Rational control on the D(donor)–A(acceptor)system of photocatalyst for boosting sacrificial-agentfree photosynthesis of hydrogen peroxide(H_(2)O_(2))from open air and water is highly desirable for H_(2)O_(2) product...Rational control on the D(donor)–A(acceptor)system of photocatalyst for boosting sacrificial-agentfree photosynthesis of hydrogen peroxide(H_(2)O_(2))from open air and water is highly desirable for H_(2)O_(2) production but remains a challenging issue.To this end,we developed a novel conversion strategy by controlling the reaction dynamics to rationally construct a three-component D–A–D isomer.Without any sacrificial agent,this three-component D–A–D isomer was found to enable an H_(2)O_(2) production rate of 4463μmol g^(−1) h^(−1) in open air and water,which was 1.9-and 1.5-fold higher,respectively,than the corresponding two-component D–A isomers.Accompanied is the O_(2) utilization and conversion efficiency of 99.8%,exceeding all established photocatalysts for such usage.The catalytic mechanism stemmed from a dual-channel pathway from both oxygen reduction reaction(ORR)and water oxidation reaction(WOR).The construction of a threecomponent D–A–D isomer was found to not only enhance the efficiency in the generation,transmission,and separation of photogenerated carriers but also optimize the O_(2) fixing site relative to the two-component D–A isomers.In addition,we further confirmed the application of this three-component D–A–D isomerization for real-time H_(2)O_(2) production from various real-life environments in open air and sunlight.展开更多
Frequency generation in highly multimode nonlinear optical systems is inherently a complex process,giving rise to an exceedingly convoluted landscape of evolution dynamics.While predicting and controlling the global c...Frequency generation in highly multimode nonlinear optical systems is inherently a complex process,giving rise to an exceedingly convoluted landscape of evolution dynamics.While predicting and controlling the global conversion efficiencies in such nonlinear environments has long been considered impossible,here,we formally address this challenge even in scenarios involving a very large number of spatial modes.By utilizing fundamental notions from optical statistical mechanics,we develop a universal theoretical framework that effectively treats all frequency components as chemical reactants/products,capable of undergoing optical thermodynamic reactions facilitated by a variety of multi-wave mixing effects.These photon-photon reactions are governed by conservation laws that directly determine the optical temperatures and chemical potentials of the ensued chemical equilibria for each frequency species.In this context,we develop a comprehensive stoichiometric model and formally derive an expression that relates the chemical potentials to the optical stoichiometric coefficients,in a manner akin to atomic/molecular chemical reactions.This advancement unlocks new predictive capabilities that can facilitate the optimization of frequency generation in highly multimode photonic arrangements,surpassing the limitations of conventional schemes that rely exclusively on nonlinear optical dynamics.Notably,we identify a universal regime of Rayleigh-Jeans thermalization where an optical reaction at near-zero optical temperatures can promote the complete and entropically irreversible conversion of light to the fundamental mode at a target frequency.Our theoretical results are corroborated by numerical simulations in settings where second-harmonic generation,sum-frequency generation and four-wave mixing processes can manifest.展开更多
基金supported financially by the Open Project Program of the National Key Laboratory of Uranium Resources Exploration-Mining and Nuclear Remote Sensing,China(grant no.2024QZ-TD-18)the National Natural Science Foundations of China(NSFC+1 种基金grant no.22376024)the Jiangxi project,China(grant no.DHSQT22021007).The authors would also like to thank Wenqian Liu from Shiyanjia Lab,China(www.Shiyanjia.com)for help with X-ray diffraction(XRD)and SEM analysis.
文摘Rational control on the D(donor)–A(acceptor)system of photocatalyst for boosting sacrificial-agentfree photosynthesis of hydrogen peroxide(H_(2)O_(2))from open air and water is highly desirable for H_(2)O_(2) production but remains a challenging issue.To this end,we developed a novel conversion strategy by controlling the reaction dynamics to rationally construct a three-component D–A–D isomer.Without any sacrificial agent,this three-component D–A–D isomer was found to enable an H_(2)O_(2) production rate of 4463μmol g^(−1) h^(−1) in open air and water,which was 1.9-and 1.5-fold higher,respectively,than the corresponding two-component D–A isomers.Accompanied is the O_(2) utilization and conversion efficiency of 99.8%,exceeding all established photocatalysts for such usage.The catalytic mechanism stemmed from a dual-channel pathway from both oxygen reduction reaction(ORR)and water oxidation reaction(WOR).The construction of a threecomponent D–A–D isomer was found to not only enhance the efficiency in the generation,transmission,and separation of photogenerated carriers but also optimize the O_(2) fixing site relative to the two-component D–A isomers.In addition,we further confirmed the application of this three-component D–A–D isomerization for real-time H_(2)O_(2) production from various real-life environments in open air and sunlight.
基金supported by the Air Force Offce of Scientific Research(AFOSR)Multidisciplinary University Research Initiative(MURI)award on Novel light-matter interactions in topologically non-trivial Weyl semimetal structures and systems(award No.FA9550-20-1-0322)AFOSR MURI award on Programmable systems with non-Hermitian quantum dynamics(award no.FA9550-21-1-0202)+5 种基金ONR MURI award on the classical entanglement of light(award No.N00014-20-1-2789)the Army Research Offce(W911NF-23-1-0312)the Department of Energy(DE-SCo022282)W.M.Keck Foundation,the Department of Energy(DE-SCo025224),MPS Simons collaboration(Simons grant No.733682)US Air Force Research Laboratory(FA86511820019)AFRL-Applied Research Solutions(S03015)(FA8650-19-C-1692).
文摘Frequency generation in highly multimode nonlinear optical systems is inherently a complex process,giving rise to an exceedingly convoluted landscape of evolution dynamics.While predicting and controlling the global conversion efficiencies in such nonlinear environments has long been considered impossible,here,we formally address this challenge even in scenarios involving a very large number of spatial modes.By utilizing fundamental notions from optical statistical mechanics,we develop a universal theoretical framework that effectively treats all frequency components as chemical reactants/products,capable of undergoing optical thermodynamic reactions facilitated by a variety of multi-wave mixing effects.These photon-photon reactions are governed by conservation laws that directly determine the optical temperatures and chemical potentials of the ensued chemical equilibria for each frequency species.In this context,we develop a comprehensive stoichiometric model and formally derive an expression that relates the chemical potentials to the optical stoichiometric coefficients,in a manner akin to atomic/molecular chemical reactions.This advancement unlocks new predictive capabilities that can facilitate the optimization of frequency generation in highly multimode photonic arrangements,surpassing the limitations of conventional schemes that rely exclusively on nonlinear optical dynamics.Notably,we identify a universal regime of Rayleigh-Jeans thermalization where an optical reaction at near-zero optical temperatures can promote the complete and entropically irreversible conversion of light to the fundamental mode at a target frequency.Our theoretical results are corroborated by numerical simulations in settings where second-harmonic generation,sum-frequency generation and four-wave mixing processes can manifest.
