In the global carbon neutrality context,green hydrogen,a key carrier of clean energy,requires urgent breakthroughs in production technology.In water electrolysis,the high energy consumption and low efficiency of the o...In the global carbon neutrality context,green hydrogen,a key carrier of clean energy,requires urgent breakthroughs in production technology.In water electrolysis,the high energy consumption and low efficiency of the oxygen evolution reaction(OER)at the anode severely limit overall energy conversion efficiency.The electrocatalytic selective oxidation of aldehydes shows potential to replace the OER due to its low thermodynamic potential and fast kinetics,and it can transform aldehydes into high-value carboxylic acids through precise catalyst control.This paper reviews catalyst design strategies for this process,focusing on reaction mechanisms,design principles,and structure-performance relationships.By analyzing the activation of CvO bonds and C-H bond cleavage kinetics,core design principles based on electronic structure regulation and synergistic effects are proposed,and a catalyst performance model is established using in situ characterization and theoretical calculations.This provides theoretical guidance for designing efficient catalysts and prospects for future research directions,such as non-precious metal catalyst development and complex reaction network regulation,offering new ideas for the industrial application of“green hydrogen-high-value chemicals”co-production technology.展开更多
It is an important and challenging task to develop new infrared(IR)birefringent materials to promote the development of laser technology.In this work,a novel thioantimonate with the highest Cu-to-Sb ratio in the quate...It is an important and challenging task to develop new infrared(IR)birefringent materials to promote the development of laser technology.In this work,a novel thioantimonate with the highest Cu-to-Sb ratio in the quaternary X/Cu/Sb/Q(X=cations;Q=chalcogen)system,namely CsCu_(3)SbS_(4),was structurally designed and prepared by the strategy of alkali metal introduction into known Cu_(3)SbS_(4).Interestingly,CsCu_(3)SbS_(4)has novel two-dimensional anionic[Cu_(3)SbS_(4)]^(−)layers formed by the unprecedented onedimensional[Cu_(3)S_(3)S_(3/2)]^(6−)chains and discrete[SbS_(3)]_(3)−clusters.Meanwhile,compared with the prototype Cu_(3)SbS_(4),CsCu_(3)SbS_(4)realizes an enormous birefringence boost from 0 to 0.232,which was confirmed by both experimental results and theoretical calculations.This study enriches the sources of thioantimonates and sheds more light on the structure–property relationships of IR birefringent materials.展开更多
Inorganic nonlinear optical(NLO)crystals have attracted considerable attention due to their profound applications in laser technology.In this study,we present the synthesis of a novel cadmium bismuth vanadate crystal,...Inorganic nonlinear optical(NLO)crystals have attracted considerable attention due to their profound applications in laser technology.In this study,we present the synthesis of a novel cadmium bismuth vanadate crystal,Cd_(2)BiVO_(6),through a spontaneous crystallization approach.The title compound,containing d^(0) V^(5+),d^(10) Cd^(2+),and stereo-active lone pair effect(Bi^(3+))cations,crystallizes in the non-centrosymmetric orthorhombic space group Cmc2_(1)(No.36),characterized by isolated[VO_(4)]tetrahedra,twisted 1D chains[Bi_(2)O_(8)]_(∞)and pseudo-2D layers[Cd_(6)O_(30)]_(∞).Remarkably,the structural characteristics endow Cd_(2)BiVO_(6)with a strong second harmonic generation response of around 1.4×KDP(25-53μm),and a notably enlarged birefringence of 0.127 at 1064 nm,exceeding 6 times that of the vanadate NLO crystal Li_(3)VO_(4)(~0.021).Thermophysical analyses unveil its exceptional thermal stability up to 900℃with a commendable congruent nature.Moreover,Cd_(2)BiVO_(6)features a wide transparency range,with the UV and IR cutoff absorption edges observed at 0.395 and~5.8μm,respectively.Besides,the observed optical characteristics associated with the microstructure of Cd_(2)BiVO_(6)are explained through electronic structure calculations.展开更多
Laser-sensitive primary explosives(LSPEs)have long been a focus of attention as the material foundation for safer and more efficient laser-initiation technology.However,LSPEs often have poor safety due to their struct...Laser-sensitive primary explosives(LSPEs)have long been a focus of attention as the material foundation for safer and more efficient laser-initiation technology.However,LSPEs often have poor safety due to their structural characteristics,which greatly limits the development and application of laser initiating technology.In this work,we introduced the concept of multidentate chelates into LSPEs and innovatively propose the concept of energetic quadridentate chelates.To achieve this highly creative idea,we synthesized an energetic flexible chelating ligand,namely,1,2-bis(3-nitroamino-1,2,4-triazol-5-yl)ethane(BNATE),and prepared a novel metal quadridentate chelate,namely,[Cu(BNATE)·2H_(2)O](1),by chelating it with Cu^(2+).Through a series of tests,including X-ray single-crystal diffraction analysis,thermogravimetric analysis,and differential scanning calorimetry(TG-DSC),and evaluation of the safety and detonation performance,it was proven that this compound adhered to the high stability characteristics of the chelate,and its safety and detonation performance were superior to previous LSPEs.Moreover,through laserinitiation experiments,it was determined that the compound had excellent photosensitivity and a lower laser-initiation threshold.To explain the reason why the chelate structure is specifically sensitive to a laser,diffuse reflection ultraviolet and TD-DFT simulations were conducted,which not only demonstrated experimentally that chelation had a good enhancement effect on the laser photosensitivity but also confirmed the mode of electron transfer in the quadridentate chelate structure.展开更多
基金supported by the National Natural Science Foundation of China(52272222)the Taishan Scholar Young Talent Program(tsqn201909114,tsqn201909123)the University Youth Innovation Team of Shandong Province(202201010318).
文摘In the global carbon neutrality context,green hydrogen,a key carrier of clean energy,requires urgent breakthroughs in production technology.In water electrolysis,the high energy consumption and low efficiency of the oxygen evolution reaction(OER)at the anode severely limit overall energy conversion efficiency.The electrocatalytic selective oxidation of aldehydes shows potential to replace the OER due to its low thermodynamic potential and fast kinetics,and it can transform aldehydes into high-value carboxylic acids through precise catalyst control.This paper reviews catalyst design strategies for this process,focusing on reaction mechanisms,design principles,and structure-performance relationships.By analyzing the activation of CvO bonds and C-H bond cleavage kinetics,core design principles based on electronic structure regulation and synergistic effects are proposed,and a catalyst performance model is established using in situ characterization and theoretical calculations.This provides theoretical guidance for designing efficient catalysts and prospects for future research directions,such as non-precious metal catalyst development and complex reaction network regulation,offering new ideas for the industrial application of“green hydrogen-high-value chemicals”co-production technology.
基金supported by the National Natural Science Foundation of China(No.52171277,51778570,51879230,21771179,and 22175175)the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZR118)+2 种基金the Natural Science Foundation of Fujian Province(2019J01133)the Natural Science Basic Research Program of Shaanxi(2020JQ-710)the Doctoral Scientific Research Startup Foundation of Shaanxi University of Science and Technology(2018BJ-07).
文摘It is an important and challenging task to develop new infrared(IR)birefringent materials to promote the development of laser technology.In this work,a novel thioantimonate with the highest Cu-to-Sb ratio in the quaternary X/Cu/Sb/Q(X=cations;Q=chalcogen)system,namely CsCu_(3)SbS_(4),was structurally designed and prepared by the strategy of alkali metal introduction into known Cu_(3)SbS_(4).Interestingly,CsCu_(3)SbS_(4)has novel two-dimensional anionic[Cu_(3)SbS_(4)]^(−)layers formed by the unprecedented onedimensional[Cu_(3)S_(3)S_(3/2)]^(6−)chains and discrete[SbS_(3)]_(3)−clusters.Meanwhile,compared with the prototype Cu_(3)SbS_(4),CsCu_(3)SbS_(4)realizes an enormous birefringence boost from 0 to 0.232,which was confirmed by both experimental results and theoretical calculations.This study enriches the sources of thioantimonates and sheds more light on the structure–property relationships of IR birefringent materials.
基金supported by the National Key R&D Program of China(2021YFA0717800)National Natural Science Foundation of China(Grant No.52002273 and 62104124)State Key Laboratory of Crystal Materials,Shandong University(No.KF2303).
文摘Inorganic nonlinear optical(NLO)crystals have attracted considerable attention due to their profound applications in laser technology.In this study,we present the synthesis of a novel cadmium bismuth vanadate crystal,Cd_(2)BiVO_(6),through a spontaneous crystallization approach.The title compound,containing d^(0) V^(5+),d^(10) Cd^(2+),and stereo-active lone pair effect(Bi^(3+))cations,crystallizes in the non-centrosymmetric orthorhombic space group Cmc2_(1)(No.36),characterized by isolated[VO_(4)]tetrahedra,twisted 1D chains[Bi_(2)O_(8)]_(∞)and pseudo-2D layers[Cd_(6)O_(30)]_(∞).Remarkably,the structural characteristics endow Cd_(2)BiVO_(6)with a strong second harmonic generation response of around 1.4×KDP(25-53μm),and a notably enlarged birefringence of 0.127 at 1064 nm,exceeding 6 times that of the vanadate NLO crystal Li_(3)VO_(4)(~0.021).Thermophysical analyses unveil its exceptional thermal stability up to 900℃with a commendable congruent nature.Moreover,Cd_(2)BiVO_(6)features a wide transparency range,with the UV and IR cutoff absorption edges observed at 0.395 and~5.8μm,respectively.Besides,the observed optical characteristics associated with the microstructure of Cd_(2)BiVO_(6)are explained through electronic structure calculations.
基金financial support from the National Natural Science Foundation of China(21975232).
文摘Laser-sensitive primary explosives(LSPEs)have long been a focus of attention as the material foundation for safer and more efficient laser-initiation technology.However,LSPEs often have poor safety due to their structural characteristics,which greatly limits the development and application of laser initiating technology.In this work,we introduced the concept of multidentate chelates into LSPEs and innovatively propose the concept of energetic quadridentate chelates.To achieve this highly creative idea,we synthesized an energetic flexible chelating ligand,namely,1,2-bis(3-nitroamino-1,2,4-triazol-5-yl)ethane(BNATE),and prepared a novel metal quadridentate chelate,namely,[Cu(BNATE)·2H_(2)O](1),by chelating it with Cu^(2+).Through a series of tests,including X-ray single-crystal diffraction analysis,thermogravimetric analysis,and differential scanning calorimetry(TG-DSC),and evaluation of the safety and detonation performance,it was proven that this compound adhered to the high stability characteristics of the chelate,and its safety and detonation performance were superior to previous LSPEs.Moreover,through laserinitiation experiments,it was determined that the compound had excellent photosensitivity and a lower laser-initiation threshold.To explain the reason why the chelate structure is specifically sensitive to a laser,diffuse reflection ultraviolet and TD-DFT simulations were conducted,which not only demonstrated experimentally that chelation had a good enhancement effect on the laser photosensitivity but also confirmed the mode of electron transfer in the quadridentate chelate structure.
