379070. Fax: 86-411-84694447. E-mail: [email protected]*Phone: 86-411-84379760. Fax: 86-411-84694447. E-mail: [email protected]Cite this: Chem. Rev. 2014, 114, 19, 9987–10043Publication Date (Web):August 7, 2014Publication History Received4 January 2014Published online7 August 2014Published inissue 8 October 2014https://pubs.acs.org/doi/10.1021/cr500008uhttps://doi.org/10.1021/cr500008ureview-articleACS PublicationsCopyright © 2014 American Chemical SocietyRequest reuse permissionsArticle Views32869Altmetric-Citations2093LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information SUBJECTS:Minerals,Oxides,Photocatalysis,Photocatalysts,Redox reactions Get e-Alerts

Commercial lithium-ion (Li-ion) batteries suffer from low energy density and do not meet the growing demands of the energy storage market. Therefore, building next-generation rechargeable Li and Li-ion batteries with higher energy densities, better safety characteristics, lower cost and longer cycle life is of outmost importance. To achieve smaller and lighter next-generation rechargeable Li and Li-ion batteries that can outperform commercial Li-ion batteries, several new energy storage chemistries are being extensively studied. In this review, we summarize the current trends and provide guidelines towards achieving this goal, by addressing batteries using high-voltage cathodes, metal fluoride electrodes, chalcogen electrodes, Li metal anodes, high-capacity anodes as well as useful electrolyte solutions. We discuss the choice of active materials, practically achievable energy densities and challenges faced by the respective battery systems. Furthermore, strategies to overcome remaining challenges for achieving energy characteristics are addressed in the hope of providing a useful and balanced assessment of current status and perspectives of rechargeable Li and Li-ion batteries.

Abstract Improving the long-term stability of perovskite solar cells is critical to the deployment of this technology. Despite the great emphasis laid on stability-related investigations, publications lack consistency in experimental procedures and parameters reported. It is therefore challenging to reproduce and compare results and thereby develop a deep understanding of degradation mechanisms. Here, we report a consensus between researchers in the field on procedures for testing perovskite solar cell stability, which are based on the International Summit on Organic Photovoltaic Stability (ISOS) protocols. We propose additional procedures to account for properties specific to PSCs such as ion redistribution under electric fields, reversible degradation and to distinguish ambient-induced degradation from other stress factors. These protocols are not intended as a replacement of the existing qualification standards, but rather they aim to unify the stability assessment and to understand failure modes. Finally, we identify key procedural information which we suggest reporting in publications to improve reproducibility and enable large data set analysis.

The methanol-to-olefins (MTO) reaction is an interesting and important reaction for both fundamental research and industrial application. The Dalian Institute of Chemical Physics (DICP) has developed a MTO technology that led to the successful construction and operation of the world's first coal to olefin plant in 2010. This historical perspective gives a brief summary on the key issues for the process development, including studies on the reaction mechanism, molecular sieve synthesis and crystallization mechanism, catalyst and its manufacturing scale up, reactor selection and reactor scale up, process demonstration, and commercialization. Further challenges on the fundamental research and the directions for future catalyst improvement are also suggested.

Abstract Even though the mesoporous-type perovskite solar cell (PSC) is known for high efficiency, its planar-type counterpart exhibits lower efficiency and hysteretic response. Herein, we report success in suppressing hysteresis and record efficiency for planar-type devices using EDTA-complexed tin oxide (SnO 2 ) electron-transport layer. The Fermi level of EDTA-complexed SnO 2 is better matched with the conduction band of perovskite, leading to high open-circuit voltage. Its electron mobility is about three times larger than that of the SnO 2 . The record power conversion efficiency of planar-type PSCs with EDTA-complexed SnO 2 increases to 21.60% (certified at 21.52% by Newport) with negligible hysteresis. Meanwhile, the low-temperature processed EDTA-complexed SnO 2 enables 18.28% efficiency for a flexible device. Moreover, the unsealed PSCs with EDTA-complexed SnO 2 degrade only by 8% exposed in an ambient atmosphere after 2880 h, and only by 14% after 120 h under irradiation at 100 mW cm −2 .

capture as well as utilization were systematically discussed and compared. With our great effort, this review would be of significant importance for academic researchers for obtaining an overall understanding of the current developments and future trends of CCU. This work is bound to benefit researchers in fields relating to CCU and facilitate the progress of significant breakthroughs in both fundamental research and commercial applications to deliver perspective views for future scientific and industrial advances in CCU.

Two-inch-sized perovskite crystals, CH3NH3PbX3 (X=I, Br, Cl), with high crystalline quality are prepared by a solution-grown strategy. The availability of large perovskite crystals is expected to transform its broad applications in photovoltaics, optoelectronics, lasers, photodetectors, LEDs, etc., just as crystalline silicon has done in revolutionizing the modern electronics and photovoltaic industries. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Abstract The direct production of liquid fuels from CO 2 hydrogenation has attracted enormous interest for its significant roles in mitigating CO 2 emissions and reducing dependence on petrochemicals. Here we report a highly efficient, stable and multifunctional Na–Fe 3 O 4 /HZSM-5 catalyst, which can directly convert CO 2 to gasoline-range (C 5 –C 11 ) hydrocarbons with selectivity up to 78% of all hydrocarbons while only 4% methane at a CO 2 conversion of 22% under industrial relevant conditions. It is achieved by a multifunctional catalyst providing three types of active sites (Fe 3 O 4 , Fe 5 C 2 and acid sites), which cooperatively catalyse a tandem reaction. More significantly, the appropriate proximity of three types of active sites plays a crucial role in the successive and synergetic catalytic conversion of CO 2 to gasoline. The multifunctional catalyst, exhibiting a remarkable stability for 1,000 h on stream, definitely has the potential to be a promising industrial catalyst for CO 2 utilization to liquid fuels.

The efficiency of planar CH₃NH₃PbI₃ perovskite solar cells has been improved up to 19.62% using an ionic liquid to modify the TiO₂ electron transport layer, and the <italic>J</italic>–<italic>V</italic> hysteresis is completely eliminated.

Abstract Solid polymer electrolytes (SPEs) have aroused wide interest in lithium batteries because of their sufficient mechanical properties, superior safety performances, and excellent processability. However, ionic conductivity and high‐voltage compatibility of SPEs are still yet to meet the requirement of future energy‐storage systems, representing significant barriers to progress. In this regard, intermolecular interactions in SPEs have attracted attention, and they can significantly impact on the Li + motion and frontier orbital energy level of SPEs. Recent advances in improving electrochemcial performance of SPEs are reviewed, and the underlying mechanism of these proposed strategies related to intermolecular interaction is discussed, including ion–dipole, hydrogen bonds, π–π stacking, and Lewis acid–base interactions. It is hoped that this review can inspire a deeper consideration on this critical issue, which can pave new pathway to improve ionic conductivity and high‐voltage performance of SPEs.

Valorization of native birch wood lignin into monomeric phenols over nickel-based catalysts has been studied. High chemoselectivity to aromatic products was achieved by using Ni-based catalysts and common alcohols as solvents. The results show that lignin can be selectively cleaved into propylguaiacol and propylsyringol with total selectivity >90% at a lignin conversion of about 50%. Alcohols, such as methanol, ethanol and ethylene glycol, are suitable solvents for lignin conversion. Analyses with MALDI-TOF and NMR show that birch lignin is first fragmented into smaller lignin species consisting of several benzene rings with a molecular weight of m/z ca. 1100 to ca. 1600 via alcoholysis reaction. The second step involves the hydrogenolysis of the fragments into phenols. The presence of gaseous H2 has no effect on lignin conversion, indicating that alcohols provide active hydrogen species, which is further confirmed by isotopic tracing experiments. Catalysts are recycled by magnetic separation and can be reused four times without losing activity. The mechanistic insights from this work could be helpful in understanding native lignin conversion and the formation of monomeric phenolics via reductive depolymerization.

With these guidelines, we aim to unite the lignin-first biorefining research field around best practices for performing or reporting feedstock analysis, reactor design, catalyst performance, and product yields.

artificial photosynthesis holds significant potential for optimizing the energy situation and mitigating the global warming effect. Photocatalytic water splitting utilizing particulate semiconductors offers great potential for the production of renewable hydrogen, while this cross-road among biology, chemistry, and physics features a topic with fascinating interdisciplinary challenges. Progress in photocatalytic water splitting has been achieved in recent years, ranging from fundamental scientific research to pioneering scalable practical applications. In this review, we focus mainly on the recent advancements in terms of the development of new light-absorption materials, insights and strategies for photogenerated charge separation, and studies towards surface catalytic reactions and mechanisms. In particular, we emphasize several efficient charge separation strategies such as surface-phase junction, spatial charge separation between facets, and polarity-induced charge separation, and also discuss their unique properties including ferroelectric and photo-Dember effects on spatial charge separation. By integrating time- and space-resolved characterization techniques, critical issues in photocatalytic water splitting including photoinduced charge generation, separation and transfer, and catalytic reactions are analyzed and reviewed. In addition, photocatalysts with state-of-art efficiencies in the laboratory stage and pioneering scalable solar water splitting systems for hydrogen production using particulate photocatalysts are presented. Finally, some perspectives and outlooks on the future development of photocatalytic water splitting using particulate photocatalysts are proposed.

Developing sustainable energy resources is one of the most urgent missions for human beings as increasing energy demand is in drastic conflict with limited global fossil fuels. Among the various types of sustainable energy resources, solar energy is considered to be promising due to its inexhaustible supply, universality, high capacity, and environmental friendliness. However, natural solar irradiation is decentralized, intermittent and fluctuates constantly. Therefore, effective utilization of solar energy in a clean, economic, and convenient way remains a grand challenge.

The trap states at grain boundaries (GBs) within polycrystalline perovskite films deteriorate their optoelectronic properties, making GB engineering particularly important for stable high-performance optoelectronic devices. It is demonstrated that trap states within bulk films can be effectively passivated by semiconducting molecules with Lewis acid or base functional groups. The perovskite crystallization kinetics are studied using in situ synchrotron-based grazing-incidence X-ray scattering to explore the film formation mechanism. A model of the passivation mechanism is proposed to understand how the molecules simultaneously passivate the Pb-I antisite defects and vacancies created by under-coordinated Pb atoms. In addition, it also explains how the energy offset between the semiconducting molecules and the perovskite influences trap states and intergrain carrier transport. The superior optoelectronic properties are attained by optimizing the molecular passivation treatments. These benefits are translated into significant enhancements of the power conversion efficiencies to 19.3%, as well as improved environmental and thermal stability of solar cells. The passivated devices without encapsulation degrade only by ≈13% after 40 d of exposure in 50% relative humidity at room temperature, and only ≈10% after 24 h at 80 °C in controlled environment.

A frigostable aqueous hybrid electrolyte enabled by the solvation interaction of Zn²⁺–EG is proposed for low-temperature zinc-based energy storage devices.

In the search of alternative resources to make commodity chemicals and transportation fuels for a low carbon future, lignocellulosic biomass with over 180-billion-ton annual production rate has been identified as a promising feedstock. This review focuses on the state-of-the-art catalytic transformation of lignocellulosic biomass into value-added chemicals and fuels. Following a brief introduction on the structure, major resources and pretreatment methods of lignocellulosic biomass, the catalytic conversion of three main components, i.e., cellulose, hemicellulose and lignin, into various compounds are comprehensively discussed. Either in separate steps or in one-pot, cellulose and hemicellulose are hydrolyzed into sugars and upgraded into oxygen-containing chemicals such as 5-HMF, furfural, polyols, and organic acids, or even nitrogen-containing chemicals such as amino acids. On the other hand, lignin is first depolymerized into phenols, catechols, guaiacols, aldehydes and ketones, and then further transformed into hydrocarbon fuels, bioplastic precursors and bioactive compounds. The review then introduces the transformations of whole biomass via catalytic gasification, catalytic pyrolysis, as well as emerging strategies. Finally, opportunities, challenges and prospective of woody biomass valorization are highlighted.

Conjugated microporous polymers are a new class of porous materials with an extended π-conjugation in an amorphous organic framework. Owing to the wide-ranging flexibility in the choice and design of components and the available control of pore parameters, these polymers can be tailored for use in various applications, such as gas storage, electronics and catalysis. Here we report a class of cobalt/aluminium-coordinated conjugated microporous polymers that exhibit outstanding CO2 capture and conversion performance at atmospheric pressure and room temperature. These polymers can store CO2 with adsorption capacities comparable to metal-organic frameworks. The cobalt-coordinated conjugated microporous polymers can also simultaneously function as heterogeneous catalysts for the reaction of CO2 and propylene oxide at atmospheric pressure and room temperature, wherein the polymers demonstrate better efficiency than a homogeneous salen-cobalt catalyst. By combining the functions of gas storage and catalysts, this strategy provides a direction for cost-effective CO2 reduction processes. Conjugated microporous polymers are highly flexible materials that may be used for gas storage and catalysis applications. Here, the authors report metal-functionalized conjugated microporous polymers capable of both capturing CO2and functioning as a heterogeneous catalyst in its conversion to propylene carbonate.

Abstract For the large-scale sustainable implementation of polymer electrolyte membrane fuel cells in vehicles, high-performance electrocatalysts with low platinum consumption are desirable for use as cathode material during the oxygen reduction reaction in fuel cells. Here we report a carbon black-supported cost-effective, efficient and durable platinum single-atom electrocatalyst with carbon monoxide/methanol tolerance for the cathodic oxygen reduction reaction. The acidic single-cell with such a catalyst as cathode delivers high performance, with power density up to 680 mW cm −2 at 80 °C with a low platinum loading of 0.09 mg Pt cm −2 , corresponding to a platinum utilization of 0.13 g Pt kW −1 in the fuel cell. Good fuel cell durability is also observed. Theoretical calculations reveal that the main effective sites on such platinum single-atom electrocatalysts are single-pyridinic-nitrogen-atom-anchored single-platinum-atom centres, which are tolerant to carbon monoxide/methanol, but highly active for the oxygen reduction reaction.