The synergy of single atoms(SAs)and nanoparticles(NPs)has demonstrated great potential in promoting the electrocatalytic carbon dioxide reduction reaction(CO_(2)RR);however,the rationalization of the SAs/NPs proportio...The synergy of single atoms(SAs)and nanoparticles(NPs)has demonstrated great potential in promoting the electrocatalytic carbon dioxide reduction reaction(CO_(2)RR);however,the rationalization of the SAs/NPs proportion remains one challenge for the catalyst design.Herein,a Ni2+-loaded porous poly(ionic liquids)(PIL)precursor synthesized through the free radical self-polymerization of the ionic liquid monomer,1-allyl-3-vinylimidazolium chloride,was pyrolyzed to prepare the Ni,N co-doped carbon materials,in which the proportion of Ni SAs and NPs could be facilely modulated by controlling the annealing temperature.The catalyst Ni-NC-1000 with a moderate proportion of Ni SAs and NPs exhibited high efficiency in the electrocatalytic conversion of CO_(2)into CO.Operando Ni K-edge X-ray absorption near-edge structure(XANES)spectra and theoretical calculations were conducted to gain insight into the synergy of Ni SAs and NPs.The charge transfer from Ni NPs to the surrounding carbon layer and then to the Ni SAs resulted in the electron-enriched Ni SAs active sites.In the electroreduction of CO_(2),the coexistence of Ni SAs and NPs strengthened the CO_(2)activation and the affinity towards the key intermediate of*COOH,lowering the free energy for the potential-determining*CO_(2)→*COOH step,and therefore promoted the catalysis efficiency.展开更多
The solar-driven catalytic conversion of CO2 to useful chemical fuels is regarded as an environmentally friendly approach to reduce the consumption of fossil fuels and mitigate the greenhouse effect.However,it is high...The solar-driven catalytic conversion of CO2 to useful chemical fuels is regarded as an environmentally friendly approach to reduce the consumption of fossil fuels and mitigate the greenhouse effect.However,it is highly intriguing and challenging to promote the selectivity and efficiency of visible-light-responsive photocatalysts that favor the adsorption of CO2 in photoreduction processes.In this work,three-dimensional hierarchical Cd0.8Zn0.2S flowers(C8Z2S-F)with ultrathin petals were successfully synthesized through an in-situ self-assembly growth process using sodium citrate as a morphology director.The flower-like Cd0.8Zn0.2S solid solution exhibited remarkable photocatalytic performance in the reduction of CO2,generating CO up to 41.4μmol g^−1 under visible-light illumination for 3 h;this was nearly three times greater than that of Cd0.8Zn0.2S nanoparticles(C8Z2S-NP)(14.7μmol g^−1).Particularly,a comparably high selectivity of 89.9%for the conversion of CO2 to CO,with a turnover number of 39.6,was obtained from the solar-driven C8Z2S-F system in the absence of any co-catalyst or sacrificial agent.Terahertz time-domain spectroscopy indicated that the introduction of flower structures enhanced the light-harvesting capacity of C8Z2S-F.The in situ diffuse reflectance infrared Fourier transform spectroscopy unveiled the existence of surface-adsorbed species and the conversion of photoreduction intermediates during the photocatalytic process.Empirical characterizations and predictions of the photocatalytic mechanism demonstrated that the flower-like Cd0.8Zn0.2S solid solution possessed desirable CO2 adsorption properties and an enhanced charge-transfer capability,thus providing a highly effective photocatalytic reduction of CO2.展开更多
Herein,we prepa red novel three-dimensional(3D)gear-s haped Co3O4@C(Co3O4 modified by amorphous carbon)and sheet-like SnO2/CC(SnO2 grow on the carbon cloth)as anode and cathode to achieve efficient removal of 4-nitrop...Herein,we prepa red novel three-dimensional(3D)gear-s haped Co3O4@C(Co3O4 modified by amorphous carbon)and sheet-like SnO2/CC(SnO2 grow on the carbon cloth)as anode and cathode to achieve efficient removal of 4-nitrophenol(4-NP)in the presence of peroxymonosulfate(PMS)and simultaneous electrocatalytic reduction of CO2,respectively.In this process,4-NP was mineralized into CO2 by the Co3O4@C,and the generated CO2 was reduced into HCOOH by the sheet-like SnO2/CC cathode.Compared with the pure Co0.5(Co3O4 was prepared using 0.5 g urea)with PMS(30 mg,0.5 g/L),the degradation efficiency of 4-NP(60 mL,10 mg/L)increased from 74.5%-85.1%in 60 min using the Co0.5 modified by amorphous carbon(Co0.5@C).Furthermore,when the voltage of 1.0 V was added in the anodic system of Co0.5@C with PMS(30 mg,0.5 g/L),the degradation efficiency of 4-NP increased from 85.1%-99.1%when Pt was used as cathode.In the experiments of 4-NP degradation coupled with simultaneous electrocatalytic CO2 reduction,the degradation efficiency of 4-NP was 99.0%in the anodic system of Co0.5@C with addition of PMS(30 mg,0.5 g/L),while the Faraday efficiency(FE)of HCOOH was 24.1%at voltage of-1.3 V using the SnO2/CC as cathode.The results showed that the anode of Co3O4 modified by amorphous carbon can markedly improve the degradation efficiency of 4-NP,while the cathode of SnO2/CC can greatly improve the FE and selectivity of CO2 reduction to HCOOH and the stability of cathode.Finally,the promotion mechanism was proposed to explain the degradation of organic pollutants and reduction of CO2 into HCOOH in the process of electrocatalysis coupled with advanced oxidation processes(AOPs)and simultaneous CO2 reduction.展开更多
Electrocatalytic carbon dioxide(CO2)reduction(ECR)has become one of the main methods to close the broken carbon cycle and temporarily store renewable energy,but there are still some problems such as poor stability,low...Electrocatalytic carbon dioxide(CO2)reduction(ECR)has become one of the main methods to close the broken carbon cycle and temporarily store renewable energy,but there are still some problems such as poor stability,low activity,and selectivity.While the most promising strategy to improve ECR activity is to develop electrocatalysts with low cost,high activity,and long-term stability.Recently,defective carbon-based nanomaterials have attracted extensive attention due to the unbalanced electron distribution and electronic structural distortion caused by the defects on the carbon materials.Here,the present review mainly summarizes the latest research progress of the construction of the diverse types of defects(intrinsic carbon defects,heteroatom doping defects,metal atomic sites,and edges detects)for carbon materials in ECR,and unveil the structure-activity relationship and its catalytic mechanism.The current challenges and opportunities faced by high-performance carbon materials in ECR are discussed,as well as possible future solutions.It can be believed that this review can provide some inspiration for the future of development of high-performance ECR catalysts.展开更多
Highly efficient photocatalytic reduction of CO2 is essential for solving the greenhouse effect and energy crisis.In this paper,the Sm-TiO2 nanocomposites were successfully prepared via sol-gel method.The CO2 photored...Highly efficient photocatalytic reduction of CO2 is essential for solving the greenhouse effect and energy crisis.In this paper,the Sm-TiO2 nanocomposites were successfully prepared via sol-gel method.The CO2 photoreduction activities of synthesized samples were tested under irradiation for 6 h and the results indicate that the 0.5% Sm-TiO2 catalyst has superior performance and stability.The CO and CH4 yields of0.5% Sm-TiO2 catalyst are 55.47 and 3.82 μmol/g·cat respectively,which are 5.02 and 2.67 times the yield of TiO2.The possible mechanism of Sm doped TiO2 was investigated through comprehensive characterization and photoetectrochemical analysis,After the Sm doping,the photo-generated electrons in TiO2 could migrate to Sm 4 f,and some of them can be captured by reducing Sm3+ o Sm2+,which can lower the recombination rate of electron and hole pairs.Therefore,the enhanced photocatalytic performance could be ascribed to large specific surface area,fast separation rate of electron-hole pairs and high visible light response.This report provides some meaningful attempts in researching the CO2 photocatalytic reduction.展开更多
Photoelectrocatalytic reduction of CO2 to fuels has great potential for reducing anthropogenic CO2 emissions and also lessening our dependence on fossil fuel energy.Herein,we report the successful development of a nov...Photoelectrocatalytic reduction of CO2 to fuels has great potential for reducing anthropogenic CO2 emissions and also lessening our dependence on fossil fuel energy.Herein,we report the successful development of a novel photoelectrocatalytic catalyst for the selective reduction of CO2 to methanol,comprising a copper catalyst modified with flower-like cerium oxide nanoparticles(CeO2 NPs)(a n-type semiconductor)and copper oxide nanoparticles(CuO NPs)(a p-type semiconductor).At an applied potential of−1.0 V(vs SCE)under visible light irradiation,the CeO2 NPs/CuO NPs/Cu catalyst yielded methanol at a rate of 3.44μmol cm^−2 h^−1,which was approximately five times higher than that of a CuO NPs/Cu catalyst(0.67μmol cm^−2 h^−1).The carrier concentration increased by^108 times when the flower-like CeO2 NPs were deposited on the CuO NPs/Cu catalyst,due to synergistic transfer of photoexcited electrons from the conduction band of CuO to that of CeO2,which enhanced both photocatalytic and photoelectrocatalytic CO2 reduction on the CeO2 NPs.The facile migration of photoexcited electrons and holes across the p–n heterojunction that formed between the CeO2 and CuO components was thus critical to excellent light-induced CO2 reduction properties of the CeO2 NPs/CuO NPs/Cu catalyst.Results encourage the wider application of composite semiconductor electrodes in carbon dioxide reduction.展开更多
The electrochemical reduction of CO2(CO2 RR) can substantially contribute to the production of useful chemicals and reduction of global CO2 emissions. Herein, we presented N and S dual-doped high-surface-area carbon m...The electrochemical reduction of CO2(CO2 RR) can substantially contribute to the production of useful chemicals and reduction of global CO2 emissions. Herein, we presented N and S dual-doped high-surface-area carbon materials(SZ-HCN) as CO2 RR catalysts. N and S were doped by one-step pyrolysis of a N-containing polymer and S powder. ZnCl2 was applied as a volatile porogen to prepare porous SZ-HCN. SZ-HCN with a high specific surface area(1510 m2 g–1) exhibited efficient electrocatalytic activity and selectivity for CO2 RR. Electrochemical measurements demonstrated that SZ-HCN showed excellent catalytic performance for CO2-to-CO reduction with a high CO Faradaic efficiency(~93%) at-0.6 V. Furthermore, SZ-HCN offered a stable current density and high CO selectivity over at least 20 h continuous operation, revealing remarkable electrocatalytic durability. The experimental results and density functional theory calculations indicated that N and S dual-doped carbon materials required lower Gibbs free energy to form the COOH* intermediate than that for single-N-doped carbon for CO2-to-CO reduction, thereby enhancing CO2 RR activity.展开更多
Photocatalytic reduction of CO2 with H2 O to syngas is an effective way for producing high value-added chemical feedstocks such as methanol and light olefins in industry.Nevertheless,the precise control of CO/H2 ratio...Photocatalytic reduction of CO2 with H2 O to syngas is an effective way for producing high value-added chemical feedstocks such as methanol and light olefins in industry.Nevertheless,the precise control of CO/H2 ratio from photocatalytic CO2 reduction reaction still poses a great challenge for the further application.Herein,we prepared a series of highly efficient heterostructure based on highly dispersed palladium supported on ultrathin Co Al-layered double hydroxide(LDH).In conjunction with a Ru-complex sensitizer,the molar ratios of CO/H2 can be tuned from 1:0.74 to 1:3 under visible-light irradiation(λ>400 nm).More interestingly,the syngas can be obtained under light irradiation atλ>600 nm.Structure characterization and density functional theory calculations revealed that the remarkable catalytic activity can be due to the supported palladium,which improved the charge transfer efficiency.Meanwhile,more H atoms were used to generate H2 on the supported palladium for further tunable CO/H2 ratio.This work demonstrates a new strategy for harnessing abundant solar-energy to produce syngas from a CO2 feedstock.展开更多
Cobalt-based oxides,with high abundance,good stability and excellent catalytic performance,are regarded as promising photocatalysts for artificial photosynthetic systems to alleviate foreseeable energy shortages and g...Cobalt-based oxides,with high abundance,good stability and excellent catalytic performance,are regarded as promising photocatalysts for artificial photosynthetic systems to alleviate foreseeable energy shortages and global warming.Herein,for the first time,a series of novel spongy porous CDs@CoOx materials were synthesized to act as an efficient and stable bifunctional photocatalyst for water oxidation and CO2 reduction.Notably,the preparation temperatures visibly influence the morphologies and photocatalytic performances of the CDs@CoOx.Under the optimal conditions,a maximum O2 yield of 40.4% and pretty apparent quantum efficiency(AQE)of 58.6% at 460 nm were obtained over CDs@CoOx-300 for water oxidation.Similarly,the optimized sample CDs@CoOx-300 manifests significant enhancement on the CO2-to-CO conversion with a high selectivity of 89.3% and CO generation rate of 8.1μmol/h,which is superior to most previous cobalt-based catalysts for CO2 reduction.The composite CDs@CoOx-300 not only exposes more active sites but also facilitates electron transport,which results in excellent photocatalytic activity.In addition,the boosted photocatalytic behavior is attributed to the synergistic effect between CoOx and CDs,which was verified by the photocatalytic activity control experiments and electrochemical characterization.The work offers a novel strategy to fabricate a high performance bifunctional photocatalyst for water oxidation and CO2 reduction.展开更多
In terms of the reaction of COreduction to CO with hydrogen, COconversion is very low at low temperature due to the limitation of thermodynamic equilibrium（TE）. To overcome this limitation, plasma catalytic reductio...In terms of the reaction of COreduction to CO with hydrogen, COconversion is very low at low temperature due to the limitation of thermodynamic equilibrium（TE）. To overcome this limitation, plasma catalytic reduction of COto CO in a catalyst-filled dielectric barrier discharge（DBD） reactor is studied. An enhanced effect of plasma on the reaction over Au/CeOcatalysts is observed. For both the conventionally catalytic（CC） and plasma catalytic（PC, Pin= 15 W） reactions under conditions of 400 °C, H/CO= 1,200 SCCM, GHSV = 12,000 mL·gcat·h, COconversions over Au/CeOreach 15.4% and 25.5% due to the presence of Au, respectively, however, those over CeOare extremely low and negligible. Moreover,COconversion over Au/CeOin the PC reaction exceeds 22.4% of the TE conversion. Surface intermediate species formed on the catalyst samples during the reactions are determined by in-situ temperatureprogrammed decomposition（TPD） technique. Interestingly, it disclosed that in the PC reaction, the formation of formate intermediate is enhanced by plasma, and the acceleration by plasma in the decomposition of formate species is much greater than that in the formation of formate species on Au/CeO. Enhancement factor is introduced to quantify the enhanced effect of plasma. Lower reactor temperature, higher gas hourly space velocity（GHSV）, and lower molar ratio of H/COwould be associated with larger enhancement factor.展开更多
Zero or negative emissions of carbon dioxide(CO2)is the need of the times,as inexorable rising and alarming levels of CO2 in the atmosphere lead to global warming and severe climate change.The electrochemical CO2 redu...Zero or negative emissions of carbon dioxide(CO2)is the need of the times,as inexorable rising and alarming levels of CO2 in the atmosphere lead to global warming and severe climate change.The electrochemical CO2 reduction(eCO2R)to value‐added fuels and chemicals by using renewable electricity provides a cleaner and more sustainable route with economic benefits,in which the key is to develop clean and economical electrocatalysts.Carbon‐based catalyst materials possess desirable properties such as high offset potential for H2 evolution and chemical stability at the negative applied potential.Although it is still challenging to achieve highly efficient carbon‐based catalysts,considerable efforts have been devoted to overcoming the low selectivity,activity,and stability.Here,we summarize and discuss the recent progress in carbon‐based metal‐free catalysts including carbon nanotubes,carbon nanofibers,carbon nanoribbons,graphene,carbon nitride,and diamonds with an emphasis on their activity,product selectivity,and stability.In addition,the key challenges and future potential approaches for efficient eCO2R to low carbon‐based fuels are highlighted.For a good understanding of the whole history of the development of eCO2R,the CO2 reduction reactions,principles,and techniques including the role of electrolytes,electrochemical cell design and evaluation,product selectivity,and structural composition are also discussed.The metal/metal oxides decorated with carbon‐based electrocatalysts are also summarized.We aim to provide insights for further development of carbon‐based metal‐free electrocatalysts for CO2 reduction from the perspective of both fundamental understanding and technological applications in the future.展开更多
Preciously tuning the surface composition of noble metal nanoparticles with the particle size of only 2 nm or less by alloying with other metals represents a powerful strategy to boost their electrocatalytic selectivi...Preciously tuning the surface composition of noble metal nanoparticles with the particle size of only 2 nm or less by alloying with other metals represents a powerful strategy to boost their electrocatalytic selectivity.However,the synthesis of ultrafine nanoalloys and tuning their surface composition remain challenging.In this report,ultrafine CuPd nanoalloys with the particle size of ca.2 nm are synthesized based on the galvanic replacement reaction between presynthesized Cu nanoparticles and Pd2+precursors,and the tuning of their surface compositions is also achieved by changing the atom ratios of Cu/Pd.For the electrocatalytic reduction of CO2,Cu5Pd5 nanoalloys show the CO Faradaic efficiency(FE)of 88%at−0.87 V,and the corresponding mass activity reaches 56 A/g that is much higher than those of Cu8Pd2 nanoalloys,Cu3Pd7 nanoalloys and most of previously reported catalysts.Density functional theory uncovers that with the increase of Pd on the surface of the ultrafine CuPd nanoalloys,the adsorbed energy of both of intermediate COOH*and CO*to the Pd sites is strengthened.The Cu5Pd5 nanoalloys with the optimal surface composition better balance the adsorption of COOH*and desorption of CO*,achieving the highest selectivity and activity.The difficult liberation of absorbed CO*on the surface of Cu3Pd7 nanoalloys provides carbon source to favor the production of ethylene,endowing the Cu3Pd7 nanoalloys with the highest selectivity for ethylene among these ultrafine CuPd nanoalloys.展开更多
Crystalline TiO（P25） and isolated titanate species in a ZSM-5 structure（TS-1） were modified with Au and Ag, respectively, and tested in the gas-phase photocatalytic COreduction under high purity conditions. The no...Crystalline TiO（P25） and isolated titanate species in a ZSM-5 structure（TS-1） were modified with Au and Ag, respectively, and tested in the gas-phase photocatalytic COreduction under high purity conditions. The noble metal modification was performed by photodeposition. Light absorbance properties of the catalysts are examined with UV–Vis spectroscopy before and after the activity test. In the gas-phase photocatalytic COreduction, it was observed that the catalysts with Ag nanostructures are more active than those with Au nanostructures. It is thus found that the energetic difference between the band gap energy of the semiconductor and the position of the plasmon is influencing the photocatalytic activity.Potentially, plasmon excitation due to visible light absorption results in plasmon resonance energy, which affects the excitation of the semiconductor positively. Therefore, an overlap between band gap energy of the semiconductor and metal plasmon is needed.展开更多
Photocatalytic H2 production and CO2 reduction have attracted considerable attention for clean energy development.In this work,we designed an efficient photocatalyst by integrating lamellar oxygen-doped carbon nitride...Photocatalytic H2 production and CO2 reduction have attracted considerable attention for clean energy development.In this work,we designed an efficient photocatalyst by integrating lamellar oxygen-doped carbon nitride(CNO)nanosheets into ZnIn2S4(ZIS)microflowers by a one-step hydrothermal method.A well-fitted 2D hierarchical hybrid heterostructure was fabricated.Under visible light irradiation,the ZIS@CNO composite with 40 wt%CNO(ZC 40%)showed the highest hydrogen evolution rate from water(188.4μmol·h-1),which was approximately 2.1 times higher than those of CNO and ZIS(88.6 and 90.2μmol·h-1,respectively).Furthermore,the selective CO production rates of ZC 40%(12.69μmol·h-1)were 2.2 and 14.0 times higher than those of ZIS(5.85μmol·h-1)and CNO(0.91μmol·h-1),respectively,and the CH4 production rate of ZC 40%was 1.18μmol·h-1.This enhanced photocatalytic activity of CNO@ZIS is due mainly to the formation of a heterostructure that can promote the transfer of photoinduced electrons and holes between CNO and ZIS,thereby efficiently avoiding recombination of electron-hole pairs.展开更多
Converting carbon dioxide(CO2)into value-added chemicals by CO2 reduction has been considered as a potential way to solve the current energy crisis and environmental problem.Among the methods of CO2 reduction,the elec...Converting carbon dioxide(CO2)into value-added chemicals by CO2 reduction has been considered as a potential way to solve the current energy crisis and environmental problem.Among the methods of CO2 reduction,the electrochemical method has been widely used due to its mild reaction condition and high reaction efficiency.In the electrochemical reduction system,the CO2 electrocatalyst is the most important part.Although many CO2 electrocatalysts have been developed,efficient catalysts with high activity,selectivity and stability are still lacking.Copper sulfide compound,as a low-toxicity and emerging material,has broad prospects in the field of CO2 reduction due to its unique structural and electrochemical properties.Much progress has been achieved with copper sulfide nanocrystalline and the field is rapidly developing.This paper summarizes the preparation,recent progress in development,and factors affecting the electrocatalytic CO2 reduction performance with copper sulfide compound as a catalyst.Prospects for future development are also outlined,with the aim of using copper sulfide compound as a highly active and stable electrocatalyst for CO2 reduction.展开更多
A solar-light double illumination photoelectrocatalytic cell（SLDIPEC） was fabricated for autonomous CO2 reduction and O2 evolution with the aid of photosystem II（PS-II, an efficient light-driven water-oxidized enzy...A solar-light double illumination photoelectrocatalytic cell（SLDIPEC） was fabricated for autonomous CO2 reduction and O2 evolution with the aid of photosystem II（PS-II, an efficient light-driven water-oxidized enzyme from nature） and utilized in a photoanode solution. The proposed SLPEC system was composed of Cu foam as the photoanode and p-Si nanowires（Si-NW） as the photocathode. Under solar irradiation, it exhibited a super-photoelectrocatalytic performance for CO2 conversion to methanol, with a high evolution rate（41.94 mmol/hr）, owing to fast electron transfer from PS-II to Cu foam.Electrons were subsequently trapped by Si-NW through an external circuit via bias voltage（0.5 V）, and a suitable conduction band potential of Si（-0.6 e V） allowed CO2 to be easily reduced to CH3 OH at the photocathode. The constructed Z-scheme between Cu foam and Si-NW can allow the SLDIPEC system to reduce CO2（8.03 mmol/hr） in the absence of bias voltage. This approach makes full use of the energy band mismatch of the photoanode and photocathode to design a highly efficient device for solving environmental issues and producing clean energy.展开更多
It is desirable to develop highly efficient and sustainable catalytic systems for CO_(2) photoreduction using efficient heterogeneous photosensitizers(PSs);however,this remains a great challenge.In this study,we doped...It is desirable to develop highly efficient and sustainable catalytic systems for CO_(2) photoreduction using efficient heterogeneous photosensitizers(PSs);however,this remains a great challenge.In this study,we doped[Ru(bpy)3]^(2+) into UiO-metal-organic frameworks(MOFs)to facilitate the separation and reuse of noble metal PS.By simply adjusting the loading amount,a series of heterogeneous photoactive MOFs,namely,UiO-Ru-1,UiO-Ru-2,and UiO-Ru-3,were constructed to act as heterogeneous PSs to drive the efficient CO_(2) photoreduction under visible-light irradiation.Remarkably,UiO-Ru-2 exhibited the best photosensitizing ability among the prepared MOFs in sensitizing the iron quarterpyridine catalyst(C-l),and the CO yield reached as high as 171 mmol/g with ca.100%selectivity,which is a record value among all the MOF-based photocatalysts.This photoactive MOF can be recycled and reused three times without any obvious activity loss,signifying its good photochemical stability.Experimental investigations confirmed that the strong visible absorption,long-lived excited state,appropriate redox potential,good photocatalytic stability,and excellent collaboration with C-l were attributable to the superior catalytic activity.This work highlights an avenue for constructing heterogeneous PSs with excellent recyclability using MOF as the platform for efficient CO_(2) reduction.展开更多
Photocatalytic reduction of CO2 into various types of fuels has attracted great interest,and serves as a potential solution to addressing current global warming and energy challenges.In this work,Ag-Cu nanoparticles a...Photocatalytic reduction of CO2 into various types of fuels has attracted great interest,and serves as a potential solution to addressing current global warming and energy challenges.In this work,Ag-Cu nanoparticles are densely supported on N-doped TiO2 nanowire through a straightforward nanofabrication approach.The range of light absorption by N-doped TiO2 can be tuned to match the plasmonic band of Ag nanoparticles,which allows synergizing a resonant energy transfer process with the Schottky junction.Meanwhile,Cu nanoparticles can provide active sites for the reduction of CO2 molecules.Remarkably,the performance of photocatalytic CO2 reduction is improved to produce CH4 at a rate of 720μmol·g-1·h-1 under full-spectrum irradiation.展开更多
Converting CO2 to carbon-containing fuels is an effective approach to relieving energy shortages.Carbon quantum dots(CQDs) have shown distinct properties and attracted tremendous interest in CO2 reduction.Herein,we re...Converting CO2 to carbon-containing fuels is an effective approach to relieving energy shortages.Carbon quantum dots(CQDs) have shown distinct properties and attracted tremendous interest in CO2 reduction.Herein,we report a joint experimental-computational mechanistic study of photoreduction CO2 to CO on the model catalyst 9-hydroxyphenal-1-one(HPHN) CQDs with known structure.Our theoretical calculations reveal that the rate-determining step is COOH·formation,which is closely related to the proton and electron transfer induced by hydrogen bonding in the excited state.According to the calculated volcano plot,the solution we proposed is addition Zn^(2+) ions.The active center changed from the hydroxyl oxygen atom to the Zn atom and the barrier of the COOH·formation step is noticeably decreased when Zn^(2+) ions are added.It is further confirmed by the experimental data that the activity of CO2 reduction increases 2.9 times when Zn^(2+) ions are added.展开更多
Hydrogen evolution reaction(HER)is the major cathodic reaction which competes CO2 reduction reaction(CO2 RR)on Pt electrode.Molecular level understanding on how these two reactions interact with each other and what th...Hydrogen evolution reaction(HER)is the major cathodic reaction which competes CO2 reduction reaction(CO2 RR)on Pt electrode.Molecular level understanding on how these two reactions interact with each other and what the key factors are of CO2 RR kinetics and selectivity will be of great help in optimizing electrolysers for CO2 reduction.In this work,we report our results of hydrogen evolution and CO2 reduction on Pt(111)and Pt film electrodes in CO2 saturated acid solution by cyclic voltammetry and infrared spectroscopy.In solution with pH>2,the major process is HER and the interfacial pH increases abruptly during HER;COad is the only adsorbed intermediate detected in CO2 reduction by infrared spectroscopy;the rate for COad formation increases with the coverage of UPD-H and reaches maximum at the onset potential for HER;the decrease of COad formation under HER is attributed to the available limited sites and the limited residence time for the reduction intermediate(Had),which is necessary for CO2 adsorption and reduction.展开更多
基金National Natural Science Foundation of China(grants 22072065,22178162,and 22222806)Distinguished Youth Foundation of Jiangsu Province(grant BK20220053)Six talent peaks project in Jiangsu Province(grant JNHB-035)。
文摘The synergy of single atoms(SAs)and nanoparticles(NPs)has demonstrated great potential in promoting the electrocatalytic carbon dioxide reduction reaction(CO_(2)RR);however,the rationalization of the SAs/NPs proportion remains one challenge for the catalyst design.Herein,a Ni2+-loaded porous poly(ionic liquids)(PIL)precursor synthesized through the free radical self-polymerization of the ionic liquid monomer,1-allyl-3-vinylimidazolium chloride,was pyrolyzed to prepare the Ni,N co-doped carbon materials,in which the proportion of Ni SAs and NPs could be facilely modulated by controlling the annealing temperature.The catalyst Ni-NC-1000 with a moderate proportion of Ni SAs and NPs exhibited high efficiency in the electrocatalytic conversion of CO_(2)into CO.Operando Ni K-edge X-ray absorption near-edge structure(XANES)spectra and theoretical calculations were conducted to gain insight into the synergy of Ni SAs and NPs.The charge transfer from Ni NPs to the surrounding carbon layer and then to the Ni SAs resulted in the electron-enriched Ni SAs active sites.In the electroreduction of CO_(2),the coexistence of Ni SAs and NPs strengthened the CO_(2)activation and the affinity towards the key intermediate of*COOH,lowering the free energy for the potential-determining*CO_(2)→*COOH step,and therefore promoted the catalysis efficiency.
文摘The solar-driven catalytic conversion of CO2 to useful chemical fuels is regarded as an environmentally friendly approach to reduce the consumption of fossil fuels and mitigate the greenhouse effect.However,it is highly intriguing and challenging to promote the selectivity and efficiency of visible-light-responsive photocatalysts that favor the adsorption of CO2 in photoreduction processes.In this work,three-dimensional hierarchical Cd0.8Zn0.2S flowers(C8Z2S-F)with ultrathin petals were successfully synthesized through an in-situ self-assembly growth process using sodium citrate as a morphology director.The flower-like Cd0.8Zn0.2S solid solution exhibited remarkable photocatalytic performance in the reduction of CO2,generating CO up to 41.4μmol g^−1 under visible-light illumination for 3 h;this was nearly three times greater than that of Cd0.8Zn0.2S nanoparticles(C8Z2S-NP)(14.7μmol g^−1).Particularly,a comparably high selectivity of 89.9%for the conversion of CO2 to CO,with a turnover number of 39.6,was obtained from the solar-driven C8Z2S-F system in the absence of any co-catalyst or sacrificial agent.Terahertz time-domain spectroscopy indicated that the introduction of flower structures enhanced the light-harvesting capacity of C8Z2S-F.The in situ diffuse reflectance infrared Fourier transform spectroscopy unveiled the existence of surface-adsorbed species and the conversion of photoreduction intermediates during the photocatalytic process.Empirical characterizations and predictions of the photocatalytic mechanism demonstrated that the flower-like Cd0.8Zn0.2S solid solution possessed desirable CO2 adsorption properties and an enhanced charge-transfer capability,thus providing a highly effective photocatalytic reduction of CO2.
基金the National Natural Science Foundation of China(Nos.51878325,51868050,51622806,51378246 and 51720105001)the Natural Science Foundation of Jiangxi Province(Nos.20162BCB22017,20165BCB18008,20171ACB20017,20133ACB21001 and 20171BAB206049)the Graduate Innovation Fund of Jiangxi Province(No.YC2018-S360)。
文摘Herein,we prepa red novel three-dimensional(3D)gear-s haped Co3O4@C(Co3O4 modified by amorphous carbon)and sheet-like SnO2/CC(SnO2 grow on the carbon cloth)as anode and cathode to achieve efficient removal of 4-nitrophenol(4-NP)in the presence of peroxymonosulfate(PMS)and simultaneous electrocatalytic reduction of CO2,respectively.In this process,4-NP was mineralized into CO2 by the Co3O4@C,and the generated CO2 was reduced into HCOOH by the sheet-like SnO2/CC cathode.Compared with the pure Co0.5(Co3O4 was prepared using 0.5 g urea)with PMS(30 mg,0.5 g/L),the degradation efficiency of 4-NP(60 mL,10 mg/L)increased from 74.5%-85.1%in 60 min using the Co0.5 modified by amorphous carbon(Co0.5@C).Furthermore,when the voltage of 1.0 V was added in the anodic system of Co0.5@C with PMS(30 mg,0.5 g/L),the degradation efficiency of 4-NP increased from 85.1%-99.1%when Pt was used as cathode.In the experiments of 4-NP degradation coupled with simultaneous electrocatalytic CO2 reduction,the degradation efficiency of 4-NP was 99.0%in the anodic system of Co0.5@C with addition of PMS(30 mg,0.5 g/L),while the Faraday efficiency(FE)of HCOOH was 24.1%at voltage of-1.3 V using the SnO2/CC as cathode.The results showed that the anode of Co3O4 modified by amorphous carbon can markedly improve the degradation efficiency of 4-NP,while the cathode of SnO2/CC can greatly improve the FE and selectivity of CO2 reduction to HCOOH and the stability of cathode.Finally,the promotion mechanism was proposed to explain the degradation of organic pollutants and reduction of CO2 into HCOOH in the process of electrocatalysis coupled with advanced oxidation processes(AOPs)and simultaneous CO2 reduction.
基金the National Natural Science Foundation of China(No.21875221,21571157,U1604123,and 21773016)the Youth Talent Support Program of High-Level Talents Special Support Plan in Henan Province(ZYQR201810148)+1 种基金Creative talents in the Education Department of Henan Province(19HASTIT039)the project supported by State Key Laboratory of Advanced Technology for Materials Synthesis and Processing(Wuhan University of Technology)(2019-KF-13).
文摘Electrocatalytic carbon dioxide(CO2)reduction(ECR)has become one of the main methods to close the broken carbon cycle and temporarily store renewable energy,but there are still some problems such as poor stability,low activity,and selectivity.While the most promising strategy to improve ECR activity is to develop electrocatalysts with low cost,high activity,and long-term stability.Recently,defective carbon-based nanomaterials have attracted extensive attention due to the unbalanced electron distribution and electronic structural distortion caused by the defects on the carbon materials.Here,the present review mainly summarizes the latest research progress of the construction of the diverse types of defects(intrinsic carbon defects,heteroatom doping defects,metal atomic sites,and edges detects)for carbon materials in ECR,and unveil the structure-activity relationship and its catalytic mechanism.The current challenges and opportunities faced by high-performance carbon materials in ECR are discussed,as well as possible future solutions.It can be believed that this review can provide some inspiration for the future of development of high-performance ECR catalysts.
基金Project supported by the National Key R&D Program of China(2018YFB0605002)the National Natural Science Foundation of Shanghai(14ZR1417800)。
文摘Highly efficient photocatalytic reduction of CO2 is essential for solving the greenhouse effect and energy crisis.In this paper,the Sm-TiO2 nanocomposites were successfully prepared via sol-gel method.The CO2 photoreduction activities of synthesized samples were tested under irradiation for 6 h and the results indicate that the 0.5% Sm-TiO2 catalyst has superior performance and stability.The CO and CH4 yields of0.5% Sm-TiO2 catalyst are 55.47 and 3.82 μmol/g·cat respectively,which are 5.02 and 2.67 times the yield of TiO2.The possible mechanism of Sm doped TiO2 was investigated through comprehensive characterization and photoetectrochemical analysis,After the Sm doping,the photo-generated electrons in TiO2 could migrate to Sm 4 f,and some of them can be captured by reducing Sm3+ o Sm2+,which can lower the recombination rate of electron and hole pairs.Therefore,the enhanced photocatalytic performance could be ascribed to large specific surface area,fast separation rate of electron-hole pairs and high visible light response.This report provides some meaningful attempts in researching the CO2 photocatalytic reduction.
基金financially supported by the National Natural Science Foundation of China(21802089)Natural Science Foundation of Shandong Province(ZR2019BB015)+5 种基金The Science and Technology Plan of Shandong Province Colleges and Universities under Grant(No.J14LC16)the Natural Science Foundation of Shandong Province under Grant(No.ZR2017MB018)funding support from the Shandong Province Double Hundred Talents Program for Foreign Expertsthe Energy Education Trust of New Zealandthe Dodd Walls Centre for Photonic and Quantum Technologiesthe Mac Diarmid Institute for Advanced Materials and Nanotechnology
文摘Photoelectrocatalytic reduction of CO2 to fuels has great potential for reducing anthropogenic CO2 emissions and also lessening our dependence on fossil fuel energy.Herein,we report the successful development of a novel photoelectrocatalytic catalyst for the selective reduction of CO2 to methanol,comprising a copper catalyst modified with flower-like cerium oxide nanoparticles(CeO2 NPs)(a n-type semiconductor)and copper oxide nanoparticles(CuO NPs)(a p-type semiconductor).At an applied potential of−1.0 V(vs SCE)under visible light irradiation,the CeO2 NPs/CuO NPs/Cu catalyst yielded methanol at a rate of 3.44μmol cm^−2 h^−1,which was approximately five times higher than that of a CuO NPs/Cu catalyst(0.67μmol cm^−2 h^−1).The carrier concentration increased by^108 times when the flower-like CeO2 NPs were deposited on the CuO NPs/Cu catalyst,due to synergistic transfer of photoexcited electrons from the conduction band of CuO to that of CeO2,which enhanced both photocatalytic and photoelectrocatalytic CO2 reduction on the CeO2 NPs.The facile migration of photoexcited electrons and holes across the p–n heterojunction that formed between the CeO2 and CuO components was thus critical to excellent light-induced CO2 reduction properties of the CeO2 NPs/CuO NPs/Cu catalyst.Results encourage the wider application of composite semiconductor electrodes in carbon dioxide reduction.
文摘The electrochemical reduction of CO2(CO2 RR) can substantially contribute to the production of useful chemicals and reduction of global CO2 emissions. Herein, we presented N and S dual-doped high-surface-area carbon materials(SZ-HCN) as CO2 RR catalysts. N and S were doped by one-step pyrolysis of a N-containing polymer and S powder. ZnCl2 was applied as a volatile porogen to prepare porous SZ-HCN. SZ-HCN with a high specific surface area(1510 m2 g–1) exhibited efficient electrocatalytic activity and selectivity for CO2 RR. Electrochemical measurements demonstrated that SZ-HCN showed excellent catalytic performance for CO2-to-CO reduction with a high CO Faradaic efficiency(~93%) at-0.6 V. Furthermore, SZ-HCN offered a stable current density and high CO selectivity over at least 20 h continuous operation, revealing remarkable electrocatalytic durability. The experimental results and density functional theory calculations indicated that N and S dual-doped carbon materials required lower Gibbs free energy to form the COOH* intermediate than that for single-N-doped carbon for CO2-to-CO reduction, thereby enhancing CO2 RR activity.
基金supported by the Fundamental Research Funds for the Central Universities(XK1802-6,XK1902,XK1803-05,12060093063,2312018RC07)the National Natural Science Foundation of China(U1707603,21878008,21625101,20190816)。
文摘Photocatalytic reduction of CO2 with H2 O to syngas is an effective way for producing high value-added chemical feedstocks such as methanol and light olefins in industry.Nevertheless,the precise control of CO/H2 ratio from photocatalytic CO2 reduction reaction still poses a great challenge for the further application.Herein,we prepared a series of highly efficient heterostructure based on highly dispersed palladium supported on ultrathin Co Al-layered double hydroxide(LDH).In conjunction with a Ru-complex sensitizer,the molar ratios of CO/H2 can be tuned from 1:0.74 to 1:3 under visible-light irradiation(λ>400 nm).More interestingly,the syngas can be obtained under light irradiation atλ>600 nm.Structure characterization and density functional theory calculations revealed that the remarkable catalytic activity can be due to the supported palladium,which improved the charge transfer efficiency.Meanwhile,more H atoms were used to generate H2 on the supported palladium for further tunable CO/H2 ratio.This work demonstrates a new strategy for harnessing abundant solar-energy to produce syngas from a CO2 feedstock.
文摘Cobalt-based oxides,with high abundance,good stability and excellent catalytic performance,are regarded as promising photocatalysts for artificial photosynthetic systems to alleviate foreseeable energy shortages and global warming.Herein,for the first time,a series of novel spongy porous CDs@CoOx materials were synthesized to act as an efficient and stable bifunctional photocatalyst for water oxidation and CO2 reduction.Notably,the preparation temperatures visibly influence the morphologies and photocatalytic performances of the CDs@CoOx.Under the optimal conditions,a maximum O2 yield of 40.4% and pretty apparent quantum efficiency(AQE)of 58.6% at 460 nm were obtained over CDs@CoOx-300 for water oxidation.Similarly,the optimized sample CDs@CoOx-300 manifests significant enhancement on the CO2-to-CO conversion with a high selectivity of 89.3% and CO generation rate of 8.1μmol/h,which is superior to most previous cobalt-based catalysts for CO2 reduction.The composite CDs@CoOx-300 not only exposes more active sites but also facilitates electron transport,which results in excellent photocatalytic activity.In addition,the boosted photocatalytic behavior is attributed to the synergistic effect between CoOx and CDs,which was verified by the photocatalytic activity control experiments and electrochemical characterization.The work offers a novel strategy to fabricate a high performance bifunctional photocatalyst for water oxidation and CO2 reduction.
基金supported by the National Natural Science Foundation of China(21673030)the Fundamental Research Funds for the Central Universities(DUT16QY49)
文摘In terms of the reaction of COreduction to CO with hydrogen, COconversion is very low at low temperature due to the limitation of thermodynamic equilibrium（TE）. To overcome this limitation, plasma catalytic reduction of COto CO in a catalyst-filled dielectric barrier discharge（DBD） reactor is studied. An enhanced effect of plasma on the reaction over Au/CeOcatalysts is observed. For both the conventionally catalytic（CC） and plasma catalytic（PC, Pin= 15 W） reactions under conditions of 400 °C, H/CO= 1,200 SCCM, GHSV = 12,000 mL·gcat·h, COconversions over Au/CeOreach 15.4% and 25.5% due to the presence of Au, respectively, however, those over CeOare extremely low and negligible. Moreover,COconversion over Au/CeOin the PC reaction exceeds 22.4% of the TE conversion. Surface intermediate species formed on the catalyst samples during the reactions are determined by in-situ temperatureprogrammed decomposition（TPD） technique. Interestingly, it disclosed that in the PC reaction, the formation of formate intermediate is enhanced by plasma, and the acceleration by plasma in the decomposition of formate species is much greater than that in the formation of formate species on Au/CeO. Enhancement factor is introduced to quantify the enhanced effect of plasma. Lower reactor temperature, higher gas hourly space velocity（GHSV）, and lower molar ratio of H/COwould be associated with larger enhancement factor.
基金The authors thank the financial support from the“Scientific and Technical Innovation Action Plan”Basic Research Field of the Shanghai Science and Technology Committee(19JC1410500)the Fundamental ResearchFunds for the Central Universities(2232018A3‐06)the National Natural Science Foundation of China(91645110).
文摘Zero or negative emissions of carbon dioxide(CO2)is the need of the times,as inexorable rising and alarming levels of CO2 in the atmosphere lead to global warming and severe climate change.The electrochemical CO2 reduction(eCO2R)to value‐added fuels and chemicals by using renewable electricity provides a cleaner and more sustainable route with economic benefits,in which the key is to develop clean and economical electrocatalysts.Carbon‐based catalyst materials possess desirable properties such as high offset potential for H2 evolution and chemical stability at the negative applied potential.Although it is still challenging to achieve highly efficient carbon‐based catalysts,considerable efforts have been devoted to overcoming the low selectivity,activity,and stability.Here,we summarize and discuss the recent progress in carbon‐based metal‐free catalysts including carbon nanotubes,carbon nanofibers,carbon nanoribbons,graphene,carbon nitride,and diamonds with an emphasis on their activity,product selectivity,and stability.In addition,the key challenges and future potential approaches for efficient eCO2R to low carbon‐based fuels are highlighted.For a good understanding of the whole history of the development of eCO2R,the CO2 reduction reactions,principles,and techniques including the role of electrolytes,electrochemical cell design and evaluation,product selectivity,and structural composition are also discussed.The metal/metal oxides decorated with carbon‐based electrocatalysts are also summarized.We aim to provide insights for further development of carbon‐based metal‐free electrocatalysts for CO2 reduction from the perspective of both fundamental understanding and technological applications in the future.
基金National Natural Science Foundation of China,Grant/Award Numbers:21573240,21706265,21922813The would like to acknowledge the support provided by the National Natural Science Foundation of China(Grant no.:21573240 and 21706265)+2 种基金the Center for Mesoscience,Institute of Process Engineering,Chinese Academy of Sciences(MPCS-2017-A-02)State Key Laboratory of Multiphase Complex Systems(MPCS-2019-A-09)National Science Fund for Excellent Young Scholars(21922813).
文摘Preciously tuning the surface composition of noble metal nanoparticles with the particle size of only 2 nm or less by alloying with other metals represents a powerful strategy to boost their electrocatalytic selectivity.However,the synthesis of ultrafine nanoalloys and tuning their surface composition remain challenging.In this report,ultrafine CuPd nanoalloys with the particle size of ca.2 nm are synthesized based on the galvanic replacement reaction between presynthesized Cu nanoparticles and Pd2+precursors,and the tuning of their surface compositions is also achieved by changing the atom ratios of Cu/Pd.For the electrocatalytic reduction of CO2,Cu5Pd5 nanoalloys show the CO Faradaic efficiency(FE)of 88%at−0.87 V,and the corresponding mass activity reaches 56 A/g that is much higher than those of Cu8Pd2 nanoalloys,Cu3Pd7 nanoalloys and most of previously reported catalysts.Density functional theory uncovers that with the increase of Pd on the surface of the ultrafine CuPd nanoalloys,the adsorbed energy of both of intermediate COOH*and CO*to the Pd sites is strengthened.The Cu5Pd5 nanoalloys with the optimal surface composition better balance the adsorption of COOH*and desorption of CO*,achieving the highest selectivity and activity.The difficult liberation of absorbed CO*on the surface of Cu3Pd7 nanoalloys provides carbon source to favor the production of ethylene,endowing the Cu3Pd7 nanoalloys with the highest selectivity for ethylene among these ultrafine CuPd nanoalloys.
文摘Crystalline TiO（P25） and isolated titanate species in a ZSM-5 structure（TS-1） were modified with Au and Ag, respectively, and tested in the gas-phase photocatalytic COreduction under high purity conditions. The noble metal modification was performed by photodeposition. Light absorbance properties of the catalysts are examined with UV–Vis spectroscopy before and after the activity test. In the gas-phase photocatalytic COreduction, it was observed that the catalysts with Ag nanostructures are more active than those with Au nanostructures. It is thus found that the energetic difference between the band gap energy of the semiconductor and the position of the plasmon is influencing the photocatalytic activity.Potentially, plasmon excitation due to visible light absorption results in plasmon resonance energy, which affects the excitation of the semiconductor positively. Therefore, an overlap between band gap energy of the semiconductor and metal plasmon is needed.
基金supported by the National Natural Science Foundation of China(21503096,21407067)the Natural Science Foundation of Educational Committee of Anhui Province(KJ2018A0387),ChinaProject of Anhui Province for Excellent Young Talents in Universities(gxyq2019029),China
文摘Photocatalytic H2 production and CO2 reduction have attracted considerable attention for clean energy development.In this work,we designed an efficient photocatalyst by integrating lamellar oxygen-doped carbon nitride(CNO)nanosheets into ZnIn2S4(ZIS)microflowers by a one-step hydrothermal method.A well-fitted 2D hierarchical hybrid heterostructure was fabricated.Under visible light irradiation,the ZIS@CNO composite with 40 wt%CNO(ZC 40%)showed the highest hydrogen evolution rate from water(188.4μmol·h-1),which was approximately 2.1 times higher than those of CNO and ZIS(88.6 and 90.2μmol·h-1,respectively).Furthermore,the selective CO production rates of ZC 40%(12.69μmol·h-1)were 2.2 and 14.0 times higher than those of ZIS(5.85μmol·h-1)and CNO(0.91μmol·h-1),respectively,and the CH4 production rate of ZC 40%was 1.18μmol·h-1.This enhanced photocatalytic activity of CNO@ZIS is due mainly to the formation of a heterostructure that can promote the transfer of photoinduced electrons and holes between CNO and ZIS,thereby efficiently avoiding recombination of electron-hole pairs.
基金the National Postdoctoral Program for Innovative Talents of China,Postdoctoral Science Foundation of China(Grant No.2018M640759)Natural Science Foundation of China(Grant No.21872174 and U1932148)+4 种基金Project of Innovation-Driven Plan in Central South University(Grant No.20180018050001)State Key Laboratory of Powder Metallurgy,International Science and Technology Cooperation Program(Grant No.2017YFE0127800)Hunan Provincial Science and Technology Program(2017XK2026)Shenzhen Science and Technology Innovation Project(Grant No.JCYJ20180307151313532)Thousand Youth Talents Plan of China and Hundred Youth Talents Program of Hunan.
文摘Converting carbon dioxide(CO2)into value-added chemicals by CO2 reduction has been considered as a potential way to solve the current energy crisis and environmental problem.Among the methods of CO2 reduction,the electrochemical method has been widely used due to its mild reaction condition and high reaction efficiency.In the electrochemical reduction system,the CO2 electrocatalyst is the most important part.Although many CO2 electrocatalysts have been developed,efficient catalysts with high activity,selectivity and stability are still lacking.Copper sulfide compound,as a low-toxicity and emerging material,has broad prospects in the field of CO2 reduction due to its unique structural and electrochemical properties.Much progress has been achieved with copper sulfide nanocrystalline and the field is rapidly developing.This paper summarizes the preparation,recent progress in development,and factors affecting the electrocatalytic CO2 reduction performance with copper sulfide compound as a catalyst.Prospects for future development are also outlined,with the aim of using copper sulfide compound as a highly active and stable electrocatalyst for CO2 reduction.
基金supported by the National Natural Science Foundation of China (No. 21477079, 21677099, 21237003)the Shanghai Government (No. 11ZR1426300, 13YZ054, 14ZR1430900)+1 种基金the Program for Changjiang Scholars and Innovative Research Team in University (No. IRT1269)the International Joint Laboratory on Resource Chemistry (No. IJLRC)
文摘A solar-light double illumination photoelectrocatalytic cell（SLDIPEC） was fabricated for autonomous CO2 reduction and O2 evolution with the aid of photosystem II（PS-II, an efficient light-driven water-oxidized enzyme from nature） and utilized in a photoanode solution. The proposed SLPEC system was composed of Cu foam as the photoanode and p-Si nanowires（Si-NW） as the photocathode. Under solar irradiation, it exhibited a super-photoelectrocatalytic performance for CO2 conversion to methanol, with a high evolution rate（41.94 mmol/hr）, owing to fast electron transfer from PS-II to Cu foam.Electrons were subsequently trapped by Si-NW through an external circuit via bias voltage（0.5 V）, and a suitable conduction band potential of Si（-0.6 e V） allowed CO2 to be easily reduced to CH3 OH at the photocathode. The constructed Z-scheme between Cu foam and Si-NW can allow the SLDIPEC system to reduce CO2（8.03 mmol/hr） in the absence of bias voltage. This approach makes full use of the energy band mismatch of the photoanode and photocathode to design a highly efficient device for solving environmental issues and producing clean energy.
文摘It is desirable to develop highly efficient and sustainable catalytic systems for CO_(2) photoreduction using efficient heterogeneous photosensitizers(PSs);however,this remains a great challenge.In this study,we doped[Ru(bpy)3]^(2+) into UiO-metal-organic frameworks(MOFs)to facilitate the separation and reuse of noble metal PS.By simply adjusting the loading amount,a series of heterogeneous photoactive MOFs,namely,UiO-Ru-1,UiO-Ru-2,and UiO-Ru-3,were constructed to act as heterogeneous PSs to drive the efficient CO_(2) photoreduction under visible-light irradiation.Remarkably,UiO-Ru-2 exhibited the best photosensitizing ability among the prepared MOFs in sensitizing the iron quarterpyridine catalyst(C-l),and the CO yield reached as high as 171 mmol/g with ca.100%selectivity,which is a record value among all the MOF-based photocatalysts.This photoactive MOF can be recycled and reused three times without any obvious activity loss,signifying its good photochemical stability.Experimental investigations confirmed that the strong visible absorption,long-lived excited state,appropriate redox potential,good photocatalytic stability,and excellent collaboration with C-l were attributable to the superior catalytic activity.This work highlights an avenue for constructing heterogeneous PSs with excellent recyclability using MOF as the platform for efficient CO_(2) reduction.
基金supported by the National Key R&D Program of China (2017YFA0207301)National Natural Science Foundation of China (No.21725102, No.21471141,No.21601173)+3 种基金CAS Key Research Program of Frontier Sciences(QYZDB-SSWSLH018)CAS Interdisciplinary Innovation Team,Innovative Program of Development Foundation of Hefei Center for Physical Science and Technology (No.2016FXCX003)Anhui Provincial Natural Science Foundation (No.1608085QB24)Chinese Universities Scientific Fund (WK2310000067)
文摘Photocatalytic reduction of CO2 into various types of fuels has attracted great interest,and serves as a potential solution to addressing current global warming and energy challenges.In this work,Ag-Cu nanoparticles are densely supported on N-doped TiO2 nanowire through a straightforward nanofabrication approach.The range of light absorption by N-doped TiO2 can be tuned to match the plasmonic band of Ag nanoparticles,which allows synergizing a resonant energy transfer process with the Schottky junction.Meanwhile,Cu nanoparticles can provide active sites for the reduction of CO2 molecules.Remarkably,the performance of photocatalytic CO2 reduction is improved to produce CH4 at a rate of 720μmol·g-1·h-1 under full-spectrum irradiation.
基金supported by the National Natural Science Foundation of China (Grant Nos. 21677029, 21606040)the Fundamental Research Funds for the Central Universities (DUT18LK26)。
文摘Converting CO2 to carbon-containing fuels is an effective approach to relieving energy shortages.Carbon quantum dots(CQDs) have shown distinct properties and attracted tremendous interest in CO2 reduction.Herein,we report a joint experimental-computational mechanistic study of photoreduction CO2 to CO on the model catalyst 9-hydroxyphenal-1-one(HPHN) CQDs with known structure.Our theoretical calculations reveal that the rate-determining step is COOH·formation,which is closely related to the proton and electron transfer induced by hydrogen bonding in the excited state.According to the calculated volcano plot,the solution we proposed is addition Zn^(2+) ions.The active center changed from the hydroxyl oxygen atom to the Zn atom and the barrier of the COOH·formation step is noticeably decreased when Zn^(2+) ions are added.It is further confirmed by the experimental data that the activity of CO2 reduction increases 2.9 times when Zn^(2+) ions are added.
基金supported by the National Natural Science Foundation of China (No.21473175 and No.21273215)the Ministry of Science and Technology of China (No.2015CB932301)
文摘Hydrogen evolution reaction(HER)is the major cathodic reaction which competes CO2 reduction reaction(CO2 RR)on Pt electrode.Molecular level understanding on how these two reactions interact with each other and what the key factors are of CO2 RR kinetics and selectivity will be of great help in optimizing electrolysers for CO2 reduction.In this work,we report our results of hydrogen evolution and CO2 reduction on Pt(111)and Pt film electrodes in CO2 saturated acid solution by cyclic voltammetry and infrared spectroscopy.In solution with pH>2,the major process is HER and the interfacial pH increases abruptly during HER;COad is the only adsorbed intermediate detected in CO2 reduction by infrared spectroscopy;the rate for COad formation increases with the coverage of UPD-H and reaches maximum at the onset potential for HER;the decrease of COad formation under HER is attributed to the available limited sites and the limited residence time for the reduction intermediate(Had),which is necessary for CO2 adsorption and reduction.
