Photoreduction of CO2 into sustainable and green solar fuels is generally believed to be an appealing solution to simultaneously overcome both environmental problems and energy crisis. The low selectivity of challenging multi-electron CO2 photoreduction reactions makes it one of the holy grails in heterogeneous photocatalysis. This Review highlights the important roles of cocatalysts in selective photocatalytic CO2 reduction into solar fuels using semiconductor catalysts. A special emphasis in this review is placed on the key role, design considerations and modification strategies of cocatalysts for CO2 photoreduction. Various cocatalysts, such as the biomimetic, metal-based, metal-free, and multifunctional ones, and their selectivity for CO2 photoreduction are summarized and discussed, along with the recent advances in this area. This Review provides useful information for the design of highly selective cocatalysts for photo(electro)reduction and electroreduction of CO2 and complements the existing reviews on various semiconductor photocatalysts.

Cocatalysts for Selective Photoreduction of CO2 into Solar Fuels.

Photocatalysts and Photoelectrodes James L. White,† Maor F. Baruch,† James E. Pander III,† Yuan Hu,† Ivy C. Fortmeyer,† James Eujin Park,† Tao Zhang,† Kuo Liao,† Jing Gu,‡ Yong Yan,‡ Travis W. Shaw,† Esta Abelev,† and Andrew B. Bocarsly*,† †Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States ‡Chemical and Materials Science Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States

Light-Driven Heterogeneous Reduction of Carbon Dioxide: Photocatalysts and Photoelectrodes

Photocatalytic reduction of CO2 into hydrocarbon fuels, an artificial photosynthesis, is based on the simulation of natural photosynthesis in green plants, whereby O2 and carbohydrates are produced from H2 O and CO2 using sunlight as an energy source. It couples the reductive half-reaction of CO2 fixation with a matched oxidative half-reaction such as water oxidation, to achieve a carbon neutral cycle, which is like killing two birds with one stone in terms of saving the environment and supplying future energy. The present review provides an overview and highlights recent state-of-the-art accomplishments of overcoming the drawback of low photoconversion efficiency and selectivity through the design of highly active photocatalysts from the point of adsorption of reactants, charge separation and transport, light harvesting, and CO2 activation. It specifically includes: i) band-structure engineering, ii) nanostructuralization, iii) surface oxygen vacancy engineering, iv) macro-/meso-/microporous structuralization, v) exposed facet engineering, vi) co-catalysts, vii) the development of a Z-scheme system. The challenges and prospects for future development of this field are also present.

Photocatalytic Conversion of CO 2 into Renewable Hydrocarbon Fuels: State‐of‐the‐Art Accomplishment, Challenges, and Prospects

Ever-increasing fossil-fuel combustion along with massive CO2 emissions has aroused a global energy crisis and climate change. Photocatalytic CO2 reduction represents a promising strategy for clean, cost-effective, and environmentally friendly conversion of CO2 into hydrocarbon fuels by utilizing solar energy. This strategy combines the reductive half-reaction of CO2 conversion with an oxidative half reaction, e.g., H2 O oxidation, to create a carbon-neutral cycle, presenting a viable solution to global energy and environmental problems. There are three pivotal processes in photocatalytic CO2 conversion: (i) solar-light absorption, (ii) charge separation/migration, and (iii) catalytic CO2 reduction and H2 O oxidation. While significant progress is made in optimizing the first two processes, much less research is conducted toward enhancing the efficiency of the third step, which requires the presence of cocatalysts. In general, cocatalysts play four important roles: (i) boosting charge separation/transfer, (ii) improving the activity and selectivity of CO2 reduction, (iii) enhancing the stability of photocatalysts, and (iv) suppressing side or back reactions. Herein, for the first time, all the developed CO2 -reduction cocatalysts for semiconductor-based photocatalytic CO2 conversion are summarized, and their functions and mechanisms are discussed. Finally, perspectives in this emerging area are provided.

Cocatalysts in Semiconductor-based Photocatalytic CO2 Reduction: Achievements, Challenges, and Opportunities.

The use of solar energy to catalyze the photo-driven processes has attracted tremendous attention from the scientific community because of its great potential to address energy and environmental is...

Perovskite Oxide Based Materials for Energy and Environment-Oriented Photocatalysis

Carbon dioxide (CO2) photoreduction by gaseous water over silica-pillared lamellar niobic acid, viz. HNb3O8, was studied in this work. The physicochemical characteristics of samples were examined b...

Photocatalytic Reduction of Carbon Dioxide to Methane over SiO2-Pillared HNb3O8

The testing of Web services is an essential aspect of their quality assurance, however, because this testing often involves injecting only one mutant at one time, some vulnerability faults cannot be detected. To address this, the current paper presents a set of mutation operators that can be combined and defines the corresponding combinatorial strategies based on data perturbation and combinatorial testing. Based on this, multiple mutants can be injected at one time to help uncover interactive faults. To improve testing efficiency and effectiveness, a combinatorial testing approach focusing on Web service vulnerability is proposed: Firstly, initial test data are generated with perturbation techniques based on Web Services Description Language documents and Simple Object Access Protocol messages. Then, a combinatorial testing cases generation (CTCG) algorithm is used to generate the final combinatorial test data according to the proposed strategies. Furthermore, for some special Web services in which there is only one parameter or one method in service interface, a fuzzy mutation approach algorithm, as a complementary approach to CTCG, is also proposed. Finally, some testing experiments are conducted to verify the effectiveness of the proposed approaches in an integrated testing platform. The experiments show that proposed approaches are both feasible and effective: They can find more vulnerability faults than the traditional approaches.

A Web services vulnerability testing approach based on combinatorial mutation and SOAP message mutation

Web services testing is one of the most important techniques used to assure the quality of Web services at present. Currently, Web service testing has been only focused on one mutant injected at one time. Thus, based on data perturbation and combinatorial testing techniques, this paper presents a set of mutation operators that can be combined, and defines corresponding combinatorial strategies. Multiple mutants are injected at one time. In order to improve the testing efficiency and effect, a combinatorial approach for testing Web service vulnerability is proposed. Firstly, based on WSDL (Web Service Description Language) documents and SOAP (Simple Object Access Protocol) messages, the initial test data are generated by perturbation techniques. Then CTCG (Combinatorial Testing Cases Generation) algorithm is proposed and called to generate the final combinatorial test data according to combinatorial strategies. Finally, some preliminary experiments are conducted in an integration testing platform to verify the applicability of the proposed approach. The experimental results show that the approach is more cost-effective.

Combinatorial Mutation Approach to Web Service Vulnerability Testing Based on SOAP Message Mutations

This paper proposes an improved chemical abstract machine to accurately describe the behavior characteristics of components based on chemical computation model. The chemical abstract machine is analyzed from the perspective of software field, thereupon the formal description of chemical abstract machine is given based on γc computation model. Firstly, we analyze the dynamic characteristics of components and chemical computation model. Secondly, the definition of chemical abstract machine and relevant rules are extended to more accurately describe the dynamic behavior of some components. Then, the γc computation model of the component is given for accurately describing the component behavior. Finally, an actual case of component is described by using the improved component chemical abstract machine model. The case shows that the improved component chemical abstract machine model can provide a good theoretical foundation for generating effective test cases in component testing.

Describing Component Behavior Using Improved Chemical Abstract Machine

A nanocasting method using SBA-15 as a hard template was adopted to prepare mesoporous nanocrystalline ANbO3 (A = Li, Na, and K) samples. The characteristics of samples werecharacterized by techniques such asXRD, N2-sorption measurement, HRTEM and UVDRS. It was found that thealkality of the alkali metals could have profound impacts on the synthesis andthe physical properties of samples. The Li, Na, and K precursors can reacteasily with the siliceous template, and the reactivity varies with the alkalityof the alkali metal. The synthesis of KNbO3 is unsuccessful because of the high alkality ofK. The templated LiNbO3 andNaNbO3 consist of single crystalline nanoparticles that generate interparticle mesoporosity. The LiNbO3andNaNbO3 samples showed notably enhanced photocatalytic activitiesfor 2-propanol photodegradation in comparison to the counterparts prepared bythe solid state reaction.

Hard Template Synthesis of Mesoporous and Nanocrystalline Alkali Metal Niobates with Enhanced Photocatalytic Performance

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