Nitrogen-doped TiO_2 microsheets with enhanced visible light photocatalytic activity for CO_2 reduction

Nitrogen-doped anatase TiO 2 microsheets with 65%（001） and 35%（101） exposed faces were fabricated by the hydrothermal method using TiN as precursor in the presence of HF and HCl. The samples were characterized by scanning electron microscopy,X-ray diffraction,N2 adsorption,X-ray photoelectron spectroscopy,UV-visible spectroscopy,and electrochemical impedance spectroscopy. Their photocatalytic activity was evaluated using the photocatalytic reduction of CO2. The N-doped TiO 2 sample exhibited a much higher visible light photocatalytic activity for CO2 reduction than its precursor TiN and commercial TiO 2（P25）. This was due to the synergistic effect of the formation of surface heterojunctions on the TiO 2 microsheet surface,enhanced visible light absorption by nitrogen-doping,and surface fluorination.

Kinetics of CO_2 reduction in KOH/methanol electrolyte on Pb electrode

The electrochemical reduction of CO2 on a Pb electrode was investigated in 0. 1 mol/L KOH/methanol electrolyte at different temperatures and pressures. A graphite electrode was employed as the counter electrode, and an AglAgCl （sat. KCl） electrode was used as the reference electrode. The Tafel plots of the products by the electrochemical reduction of CO2 showed that the formation process of HCOOH differed from that of CO and the reduction of CO2was not limited by the diffusion of CO2 in the investigated potential range. Kinetic analysis indicated that the reaction orders were 0. 573 for electrochemical reduction of CO2 to CO and 0. 671 for CO2 to HCOOH in the cathodic direction.

Photoelectrocatalytic reduction of CO_2 into formic acid using WO_(3-x)/TiO_2 film as novel photoanode

A novel WO3-x/TiO2 film as photoanode was synthesized for photoelectrocatalytic（PEC） reduction of CO2 into formic acid（HCOOH）. The films prepared by doctor blade method were characterized with X-ray diffractometer（XRD）, scanning electron microscope（SEM） and transmission electron microscope（TEM）. The existence of oxygen vacancies in the WO3-x was confirmed with an X-ray photoelectron spectroscopy（XPS）, and the accurate oxygen index was determined by a modified potentiometric titrimetry method. After 3h of photoelectrocatalytic reduction, the formic acid yield of the WO3-x/TiO2 film is 872 nmol/cm^2, which is 1.83 times that of the WO3/TiO2 film. The results of PEC performance demonstrate that the introduction of WO3-x nanoparticles can improve the charge transfer performance so as to enhance the performance of PEC reduction of CO2 into formic acid.

Electroactive species study in the electrochemical reduction of CO_2 in KHCO_3 solution at elevated temperature

Photoelectrochemical and electrochemical reduction of CO_2 into organic chemicals is promising for directly or indirectly transforming solar energy into chemical energy for further utilization. However,research on the electroactive species in these processes has been rather limited. In this work, we investigated possible electroactive species(CO_2 or HCO_3~– ) involved in the electrochemical reduction of KHCO_3 at elevated temperatures without CO_2 bubbling. The results showed that CO, CH_4, and C_2H_4 were produced after electrochemical reduction of 3.0 mol/L KHCO_3 at elevated temperature on a Cu electrode even without CO_2 bubbling, although their faradaic efficiencies were low(< 6 %). Measurements for CO_2 generation from the decomposition of HCO_3~– showed that elevated temperature and high HCO_3~– concentration strongly promoted this process. These results suggested that the in-situ produced CO_2 from the decomposition of HCO_3~– was probably the electroactive species in the electrochemical reduction of HCO_3~– without CO_2 bubbling. Changes of the Gibbs free energy, rate constant, and activation energy of the decomposition of HCO_3~– into CO_2 were also investigated and calculated from the experimental data.

Optimal Simulation of Distributed Generation System for CO_2-Reduction in Supermarket and Restaurant

After the great east Japan earthquake in 2011, Japanese energy system has been expected to prioritize safety and trustworthiness. Now, distributed power systems are considered as one solution, but utilizing exhaust heat is an important task to be solved. The purpose of this study is to build a simulation model to harness waste heat of commercial buildings. We obtained two types of data： distributed power system in 1/15 scale model of supermarket, restaurant and real world energy consumption of the two buildings. Results showed cold cabinets, whose electricity was affected by temperatures outside and inside, consumed most in supermarket. While air conditioning, affected by air enthalpy of outside and inside, consumed most in restaurant. According to our simulation with gas engine, PV （photovoltaic） panel, PCM （phase change material）, thermal storage, FCU （fan coil unit） and refrigerated cabinets in scale model, we could reduce 27% of CO_2 emission and 25% of running cost by selecting optimal size.

Photoreduction of CO_2 to methanol over Bi_2S_3/CdS photocatalyst under visible light irradiation

The Bi2S3,CdS and Bi2S3/CdS photocatalysts were prepared by direct reactions between their corresponding salt and thiourea in a hy- drothermal autoclave.The photocatalytic activities of these photocatalysts for reducing CO2 to CH3OH under visible light irradiation have been investigated.The results show that the photocatalytic activity and visible light response of Bi2S3 are higher than those of CdS.The Bi2S3 modification can enhance the photocatalytic activity and visible light response of CdS.The photocatalytic activity of Bi2S3/CdS hetero-junction photocatalyst was the highest and the highest yields of methanol was 613μmol/g when the weight proportion of Bi2S3 to CdS was 15%,which was about three times as large as that of CdS or two times of that of Bi2S3.

Chemical Reduction of CO_2 to Different Products during Photo Catalytic Reaction on TiO_2 under Diverse Conditions:an Overview

The chemical reduction of CO2 remains a challenge with respect to the reversal of the oxidative degradation of any organic materials. The conversion of CO2 into useful substances is essential in developing alternative fuels and various raw materials for different industries. This also aids in preventing the continuous rise in tropospheric temperature due to the green house effect of CO2. In this article an overview of the growth taken place so far in the field of CO2 chemical reduction is pre- sented. The discussion comprises of photochemical methods for the development of different products, viz. CO, CH3OH and CH4, through chemical reduction of CO2. This includes the use of photo catalysts, mainly TiO2, and the role of a hole scavenger （such as 2-propanol） for this purpose.

Hierarchically nanostructured porous TiO_2(B) with superior photocatalytic CO_2 reduction activity

Hierarchically nanostructured, porous TiO_2(B) microspheres were synthesized by a microwave-assisted solvothermal method combined with subsequent heat treatment in air. The materials were carefully characterized by scanning and transmission electron microscopy, X-ray diffraction, CO_2 adsorption, and a range of spectroscopies, including Raman, infrared, X-ray photoelectron and UV-Vis spectroscopy. The hierarchical TiO_2(B) particles are constructed by ultrathin nanosheets and possess large specific surface area, which provided many active sites for CO_2 adsorption as well as CO_2 conversion. The TiO_2(B)nanostructures exhibited marked photocatalytic activity for CO_2 reduction to methane and methanol. Anatase TiO_2 and P25 were used as the reference photocatalysts. Transient photocurrent measurement also proved the higher photoactivity of TiO_2(B) than that of anatase TiO_2. In-situ infrared spectrum was measured to identify the intermediates and deduce the conversion process of CO_2 under illumination over TiO_2(B) photocatalyst.

Electrochemical reduction of CO_2 in solid oxide electrolysis cells

The effort on electrochemical reduction of COto useful chemicals using the renewable energy to drive the process is growing fast recently. In this review, we introduce the recent progresses on the electrochemical reduction of COin solid oxide electrolysis cells（SOECs）. At high temperature, only CO is produced with high current densities and Faradic efficiency while the reactor is complicated and a better sealing technique is urgently needed. The typical electrolytes such as zirconia-based oxides, ceria-based oxides and lanthanum gallates-based oxides, anodes and cathodes are introduced in this review, and the cathode materials, such as conventional metal–ceramics（cermets）, mixed ionic and electronic conductors（MIECs） are discussed in detail. In the future, to gain more value-added products, the electrolyte, cathode and anode materials should be developed to allow SOECs to be operated at temperature range of 573–873 K. At those temperatures, SOECs may combine the advantages of the low temperature system and the high temperature system to produce various products with high current densities.

Experimental and Modeling Study on de-NO_x Characteristics of Selective Non-catalytic Reduction in O_2/CO_2 Atmosphere

An experimental study of thermal de-NOx using NH3 as reductant in 02/C02 atmosphere with the effect of S02 and different additives was performed in a drop tube furnace. Results show that the optimum temperature win- dow is 841-1184 ℃, and the optimum reaction temperature is about 900 ℃ with a de-NOx efficiency of 95.4%. A certain amount of S02 has an inhibiting effect on NO reduction. The effect of additives, including Na2C03, C2H5OH and FeCI3, on NO reduction by NH3 is also explored. The addition of Na2CO3 and FeCI3 is useful to widen the tem- perature window and shift the reaction to lower temperature for the efficiency is increased from 30.5% to 74.0% and 67.4% respectively at 800 ℃. Qualitatively, the modeling results using a detailed kinetic modeling mecha- nism represent well most of the process features. The effect of Na2CO3, C2H5OH and FeCI3 addition can be reproduced well by the Na2C03, C2H5OH and Fe（CO）5 sub-mechanism respectively. The reaction mechanism analysis shows that the effects of these additives on NO reduction are achieved mainly by promoting the produc- tion of OH radicals at lower temperature.

Effect of Ni^(+2)-substituted Fe_2TiO_5 on the H_2-reduction and CO_2 Catalytic Decomposition Reactions at 500℃

CO2 is a major component of the greenhouse gases, which causes the global warming. To reduce CO2 gas, high activity nanosized Ni＋2 substituted Fe2TiO5 samples were synthesized by conventional ceramic method. The effect of the composition of the synthesized ferrite on the H2-reduction and CO2-catalytic decomposition was investigated. Fe2TiO5 （iron titanate） phase that has a nanocrystallite size of -80 nm is formed as a result of heating Fe2O3 and TiO2 while the addition of NiO leads to the formation of new phases （-80 nm） NiTiO3 and NiFe2O4, but the mixed solid of NiO and Fe2O3 results in the formation of NiFe2O4 only. Samples with Ni^＋2=0 shows the lowest reduction extent （20%）; as the extent of Ni＋2 increases, the extent of reduction increases. The increase in the reduction percent is attributed to the presence of NiTiO3 and NiFe2O4 phases, which are more reducible phases than Fe2TiO5. The CO2 decomposition reactions were monitored by thermogravimetric analysis （TGA） experiments. The oxidation of the H2-reduced Ni＋2 substituted Fe2TiO5 at 500℃ was investigated. As Ni^＋2 increases, the rate of reoxidation increases. Samples with the highest reduction extents gave the highest reoxidation extent, which is attributed to the highly porous nature and deficiency in oxygen due to the presence of metallic Fe, Ni and/or FeNi alloy. X-ray diffraction （XRD） and transmission electron microscopy （TEM） of oxidized samples show also the presence of carbon in the sample containing Ni＋2〉0, which appears in the form of nanotubes （25 nm）.

Highly efficient photocatalytic reduction of CO_2 and H_2O to CO and H_2 with a cobalt bipyridyl complex

The development of efficient molecular catalysts for visible-light driven CO2 reduction, based on abundant materials, is necessary to meet energy demands and address environment problems. In this work,a Co（bpy）2Cl2 catalyst was developed and showed high efficiency and durability for the photocatalytic reduction of CO2 and protons. Yields of CO and H2 as high as 62.3 and 69.9 μmol were achieved and the turnover numbers（TONs） reached 6230 and 6990, respectively, under light irradiation（λ 〉 420 nm）for 4 h, indicating that the mixture gases could be a candidate as syngas. The apparent quantum yield was determined to be 2.1% for CO. Mechanistic studies revealed oxidative quenching of the photosensitizer Ru（bpy）3Cl2 by the catalyst. The photocatalytic performance, flexible synthesis and non-noble metal catalyst in our system show great promise for the practical application of Co（bpy）2Cl2 to photocatalytic reduction of CO2.

Understanding Bridging Sites and Accelerating Quantum Efficiency for Photocatalytic CO_(2) Reduction

We report a novel double-shelled nanoboxes photocatalyst architecture with tailored interfaces that accelerate quantum efficiency for photocatalytic CO_(2) reduction reaction(CO_(2)RR)via Mo–S bridging bonds sites in S_(v)–In_(2)S_(3)@2H–MoTe_(2).The X-ray absorption near-edge structure shows that the formation of S_(v)–In_(2)S_(3)@2H–MoTe_(2) adjusts the coordination environment via interface engineering and forms Mo–S polarized sites at the interface.The interfacial dynamics and catalytic behavior are clearly revealed by ultrafast femtosecond transient absorption,time-resolved,and in situ diffuse reflectance–Infrared Fourier transform spectroscopy.A tunable electronic structure through steric interaction of Mo–S bridging bonds induces a 1.7-fold enhancement in S_(v)–In_(2)S_(3)@2H–MoTe_(2)(5)photogenerated carrier concentration relative to pristine S_(v)–In_(2)S_(3).Benefiting from lower carrier transport activation energy,an internal quantum efficiency of 94.01%at 380 nm was used for photocatalytic CO_(2)RR.This study proposes a new strategy to design photocatalyst through bridging sites to adjust the selectivity of photocatalytic CO_(2)RR.

Cu-Based Materials for Enhanced C_(2+) Product Selectivity in Photo-/Electro-Catalytic CO_(2) Reduction: Challenges and Prospects

Carbon dioxide conversion into valuable products using photocatalysis and electrocatalysis is an effective approach to mitigate global environmental issues and the energy shortages. Among the materials utilized for catalytic reduction of CO_(2), Cu-based materials are highly advantageous owing to their widespread availability, cost-effectiveness, and environmental sustainability. Furthermore, Cu-based materials demonstrate interesting abilities in the adsorption and activation of carbon dioxide, allowing the formation of C_(2+) compounds through C–C coupling process. Herein, the basic principles of photocatalytic CO_(2) reduction reactions(PCO_(2)RR) and electrocatalytic CO_(2) reduction reaction(ECO_(2)RR) and the pathways for the generation C_(2+) products are introduced. This review categorizes Cu-based materials into different groups including Cu metal, Cu oxides, Cu alloys, and Cu SACs, Cu heterojunctions based on their catalytic applications. The relationship between the Cu surfaces and their efficiency in both PCO_(2)RR and ECO_(2)RR is emphasized. Through a review of recent studies on PCO_(2)RR and ECO_(2)RR using Cu-based catalysts, the focus is on understanding the underlying reasons for the enhanced selectivity toward C_(2+) products. Finally, the opportunities and challenges associated with Cu-based materials in the CO_(2) catalytic reduction applications are presented, along with research directions that can guide for the design of highly active and selective Cu-based materials for CO_(2) reduction processes in the future.

Mechanism study of reduction of CO_2 into formic acid by in-situ hydrogen produced from water splitting with Zn: Zn/ZnO interface autocatalytic role

We have previously developed a new process of highly efficient conversion of COand water into formic acid with metallic Zn without the addition of catalyst, however, its mechanism is not clear, particularly in the catalytic role of Zn/ZnO interface. Herein, the autocatalytic role of Zn/ZnO interface formed in situ during the reduction of COinto formic acid with Zn in water was studied by combining high resolution transmission electron microscopy（HRTEM）, X-ray diffraction（XRD） and X-ray photoelectron spectroscopy（XPS） techniques and experimental data. The electron microscope results show that possible defects or dislocations formed on Zn/ZnO interface, in which plays a key role for Zn H-formation. Further XPS analyses indicate that oxygen vacancies on Zn/ZnO interface increased at short reaction times（less than 10 min）. These analyses and experimental results suggest that a highly efficient and rapid conversion of COand water into formic acid should involve an autocatalytic role of the Zn/ZnO interface formed in situ, particularly at the beginning of the reaction.

Engineering of oxygen vacancy and bismuth cluster assisted ultrathin Bi_(12)O_(17)Cl_(2)nanosheets with efficient and selective photoreduction of CO_(2)to CO

The photocatalytic conversion of CO_(2)into solar‐powered fuels is viewed as a forward‐looking strategy to address energy scarcity and global warming.This work demonstrated the selective photoreduction of CO_(2)to CO using ultrathin Bi_(12)O_(17)Cl_(2)nanosheets decorated with hydrothermally synthesized bismuth clusters and oxygen vacancies(OVs).The characterizations revealed that the coexistences of OVs and Bi clusters generated in situ contributed to the high efficiency of CO_(2)–CO conversion(64.3μmol g^(−1)h^(−1))and perfect selectivity.The OVs on the facet(001)of the ultrathin Bi_(12)O_(17)Cl_(2)nanosheets serve as sites for CO_(2)adsorption and activation sites,capturing photoexcited electrons and prolonging light absorption due to defect states.In addition,the Bi‐cluster generated in situ offers the ability to trap holes and the surface plasmonic resonance effect.This study offers great potential for the construction of semiconductor hybrids as multiphotocatalysts,capable of being used for the elimination and conversion of CO_(2)in terms of energy and environment.

The Emission Reduction Potential of Non-CO_2 Greenhouse Gases in China and Its Policy Implications

Using the improved Energy-Environmental Version of the GTAP Model (GTAP-E) and the sixth version of emission database of non-CO2 greenhouse gases, we simulate the emission reduction potential of non-CO2 greenhouse gases in China and its policy implications. The results show that at present, China is a country with the greatest emission of non-CO2 greenhouse gases in the world, and the emission will account for about 20% of the world's total emission in 2020. The proportion of emission of non-CO2 greenhouse gases from the agricultural sector reaches 73%. In the next 10 years, the emission of non-CO2 gases from cattle and sheep, industry and service industry will experience the highest growth rate; the growth rate of emission from service industry will be higher than that of emission from industry, and the emission from service industry will exceed that from industry after 2010. China can implement emission reduction policy of non-CO2 greenhouse gases to ease the international pressure of CO2 emission reduction. Although the high carbon tax collected can reduce considerable non-CO2 emission, there is little difference in policy efficiency between high carbon tax and low carbon tax. So, in the implementation of emission reduction carbon tax policy of non-CO2 gases, it is necessary to control the carbon tax at a low level.

Single-atom catalysts for the electrochemical reduction of carbon dioxide into hydrocarbons and oxygenates

The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.

Porous metal oxides in the role of electrochemical CO_(2) reduction reaction

The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.

Surface engineering of ZnO electrocatalyst by N doping towards electrochemical CO_(2) reduction

The discovery of efficient,selective,and stable electrocatalysts can be a key point to produce the largescale chemical fuels via electrochemical CO_(2) reduction(ECR).In this study,an earth-abundant and nontoxic ZnO-based electrocatalyst was developed for use in gas-diffusion electrodes(GDE),and the effect of nitrogen(N)doping on the ECR activity of ZnO electrocatalysts was investigated.Initially,a ZnO nanosheet was prepared via the hydrothermal method,and nitridation was performed at different times to control the N-doping content.With an increase in the N-doping content,the morphological properties of the nanosheet changed significantly,namely,the 2D nanosheets transformed into irregularly shaped nanoparticles.Furthermore,the ECR performance of Zn O electrocatalysts with different N-doping content was assessed in 1.0 M KHCO_(3) electrolyte using a gas-diffusion electrode-based ECR cell.While the ECR activity increased after a small amount of N doping,it decreased for higher N doping content.Among them,the N:ZnO-1 h electrocatalysts showed the best CO selectivity,with a faradaic efficiency(FE_(CO))of 92.7%at-0.73 V vs.reversible hydrogen electrode(RHE),which was greater than that of an undoped Zn O electrocatalyst(FE_(CO)of 63.4%at-0.78 V_(RHE)).Also,the N:ZnO-1 h electrocatalyst exhibited outstanding durability for 16 h,with a partial current density of-92.1 mA cm^(-2).This improvement of N:ZnO-1 h electrocatalyst can be explained by density functional theory calculations,demonstrating that this improvement of N:ZnO-1 h electrocatalyst comes from(ⅰ)the optimized active sites lowering the free energy barrier for the rate-determining step(RDS),and(ⅱ)the modification of electronic structure enhancing the electron transfer rate by N doping.