The development of efficient and stable bifunctional overall water-splitting is a crucial goal for clean and renewable energy,which is a challenging task.Herein,we report an Mn-incorporated RuO_(2)(MnRuO_(2))catalyst ...The development of efficient and stable bifunctional overall water-splitting is a crucial goal for clean and renewable energy,which is a challenging task.Herein,we report an Mn-incorporated RuO_(2)(MnRuO_(2))catalyst for highly efficient electrocatalytic oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)in acid and alkaline media.Benefiting from a more electrochemical active area with the incorporation of Mn,the Mn-RuO_(2)required an overpotential of 200 mV to attain a current density of 10 mA/cm^(2)for OER in acid.DFT result indicates that the doping of Mn into RuO_(2)can enhance the OER activity.An acidic overall water-splitting electrolyzer with good stability constructed by bifunctional Mn-RuO_(2)only requires a cell voltage of 1.50 V to afford 10 m A/cm^(2)and can operate stably for 50 h at50 mA/cm^(2),which is better than the state-of-the-art Ru-based catalyst.Additionally,the Mn-Ru O_(2)exhibits excellent HER and OER activity in alkaline media,and it shows superior activity and durability for overall water-splitting,only needing a cell voltage of 1.49 V to attain 10 m A/cm^(2).The present work provides an efficient approach to designing and constructing efficient Ru-based electrocatalysts for overall water-splitting.展开更多
Compared to the conventional trial-and-error approach,computational prediction is becoming an increasingly prominent approach inthe discovery of covalent organic frameworks(COFs)with specific applications,yet it has b...Compared to the conventional trial-and-error approach,computational prediction is becoming an increasingly prominent approach inthe discovery of covalent organic frameworks(COFs)with specific applications,yet it has been rarely demonstrated.Herein,we em-ployed density functional theory(DFT)to pre-screen the electronic and optical properties of thiophene-based donor-acceptor(D-A)pairs simplified from their corresponding COF structures.Theoretical calculation illustrates the BMTB-BTTC with the highest number ofthiophene units is expected to exhibit the best photocatalytic performance for hydrogen production.According to calculation predic-tion,four COFs have been prepared and their photocatalytic activities have been experimentally validated.Interestingly,the corre-sponding BMTB-BTTC-COF shows the highest photocatalytic hydrogen production rate of 12.37 mmolg^(-1)·h^(-1) among the four COFs.Combining the calculation and experimental results,it has been proven that the photocatalytic activity can be fine-tuned by modulat-ing the number of thiophene units.Our study provides a new strategy for the rational design and regulation of D-A COFs to enhancephotocatalytic activity through computational prediction.展开更多
While reliance on renewable energy resources has become a reality, there is still a need to deploy greener and more sustainable methods in order to achieve sustainable development goals. Indeed, green hydrogen is curr...While reliance on renewable energy resources has become a reality, there is still a need to deploy greener and more sustainable methods in order to achieve sustainable development goals. Indeed, green hydrogen is currently believed to be a reliable solution for global warming and the pollution challenges arising from fossil fuels, making it the resilient fuel of the future. However, the sustainability of green hydrogen technologies is yet to be achieved. In this context, generation of green hydrogen with the aid of deep eutectic solvents(DESs) as green mixtures has been demonstrated as a promising research area. This systematic review article covers green hydrogen generation through water splitting and biomass fermentation when DESs are utilized within the generation process. It also discusses the incorporation of DESs in fuel cell technologies. DESs can play a variety of roles such as solvent, electrolyte, or precursor;colloidal suspension and reaction medium;galvanic replacement, shape-controlling, decoration, or extractive agent;finally oxidant. These roles are relevant to several methods of green hydrogen generation, including electrocatalysis, photocatalysis, and fermentation. As such, it is of utmost importance to screen potential DES formulations and determine how they can function in and contribute throughout the green hydrogen mobility stages. The realization of super green hydrogen generation stands out as a pivotal milestone in our journey towards achieving a more sustainable form of development;DESs have great potential in making this milestone achievable. Overall, incorporating DESs in hydrogen generation constitutes a promising research area and offers potential scalability for green hydrogen production, storage,transport, and utilization.展开更多
Realizing the hydrogen economy by water electrolysis is an attractive approach for hydrogen production,while the efficient and stable bifunctional catalysts under high current densities are the bottleneck that limits ...Realizing the hydrogen economy by water electrolysis is an attractive approach for hydrogen production,while the efficient and stable bifunctional catalysts under high current densities are the bottleneck that limits the half-cell reactions of water splitting.Here,we propose an approach of hydrothermal and thermal annealing methods for robust MoO_(2)/MoNi_(4)@Ru/RuO_(2) heterogeneous cuboid array electrocatalyst with multiplying surface-active sites by depositing a monolayer amount of Ru.Benefiting from abundant MoO_(2)/MoNi_(4)@Ru/RuO_(2)heterointerfaces,MoO_(2)/MoNi_(4)@Ru/RuO_(2) heterogeneous cuboid array electrocatalysts effectively drive the alkaline water splitting with superior hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)performances.The synthesized MoO_(2)/MoNi_(4)@Ru/RuO_(2) has high HER activity,which realizes the working overpotentials of 48 mV at 50 mA·cm^(-2),further achieving overpotentials of 230 mv for industry-level 1000 mA·cm^(-2) in alkaline water electrolysis.Moreover,it also showed an enhanced OER activity than commercial RuO_(2) with a small overpotential of 280 mV at 200 mA·cm^(-2) in alkaline media.When building an electrolyzer with electrodes of(-)MoO_(2)/MoNi_(4)@Ru/RuO_(2)IIMo02/MoNig@Ru/RuO_(2)(+),a cell voltage of 1.63 V and 1.75 V is just required to support the current density of 200 mA·cm^(-2) and 500 mA-cm^(-2) in alkaline water electrolysis,much lower than that of the electrolyzer of(-)Pt/CIIRuO_(2)(+).This work demonstrates that MoO_(2)/MoNig@Ru/RuO_(2) heterogeneous nanosheet arrays are promising candidates for industrial water electrolysis applications,providing a possibility for the exploration of water electrolysis with a large currentdensity.展开更多
Rational design and facet-engineering of nanocrystal is an effective strategy to optimize the catalytic performance of abundant and economic semiconductorbased photocatalysts.In this study,we demonstrate a novel terna...Rational design and facet-engineering of nanocrystal is an effective strategy to optimize the catalytic performance of abundant and economic semiconductorbased photocatalysts.In this study,we demonstrate a novel ternary Cu2MoS4 nanotube with the {010} facet exposed,synthesized via a hydrothermal method.Compared with two-dimensional Cu2MoS4 nanosheet with the {001} facet exposed,this one-dimensional nanotube exhibits highly enhanced performance of photodegradation and water splitting.Both theoretical calculations and experimental results suggest that the conduction band minimum （CBM） of the {010} facet crystal shows lower potential than that of the {001} facet.In particular,the up-shifted CBM in Cu2MoS4 nanotube is significantly beneficial for the absorption of dye molecules and reduction of H＋ to H2.These results may open a new route for realizing high-efficiency photocatalysts based on Cu2MX4 by facet engineering.展开更多
CuW（1-x）MoxO4 solid solution of CuWO4 and CuMoO4, which is a copper-based multi-component oxide semiconductor, possesses much narrower band gap than CuWO4. In theory, it can absorb a larger part of the visible spect...CuW（1-x）MoxO4 solid solution of CuWO4 and CuMoO4, which is a copper-based multi-component oxide semiconductor, possesses much narrower band gap than CuWO4. In theory, it can absorb a larger part of the visible spectrum, widening the use of solar spectroscopy and obtaining a higher photo-to-chemical conversion efficiency. In this study, CuW（1-x）MoxO4 thin-film photoanodes on conducting glass were prepared using a simple and low-cost spray pyrolysis method. The resulting CuW（1-x）MoxO4 photoanodes perform higher photocurrent than CuWO4 photoanodes under AM 1.5 G simulated sunlight illumination（100 m W cm^（-2））in 0.1 mol L^（-1） phosphate buffer at pH 7. Combined with IPCE and Mott-Schottky analysis, the enhancement of the photocurrent is due to the improvement of photon utilization and the increase of carrier concentration with the incorporation of Mo atoms. Moreover, with the optimal Mo/W atomic ratio,the photocurrent density increases obviously from 0.07 to 0.46 m A cm^（-2） at 1.23 V（RHE） bias. In addition, compared with particle-assembled thin-film photoanodes prepared by solidphase reaction and drop-necking treatment, the photoanodes prepared by spray pyrolysis have obvious advantages in terms of reducing resistance and facilitating charge transport.展开更多
Non-noble metal electrocatalysts for water cracking have excellent pro-spects for development of sustainable and clean energy.Highly efficient electrocatalysts for the oxygen evolution reaction(OER)are very important ...Non-noble metal electrocatalysts for water cracking have excellent pro-spects for development of sustainable and clean energy.Highly efficient electrocatalysts for the oxygen evolution reaction(OER)are very important for various energy storage and conversion systems such as water splitting devices and metal-air batteries.This study prepared a NiMo4@C_(3)N_(4) catalyst for OER and hydrogen evolution reaction(HER)by simple methods.The catalyst exhibited an excellent OER activity based on the response at a suitable temperature.To drive a current density of 10 mA-cm^(-2) for OER and HER,the overpotentials required for NiMo4@C_(3)N_(4)-800(prepared at 800℃)were 259 and 118 mV,respectively.A two-electrode system using NiMo4@C_(3)N_(4)-800 needed a very low cell potential of 1.572 V to reach a current density of 10 mA-cm^(-2).In addition,this catalyst showed excellent durability after long-term tests.It was seen to have good catalytic activity and broad application prospects.展开更多
基金supported by the Key Research and Development Program sponsored by the Ministry of Science and Technology(MOST,Nos.2022YFB4002000,2022YFA1203400)the National Natural Science Foundation of China(Nos.21925205,22072145,22372155,22005294 and 22102172)。
文摘The development of efficient and stable bifunctional overall water-splitting is a crucial goal for clean and renewable energy,which is a challenging task.Herein,we report an Mn-incorporated RuO_(2)(MnRuO_(2))catalyst for highly efficient electrocatalytic oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)in acid and alkaline media.Benefiting from a more electrochemical active area with the incorporation of Mn,the Mn-RuO_(2)required an overpotential of 200 mV to attain a current density of 10 mA/cm^(2)for OER in acid.DFT result indicates that the doping of Mn into RuO_(2)can enhance the OER activity.An acidic overall water-splitting electrolyzer with good stability constructed by bifunctional Mn-RuO_(2)only requires a cell voltage of 1.50 V to afford 10 m A/cm^(2)and can operate stably for 50 h at50 mA/cm^(2),which is better than the state-of-the-art Ru-based catalyst.Additionally,the Mn-Ru O_(2)exhibits excellent HER and OER activity in alkaline media,and it shows superior activity and durability for overall water-splitting,only needing a cell voltage of 1.49 V to attain 10 m A/cm^(2).The present work provides an efficient approach to designing and constructing efficient Ru-based electrocatalysts for overall water-splitting.
基金supported by the National Natural Science Foundation of China(Nos.22371091,21975104,22150004,22201102,and 22302141)the Guangdong Major Project of Basic and Applied Research(No.2019B030302009)+4 种基金Zhejiang Provincial Natural Science Foundation of China(No.LY22E030008)the Open Fund of Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications(No.2020B121201005)the Postdoctoral Fellowship Program of CPSF(No.GZC20240598)China Postdoctoral Science Foundation(No.2024M751118)Q.G.is thankful for the financial support from Special Project for Peak Carbon Dioxide Emissions-Carbon Neutrality(21DZ1206900)from the Shanghai Municipal Science and Technology Commission.
文摘Compared to the conventional trial-and-error approach,computational prediction is becoming an increasingly prominent approach inthe discovery of covalent organic frameworks(COFs)with specific applications,yet it has been rarely demonstrated.Herein,we em-ployed density functional theory(DFT)to pre-screen the electronic and optical properties of thiophene-based donor-acceptor(D-A)pairs simplified from their corresponding COF structures.Theoretical calculation illustrates the BMTB-BTTC with the highest number ofthiophene units is expected to exhibit the best photocatalytic performance for hydrogen production.According to calculation predic-tion,four COFs have been prepared and their photocatalytic activities have been experimentally validated.Interestingly,the corre-sponding BMTB-BTTC-COF shows the highest photocatalytic hydrogen production rate of 12.37 mmolg^(-1)·h^(-1) among the four COFs.Combining the calculation and experimental results,it has been proven that the photocatalytic activity can be fine-tuned by modulat-ing the number of thiophene units.Our study provides a new strategy for the rational design and regulation of D-A COFs to enhancephotocatalytic activity through computational prediction.
基金the Ministry of Higher Education,Research and Innovation(MoHERI)Oman for their support of this research through TRC block funding Grant no.:BFP/RGP/EBR/22/378。
文摘While reliance on renewable energy resources has become a reality, there is still a need to deploy greener and more sustainable methods in order to achieve sustainable development goals. Indeed, green hydrogen is currently believed to be a reliable solution for global warming and the pollution challenges arising from fossil fuels, making it the resilient fuel of the future. However, the sustainability of green hydrogen technologies is yet to be achieved. In this context, generation of green hydrogen with the aid of deep eutectic solvents(DESs) as green mixtures has been demonstrated as a promising research area. This systematic review article covers green hydrogen generation through water splitting and biomass fermentation when DESs are utilized within the generation process. It also discusses the incorporation of DESs in fuel cell technologies. DESs can play a variety of roles such as solvent, electrolyte, or precursor;colloidal suspension and reaction medium;galvanic replacement, shape-controlling, decoration, or extractive agent;finally oxidant. These roles are relevant to several methods of green hydrogen generation, including electrocatalysis, photocatalysis, and fermentation. As such, it is of utmost importance to screen potential DES formulations and determine how they can function in and contribute throughout the green hydrogen mobility stages. The realization of super green hydrogen generation stands out as a pivotal milestone in our journey towards achieving a more sustainable form of development;DESs have great potential in making this milestone achievable. Overall, incorporating DESs in hydrogen generation constitutes a promising research area and offers potential scalability for green hydrogen production, storage,transport, and utilization.
基金sponsored by the National Natural Science Foundation of China(51772162,52072197)the China Postdoctoral Science Foundation(2023M732132)+4 种基金Youth Innovation Team Development Program of Shandong Higher Education Institutions(2022KJ155)Outstanding Youth Foundation of Shandong Province,China(ZR2019JQ14)Taishan Scholar Young Talent Program(tsqn201909114)Major Scientific and Technological Innovation Project(2019JZZY020405)Major Basic Research Program of Natural Science Foundation of Shandong Province under Grant(ZR2020ZD09).
文摘Realizing the hydrogen economy by water electrolysis is an attractive approach for hydrogen production,while the efficient and stable bifunctional catalysts under high current densities are the bottleneck that limits the half-cell reactions of water splitting.Here,we propose an approach of hydrothermal and thermal annealing methods for robust MoO_(2)/MoNi_(4)@Ru/RuO_(2) heterogeneous cuboid array electrocatalyst with multiplying surface-active sites by depositing a monolayer amount of Ru.Benefiting from abundant MoO_(2)/MoNi_(4)@Ru/RuO_(2)heterointerfaces,MoO_(2)/MoNi_(4)@Ru/RuO_(2) heterogeneous cuboid array electrocatalysts effectively drive the alkaline water splitting with superior hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)performances.The synthesized MoO_(2)/MoNi_(4)@Ru/RuO_(2) has high HER activity,which realizes the working overpotentials of 48 mV at 50 mA·cm^(-2),further achieving overpotentials of 230 mv for industry-level 1000 mA·cm^(-2) in alkaline water electrolysis.Moreover,it also showed an enhanced OER activity than commercial RuO_(2) with a small overpotential of 280 mV at 200 mA·cm^(-2) in alkaline media.When building an electrolyzer with electrodes of(-)MoO_(2)/MoNi_(4)@Ru/RuO_(2)IIMo02/MoNig@Ru/RuO_(2)(+),a cell voltage of 1.63 V and 1.75 V is just required to support the current density of 200 mA·cm^(-2) and 500 mA-cm^(-2) in alkaline water electrolysis,much lower than that of the electrolyzer of(-)Pt/CIIRuO_(2)(+).This work demonstrates that MoO_(2)/MoNig@Ru/RuO_(2) heterogeneous nanosheet arrays are promising candidates for industrial water electrolysis applications,providing a possibility for the exploration of water electrolysis with a large currentdensity.
基金This work is financially supported by the National Basic Research Program of China （No. 2014CB848900）, National Natural Science Foundation of China （Nos. U1532112, 11375198, 11574280, and 11605201）, CUSF （Nos. WK2310000053, 6030000031）, China Scholarship Council and Key Laboratory of Advanced Energy Materials Chemistry （Ministry of Education）, Nankai University. L. S. acknowledges the recruitment program of global experts, the CAS Hundred Talent Program. We thank the Shanghai Synchrotron Radiation Facility （14W1, SSRF）, the Beijing Synchrotron Radiation Facility （1WIB and soft-X-ray endstation, BSRF）, the Hefei Synchrotron Radiation Facility （Photoemission, MCD and Catalysis/Surface Science Endstations, NSRL）, and the USTC Center for Micro and Nanoscale Research and Fabrication for help in characterizations. The authors also thank Ms. Ying Luo, Dr. Jun Bao, and Dr. Yu Li for useful discussions.
文摘Rational design and facet-engineering of nanocrystal is an effective strategy to optimize the catalytic performance of abundant and economic semiconductorbased photocatalysts.In this study,we demonstrate a novel ternary Cu2MoS4 nanotube with the {010} facet exposed,synthesized via a hydrothermal method.Compared with two-dimensional Cu2MoS4 nanosheet with the {001} facet exposed,this one-dimensional nanotube exhibits highly enhanced performance of photodegradation and water splitting.Both theoretical calculations and experimental results suggest that the conduction band minimum （CBM） of the {010} facet crystal shows lower potential than that of the {001} facet.In particular,the up-shifted CBM in Cu2MoS4 nanotube is significantly beneficial for the absorption of dye molecules and reduction of H＋ to H2.These results may open a new route for realizing high-efficiency photocatalysts based on Cu2MX4 by facet engineering.
基金supported by the National Basic Research Program of China (973 Program, 2013CB632404)National Natural Science Foundation of China (21473090 and 51272102)a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘CuW（1-x）MoxO4 solid solution of CuWO4 and CuMoO4, which is a copper-based multi-component oxide semiconductor, possesses much narrower band gap than CuWO4. In theory, it can absorb a larger part of the visible spectrum, widening the use of solar spectroscopy and obtaining a higher photo-to-chemical conversion efficiency. In this study, CuW（1-x）MoxO4 thin-film photoanodes on conducting glass were prepared using a simple and low-cost spray pyrolysis method. The resulting CuW（1-x）MoxO4 photoanodes perform higher photocurrent than CuWO4 photoanodes under AM 1.5 G simulated sunlight illumination（100 m W cm^（-2））in 0.1 mol L^（-1） phosphate buffer at pH 7. Combined with IPCE and Mott-Schottky analysis, the enhancement of the photocurrent is due to the improvement of photon utilization and the increase of carrier concentration with the incorporation of Mo atoms. Moreover, with the optimal Mo/W atomic ratio,the photocurrent density increases obviously from 0.07 to 0.46 m A cm^（-2） at 1.23 V（RHE） bias. In addition, compared with particle-assembled thin-film photoanodes prepared by solidphase reaction and drop-necking treatment, the photoanodes prepared by spray pyrolysis have obvious advantages in terms of reducing resistance and facilitating charge transport.
基金supported by the Department of Education Basic Research Operating Costs of Heilongjiang Province,China(Grant No.300663).
文摘Non-noble metal electrocatalysts for water cracking have excellent pro-spects for development of sustainable and clean energy.Highly efficient electrocatalysts for the oxygen evolution reaction(OER)are very important for various energy storage and conversion systems such as water splitting devices and metal-air batteries.This study prepared a NiMo4@C_(3)N_(4) catalyst for OER and hydrogen evolution reaction(HER)by simple methods.The catalyst exhibited an excellent OER activity based on the response at a suitable temperature.To drive a current density of 10 mA-cm^(-2) for OER and HER,the overpotentials required for NiMo4@C_(3)N_(4)-800(prepared at 800℃)were 259 and 118 mV,respectively.A two-electrode system using NiMo4@C_(3)N_(4)-800 needed a very low cell potential of 1.572 V to reach a current density of 10 mA-cm^(-2).In addition,this catalyst showed excellent durability after long-term tests.It was seen to have good catalytic activity and broad application prospects.
