CO_(2) conversion to solar fuels and chemicals:Opening the new paths

This future article discusses the new prospects and directions of CO_(2)conversion via the photo-electrocatalytic(PEC)route.The second(2nd)generation solar fuels and chemicals(SFs)are generated directly in PEC systems via electrons/protons reactions without forming molecular H_(2)as an intermediate,overcoming the thermodynamics limitations and practical issues encountered for electro-fuels produced by multistep thermocatalytic processes(i.e.CO_(2)conversion with H_(2)coming from water electrolysis).A distributed and decentralized production of SFs requires very compact,highly integrated,and intensified technologies.Among the existing reactors of advanced design(based on artificial leaves or photosynthesis),the integrated photovoltaic plus electrocatalytic(PV-EC)device is the only system(demonstrated at large scale)to produce SFs with high solar-to-fuel(STF)efficiency.However,while the literature indicates STF efficiency as the main(and only)measure of process performance,we remark here the need to refer to productivity(in terms of current density)and make tests with reliable flow PEC systems(with electrodes of at least 5–10 cm^(2))to accelerate the scaling-up process.Using approaches that minimize downstream separation costs is also mandatory.Many limitations exist in PEC systems,but most can be overcome by proper electrode and cell engineering,thus going beyond the properties of the electrocatalysts.As examples of current developments,we present the progress of(i)artificial leaf/tree devices for green H_(2)distributed production and(ii)a PEC device producing the same chemicals at both cathode and anode parts without downstream operations for green solvent distributed production.Based on these developments,future directions,such as producing fertilizers and food components from the air,are outlined.The aim is to provide new ideas and research directions from a personal perspective.

Recent advances in Cu-based nanocomposite photocatalysts for CO_2 conversion to solar fuels

COconversion via photocatalysis is a potential solution to address global warming and energy shortage.Photocatalysis can directly utilize the inexhaustible sunlight as an energy source to catalyze the reduction of COto useful solar fuels such as CO, CH, CHOH, and CHOH. Among studied formulations, Cubased photocatalysts are the most attractive for COconversion because the Cu-based photocatalysts are low-cost and abundance comparing noble metal-based catalysts. In this literature review, a comprehensive summary of recent progress on Cu-based photocatalysts for COconversion, which includes metallic copper, copper alloy nanoparticles（NPs）, copper oxides, and copper sulfides photocatalysts, can be found. This review also included a detailed discussion on the correlations of morphology, structure, and performance for each type of Cu-based catalysts. The reaction mechanisms and possible pathways for productions of various solar fuels were analyzed, which provide insight into the nature of potential active sites for the catalysts. Finally, the current challenges and perspective future research directions were outlined, holding promise to advance Cu-based photocatalysts for COconversion with much-enhanced energy conversion efficiency and production rates.

Layered double hydroxide-based photocatalytic materials toward renewable solar fuels production

Photocatalysis is an ideal and promising green technology to drive numerous chemical reactions for valued chemicals production under very mild conditions,thereby providing solutions to global energy and environment issues related to burning fossil fuels.Over the past decade,layered double hydroxides(LDHs),as the members in two-dimensional materials family,have attracted much attention due to their many advantages in photocatalysis,such as facile synthesis,low cost and powerful tunability of composition.In this review,we provide a synthetic overview of recent research advances of LDH-based photocatalysts,with the main discussion of the design strategies to improve their photocatalytic performance,including component control,defect engineering,hybridization,and topological transformation.Structure-performance correlations and tailor-made material synthesis strategies are elaborated to discuss how to realize high-performance LDH-based photocatalysts for three important reactions(i.e.,water splitting,CO_(2)conversion,and N2 reduction)to generate desirable solar fuels.Further,the remaining challenges and future perspectives of LDH-based photocatalysts are summed up,aiming to inspire brand new solutions for pushing forward the development of LDH-based photocatalysis.

Azobenzene‑Based Solar Thermal Fuels:A Review

The energy storage mechanism of azobenzene is based on the transformation of molecular cis and trans isomerization,while NBD/QC,DHA/VHF,and fulvalene dimetal complexes realize the energy storage function by changing the molecular structure.Acting as“molecular batteries,”they can exhibit excellent charging and discharging behavior by converting between trans and cis isomers or changing molecular structure upon absorption of ultraviolet light.Key properties determining the performance of STFs are stored energy,energy density,half-life,and solar energy conversion efficiency.This review is aiming to provide a comprehensive and authoritative overview on the recent advancements of azobenzene molecular photoswitch system in STFs fields,including derivatives and carbon nano-templates,which is emphasized for its attractive performance.Although the energy storage performance of Azo-STFs has already reached the level of commercial lithium batteries,the cycling capability and controllable release of energy still need to be further explored.For this,some potential solutions to the cycle performance are proposed,and the methods of azobenzene controllable energy release are summarized.Moreover,energy stored by STFs can be released in the form of mechanical energy,which in turn can also promote the release of thermal energy from STFs,implying that there could be a relationship between mechanical and thermal energy in Azo-STFs,providing a potential direction for further research on Azo-STFs.

Surface-modified Ag@Ru-P25 for photocatalytic CO_(2) conversion with high selectivity over CH_(4) formation at the solid–gas interface

Systematic optimization of the photocatalyst and investigation of the role of each component is important to maximizing catalytic activity and comprehending the photocatalytic conversion of CO_(2) reduction to solar fuels.A surface-modified Ag@Ru-P25 photocatalyst with H_(2)O_(2) treatment was designed in this study to convert CO_(2) and H_(2)O vapor into highly selective CH4.Ru doping followed by Ag nanoparticles(NPs)cocatalyst deposition on P25(TiO_(2))enhances visible light absorption and charge separation,whereas H_(2)O_(2) treatment modifies the surface of the photocatalyst with hydroxyl(–OH)groups and promotes CO_(2) adsorption.High-resonance transmission electron microscopy,X-ray photoelectron spectroscopy,X-ray absorption near-edge structure,and extended X-ray absorption fine structure techniques were used to analyze the surface and chemical composition of the photocatalyst,while thermogravimetric analysis,CO_(2) adsorption isotherm,and temperature programmed desorption study were performed to examine the significance of H_(2)O_(2) treatment in increasing CO_(2) reduction activity.The optimized Ag1.0@Ru1.0-P25 photocatalyst performed excellent CO_(2) reduction activity into CO,CH4,and C2H6 with a~95%selectivity of CH4,where the activity was~135 times higher than that of pristine TiO_(2)(P25).For the first time,this work explored the effect of H_(2)O_(2) treatment on the photocatalyst that dramatically increases CO_(2) reduction activity.

Electrocatalytic conversion of CO_2 to liquid fuels using nanocarbon-based electrodes

Recent advances on the use of nanocarbon-based electrodes for the electrocatalytic conversion of gaseous streams of CO2 to liquid fuels are discussed in this perspective paper. A novel gas-phase electrocatalytic cell, different from the typical electrochemical systems working in liquid phase, was developed. There are several advantages to work in gas phase, e.g. no need to recover the products from a liquid phase and no problems of CO2 solubility, etc. Operating under these conditions and using electrodes based on metal nanoparticles supported over carbon nanotube （CNT） type materials, long C-chain products （in particular isopropanol under optimized conditions, but also hydrocarbons up to C8-C9） were obtained from the reduction of CO2. Pt-CNT are more stable and give in some cases a higher productivity, but Fe-CNT, particular using N-doped carbon nanotubes, give excellent properties and are preferable to noble-metal-based electrocatalysts for the lower cost. The control of the localization of metal particles at the inner or outer surface of CNT is an importact factor for the product distribution. The nature of the nanocarbon substrate also plays a relevant role in enhancing the productivity and tuning the selectivity towards long C-chain products. The electrodes for the electrocatalytic conversion of CO2 are part of a photoelectrocatalytic （PEC） solar cell concept, aimed to develop knowledge for the new generation artificial leaf-type solar cells which can use sunlight and water to convert CO2 to fuels and chemicals. The CO2 reduction to liquid fuels by solar energy is a good attempt to introduce renewables into the existing energy and chemical infrastructures, having a higher energy density and easier transport/storage than other competing solutions （i.e. H2）.

Semiconductor,molecular and hybrid systems for photoelectrochemical solar fuel production

The paper shortly reviews the basic direct approaches applied in searching for viable solutions to solar fuel production. These are generally distinguished in molecular and semiconductor(non-molecular)systems, however, hybrid strategies, proposed recently, have also been included. The most promising efforts are considered, highlighting key aspects and emerging critical issues. Special attention is paid to aspects such as electrode architecture, device design, and main differences in the scientific vision and challenges to directly produce solar fuels. This overview could be useful to orientate the readers in the wide panorama of research activities concerning water splitting, natural and artificial photosynthesis, and solar fuel production through the identification of common aspects, specialties and potentialities of the many initiatives and approaches that are developing worldwide in this field with the final aim to meet world energy demand.

Thermogravimetric Analysis of Zirconia-Doped Ceria for Thermochemical Production of Solar Fuel

Developing an efficient redox material is crucial for thermochemical cycles that produce solar fuels (e.g. H2 and CO), enabling a sustainable energy supply. In this study, zirconia-doped cerium oxide (Ce1-xZrxO2) was tested in CO2-splitting cycles for the production of CO. The impact of the Zr-content on the splitting performance was investigated within the range 0 ≤ x < 0.4. The materials were synthesized via a citrate nitrate auto combustion route and subjected to thermogravimetric experiments. The results indicate that there is an optimal zirconium content, x = 0.15, improving the specific CO2-splitting performance by 50% compared to pure ceria. Significantly enhanced performance is observed for 0.15 ≤ x ≤ 0.225. Outside this range, the performance decreases to values of pure ceria. These results agree with theoretical studies attributing the improvements to lattice modification. Introducing Zr4+ into the fluorite structure of ceria compensates for the expansion of the crystal lattice caused by the reduction of Ce4+ to Ce3+. Regarding the reaction conditions, the most efficient composition Ce0.85Zr0.15O2 enhances the required conditions by a temperature of 60 K or one order of magnitude of the partial pressure of oxygen p(O2) compared to pure ceria. The optimal composition was tested in long-term experiments of one hundred cycles, which revealed declining splitting kinetics.

Electronic/Ionic Conducting Bipolar Membranes for Solar Fuel Production under pH Gradients

The components required for artificial photosynthesis including light absorbers and catalysts are being developed at a rapid rate.In many cases,the anodic and cathodic reactions driven with these systems are optimized for significantly different pH conditions,raising the issue of how they can be made compatible.Recent work from our group has shown that large pH gradients can be maintained during electrolysis using BPM(bipolar membrane)and that electronic/ionic membranes can be used to couple the two half reactions without the use of external wiring and reducing the ohmic drop in the system.This study investigates the properties of composite BPMs designed for artificial photosynthetic devices that require half reactions to operate under different pH conditions.Details of performance as a function of the nature of the composites and methods of creating BPMs are detailed.

Recent advances in bismuth-based photocatalysts:Environment and energy applications

Photocatalysis is an effective way to solve the problems of environmental pollution and energy shortage.Numerous photocatalysts have been developed and various strategies have been proposed to improve the photocatalytic performance.Among them,Bi-based photocatalysts have become one of the most popular research topics due to their suitable band gaps,unique layered structures,and physicochemical properties.In this review,Bi-based photocatalysts(BiOX,BiVO_(4),Bi_(2)S_(3),Bi_(2)MoO_(6),and other Bi-based photocatalysts)have been summarized in the field of photocatalysis,including their applications of the removal of organic pollutants,hydrogen production,oxygen production etc.The preparation strategies on how to improve the photocatalytic performance and the possible photocatalytic mechanism are also summarized,which could supply new insights for fabricating high-efficient Bi-based photocatalysts.Finally,we summarize the current challenges and make a reasonable outlook on the future development direction of Bi-based photocatalysts.

Efficient solar-driven CO_(2)-to-fuel conversion via Ni/MgAlO_(x)@SiO_(2)nanocomposites at low temperature

Solar-driven CO_(2)-to-fuel conversion assisted by another major greenhouse gas CH_(4)is promising to concurrently tackle energy shortage and global warming problems.However,current techniques still suffer from drawbacks of low efficiency,poor stability,and low selectivity.Here,a novel nanocomposite composed of interconnected Ni/MgAlOx nanoflakes grown on SiO_(2)particles with excellent spatial confinement of active sites is proposed for direct solar-driven CO_(2)-to-fuel conversion.An ultrahigh light-to-fuel efficiency up to 35.7%,high production rates of H_(2)(136.6 mmol min^(-1)g^(-1))and CO(148.2 mmol min^(-1)g^(-1)),excellent selectivity(H_(2)/CO ratio of 0.92),and good stability are reported simultaneously.These outstanding performances are attributed to strong metal-support interactions,improved CO_(2)absorption and activation,and decreased apparent activation energy under direct light illumination.MgAlO_(x)@SiO_(2)support helps to lower the activation energy of CH^(*) oxidation to CHO^(*) and improve the dissociation of CH_(4)to CH_(3)^(*) as confirmed by DFT calculations.Moreover,the lattice oxygen of MgAlO_(x) participates in the reaction and contributes to the removal of carbon deposition.This work provides promising routes for the conversion of greenhouse gasses into industrially valuable syngas with high efficiency,high selectivity,and benign sustainability.

Analysis of the factors controlling performances of Au-modified TiO2 nanotube array based photoanode in photo-electrocatalytic(PECa)cells

The efficiency of photo-electrocatalytic（PECa） devices for the production of solar fuels depends on several limiting factors such as light harvesting, charge recombination and mass transport diffusion. We analyse here how they influence the performances in PECa cells having a photo-anode based on Au-modified TiOnanotube（TNT） arrays, with the aim of developing design criteria to optimize the photo-anode and the PECa cell configuration for water photo-electrolysis（splitting） and ethanol photo-reforming processes.The TNT samples were prepared by controlled anodic oxidation of Ti foils and then decorated with gold nanoparticles using different techniques to enhance the visible light response through heterojunction and plasmonic effects. The activity tests were made in a gas-phase reactor, as well as in a PECa cell without applied bias. Results were analysed in terms of photo-generated current, Hproduction rate and photoconversion efficiency. Particularly, a solar-to-hydrogen efficiency of 0.83% and a Faradaic efficiency of 91%were obtained without adding sacrificial reagents.

Selective CO_(2) reduction into formate using Ln-Ta oxynitrides combined with a binuclear Ru(Ⅱ)complex under visible light

Hybrid materials constructed from a visible-light-absorbing semiconductor and a functional metal complex have attracted attention as efficient photocatalysts for CO_(2) reduction with high selectivity to a desired product.In this work,defect fluorite-type Ln-Ta oxynitrides LnTaO_(x)N_(y)(Ln=Nd,Sm,Gd,Tb,Dy and Ho)were examined as the semiconductor component in a hybrid photocatalyst system combined with known Ag nanoparticle promoter and binuclear ruthenium(Ⅱ)complex(RuRu’).Among the LnTaO_(x)N_(y) examined,TbTaO_(x)N_(y) gave the highest performance for CO_(2) reduction under visible light(k>400 nm),with a Ru Ru0-based turnover number of 18 and high selectivity to formate(>99%).Physicochemical analyses indicated that high crystallinity and more negative conduction band potential of Ln Ta O_(x)N_(y)with the absence of Ln-4 f states in the band gap structure contributed to higher activity of the hybrid photocatalyst.

Perovskite-type lanthanum ferrite based photocatalysts:Preparation,properties,and applications

Clean energy and a sustainable environment are grand challenges that the world is facing which can be addressed by converting solar energy into transportable and storable fuels(chemical fuel).The main scientific and technological challenges for efficient solar energy conversion,energy storage,and environmental applications are the stability,durability,and performance of low-cost functional materials.Among different nanomaterials,perovskite type LaFeO_(3)has been extensively investigated as a photocatalyst due to its abundance,high stability,compositional and structural fexibility,high electrocatalytic activity,efficient sunlight absorption,and tunable band gap and band edges.Hence,it is urgent to write a comprehensive review to highlight the trend,challenges,and prospects of LaFeO_(3)in the field of photocatalytic solar energy conversion and environment purification.This critical review summarizes the history and basic principles of photocatalysis.Further,it reviews in detail the LaFeO_(3),applications,shortcomings,and activity enhancement strategies including the design of nanostructures,elemental doping,and heterojunctions construction such as Type-I,Type-II,Z-Type,and uncommon heterojunctions.Besides,the optical and electronic properties,charge carriers separation,electron transport phenomenon and alignment of the band gaps in LaFeO_(3)-based heterostructures are comprehensively discussed.

Air to fuel:Direct capture of CO_(2)from air and in-situ solar-driven conversion into syngas via Ni_(x)/NaA nanomaterials

Ever-increasing CO_(2)emissions and atmospheric concentration mainly due to the burning of traditional fossil fuels have caused severe global warming and climate change problems.Inspired by nature’s carbon cycle,we propose a novel dual functional catalyst-sorbent to tackle energy and environmental problems simultaneously via direct capture of CO_(2)from air and in-situ solar-driven conversion into clean fuels.Economically and operationally advantageous,the planned coupling reaction can be carried out in a single reactor without the requirement for an extra trapping device.The great CO_(2)capture and conversion performance in an integrated step is shown by the CO_(2)capacity of up to 0.38 mmol·g^(−1)for adsorption from 500 ppm CO_(2)at 25℃and the CO_(2)conversion rate of up to 95%.Importantly,the catalyst-sorbent is constituted of a nonprecious metal Ni catalyst and an inexpensive commercially available CO_(2)sorbent,viz,zeolite NaA.Furthermore,this designed dual functional material also exhibits outstanding stability performance.This work offers a novel pathway of capturing CO_(2)in the air at room temperature and converting it by CH4 into fuel,contributing to the new era of carbon neutrality.

Energy,Exergy,and Exergoeconomic Analysis of Solar-Driven Solid Oxide Electrolyzer System Integrated with Waste Heat Recovery for Syngas Production

Syngas fuel generated by solar energy integrating with fuel cell technology is one of the promising methods for future green energy solutions to carbon neutrality.This paper designs a novel solar-driven solid oxide electrolyzer system integrated with waste heat for syngas production.Solar photovoltaic and parabolic trough collecter together drive the solid oxide electrolysis cell to improve system efficiency.The thermodynamic models of components are established,and the energy,exergy,and exergoeconomic analysis are conducted to evaluate the system’s performance.Under the design work conditions,the solar photovoltaic accounts for 88.46%of total exergy destruction caused by its less conversion efficiency.The exergoeconomic analysis indicates that the fuel cell component has a high exergoeconomic factor of 89.56%due to the large capital investment cost.The impacts of key parameters such as current density,operating temperature,pressure and mole fraction on system performances are discussed.The results demonstrate that the optimal energy and exergy efficiencies are achieved at 19.04%and 19.90%when the temperature,pressure,and molar fraction of H_(2)O are 1223.15 K,0.1 MPa,and 50%,respectively.

Developing silicon-based photocathodes for CO_(2)conversion

Photoelectrochemical(PEC)conversion of CO_(2)presents a promising avenue for solar-driven chemical fuel production,with silicon emerging as a cost-effective and high-light-absorbing material pivotal to this technology.Aiming at exploring opportunities for industrializing PEC CO_(2)reduction(PEC-CO_(2)R)by minimizing reaction energy consumption,enhancing reaction efficiency and selectivity,this review summarizes recent advancements in developing Si-based photocathodes for PEC-CO_(2)R.It outlines the fundamental principles,advantages,and limitations of Si photocathodes with key performance metrics.Based on this understanding,the strategies to enhance the performance of the PEC-CO_(2)R system,including light absorption,charge separation,and catalytic reactions are categorized as the interfacial modification,active site decoration,and protective layer design.The design ideas of this advantageous three-layer structure in promoting the efficiency,stability,and selectivity have been clarified.Then,this review scrutinizes the influence of the photocathodic chemical environment.This review consolidates the mechanism insights and notable breakthroughs of various fuel generation processes within Si-based PEC-CO_(2)R systems.Providing this wealth of information offers an up-to-date perspective on the dynamic developments in silicon-based PEC-CO_(2)conversion and underscores the promising pathways toward the sustainable fuel synthesis from pollutant CO_(2).

Solar fuel generation over nature-inspired recyclable TiO_(2)/g-C_(3)N_(4)S-scheme hierarchical thin-film photocatalyst

Preparation of efficient photocatalysts with ease of recovery in solar fuel generation is highly desired to achieve carbon neutralization in carbon dioxide(CO_(2))emissions.Inspired from the forest with superior light penetration and fast gas transport,a TiO_(2)/g-C_(3)N_(4)composite nanowire arrays(NAs)film with maximized light utilization is devised.It is achieved by in-situ coating a thin layer of g-C_(3)N_(4)(as the leaf)on the vertically-oriented TiO_(2)arrays(as tree trunks)on Ti foil(as soil).Benefiting from the effective charge separation by S-scheme charge transfer,intimate contact by the in-situ growth as well as the ingenious structure,the composite,readily recyclable,displays exciting performance in photocatalytic CO_(2)reduction.It is beyond doubt that the combination of heterojunction construction and“nature-inspired biomimetic photocatalyst”design promises practical applications and industrial use.

一种新型太阳能热电化学耦合甲烷重整制氢脱碳与太阳能储能方法

Hydrogen is widely regarded as a sustainable energy carrier with tremendous potential for low-carbon energy transition.Solar photovoltaic-driven water electrolysis(PV-E)is a clean and sustainable approach of hydrogen production,but with major barriers of high hydrogen production costs and limited capacity.Steam methane reforming(SMR),the state-of-the-art means of hydrogen production,has yet to overcome key obstacles of high reaction temperature and CO_(2)emission for sustainability.This work proposes a solar thermo-electrochemical SMR approach,in which solar-driven mid/low-temperature SMR is combined with electrochemical H_(2)separation and in-situ CO_(2)capture.The feasibility of this method is verified experimentally,achieving an average methane conversion of 96.8%at a dramatically reduced reforming temperature of 400-500℃.The underlying mechanisms of this method are revealed by an experimentally calibrated model,which is further employed to predict its performance for thermoelectrochemical hydrogen production.Simulation results show that a net solar-to-H_(2)efficiency of26.25%could be obtained at 500℃,which is over 11 percentage points higher than that of PV-E;the first-law thermodynamic efficiency reaches up to 63.27%correspondingly.The enhanced efficiency also leads to decreased fuel consumption and lower CO_(2)emission of the proposed solar-driven SMR system.Such complementary conversion of solar PV electricity,solar thermal energy,and low-carbon fuel provides a synergistic and efficient means of sustainable H_(2)production with potentially long-term solar energy storage on a vast scale.

Current dilemma in photocatalytic CO_(2) reduction:real solar fuel production or false positive outcomings?

Solar driven carbon dioxide(CO_(2))recycling into hydrocarbon fuels using semiconductor photocatalysts offers an ideal energy conversion pathway to solve both the energy crisis and environmental degradation problems.However,the ubiquitous presence of carbonaceous contaminants in photocatalytic CO_(2) reduction system and the inferior yields of hydrocarbon fuels raise serious concerns about the reliability of the reported experimental results.Here in this perspective,we focus on the accurate assessment of the CO_(2) reduction products,systemically discuss the possible sources of errors in the product quantification,elaborate the common mistakes spread in the analysis of reaction products obtained in 13CO_(2) labelling experiments,and further propose reliable protocols for reporting the results of these isotopic tracing experiments.Moreover,the challenges and cautions in the precise measurement of O_(2) evolution rate are also depicted,and the amplification of the concentration of O_(2) in photoreactors well above the limit of detection is still demonstrated to be the most effective solution to this troublesome issue.We hope the viewpoints raised in this paper will help to assessment the reliability of the reported data in future,and also benefit the beginners that intend to dive in the photocatalytic CO_(2) reduction area.