The present experiment was performed with the objective of examining the effects of copper sources and levels on hydrogen peroxide(H_2O_2) generation by mitochondria from broiler hepatocytes. Treatments were applied t...The present experiment was performed with the objective of examining the effects of copper sources and levels on hydrogen peroxide(H_2O_2) generation by mitochondria from broiler hepatocytes. Treatments were applied to compare sources of copper(CuSO_4 versus Cu-Met) and 4 levels of dietary Cu (11,110,220 and 330 mg/kg).Day-old broilers(Cobb 500,Gallus domesticus,n=288) were randomly divided into 8 groups of 36 each and fed diets as follows:Controls(Cu 11 mg/kg) and high copper(Cu 110, 220,and 330 mg/kg),for 60 days under normal conditions.Sample collections were made at 12,36 and 60 days of age to investigate the changes in H_2O_2 generation by mitochondria from hepatocytes.Compared with those of the control diets,H_2O_2 generation by mitochondria in the high copper groups(110 to 330 mg/kg) of the two copper sources were increased(P<0.05 or P<0.01);At days 36 and 60,H_2O_2 generation by hepatic mitochondria from Cu-Met supplementation exceeded that from birds supplemented with CuSO_4 (P<0.05 or P<0.01).In addition,H_2O_2 generation by mitochondria from broilers fed with high dietary copper appeared to be associated with altered function of mitochondrial complexⅣ.The results indicated that dietary supplementation with copper induced oxidative stress damage in liver.At each level of copper supplementation,the organic Cu-Met led to more rapid H_2O_2 generation than did inorganic CuSO_4.The results also suggest that mitochondrial complexⅣmay be targeted under conditions of high dietary copper supplementation.展开更多
Hydrogen peroxide(H_(2)O_(2)) is a high-demand organic chemical reagent and has been widely used in various modern industrial applications. Currently,the prominent method for the preparation of H_(2)O_(2) is the anthr...Hydrogen peroxide(H_(2)O_(2)) is a high-demand organic chemical reagent and has been widely used in various modern industrial applications. Currently,the prominent method for the preparation of H_(2)O_(2) is the anthraquinone oxidation.Unfortunately, it is not conducive to economic and sustainable development since it is a complex process and involves unfriendly environment and potential hazards. In this context, numerous approaches have been developed to synthesize H_(2)O_(2). Among them, photo/electro-catalytic ones are considered as two of the most promising manners for on-site synthesis of H_(2)O_(2). These alternatives are sustainable in that only water or O_(2) is required. Namely, water oxidation(WOR) or oxygen reduction(ORR)reactions can be further coupled with clean and sustainable energy. For photo/electro-catalytic reactions for H_(2)O_(2) generation, the design of the catalysts is extremely important and has been extensively conducted with an aim to obtain ultimate catalytic performance. This article overviews the basic principles of WOR and ORR,followed by the summary of recent progresses and achievements on the design and performance of various photo/electro-catalysts for H_(2)O_(2) generation. The related mechanisms for these approaches are highlighted from theoretical and experimental aspects. Scientific challenges and opportunities of engineering photo/electro-catalysts for H_(2)O_(2) generation are also outlined and discussed.展开更多
Compared with the traditional heteroatom doping,employing heterostructure is a new modulating approach for carbon-based electrocatalysts.Herein,a facile ball milling-assisted route is proposed to synthesize porous car...Compared with the traditional heteroatom doping,employing heterostructure is a new modulating approach for carbon-based electrocatalysts.Herein,a facile ball milling-assisted route is proposed to synthesize porous carbon materials composed of abundant graphene/hexagonal boron nitride(G/h-BN)heterostructures.Metal Ni powder and nanoscale h-BN sheets are used as a catalytic substrate/hard template and“nucleation seed”for the formation of the heterostructure,respectively.As-prepared G/h-BN heterostructures exhibit enhanced electrocatalytic activity toward H_(2)O_(2) generation with 86%-95%selectivity at the range of 0.45-0.75 V versus reversible hydrogen electrode(RHE)and a positive onset potential of 0.79 versus RHE(defined at a ring current density of 0.3 mA cm^(-2))in the alkaline solution.In a flow cell,G/h-BN heterostructured electrocatalyst has a H_(2)O_(2) production rate of up to 762 mmol g_(catalyst)^(-1) h^(-1) and Faradaic efficiency of over 75%during 12 h testing,superior to the reported carbon-based electrocatalysts.The density functional theory simulation suggests that the B atoms at the interface of the G/h-BN heterostructure are the key active sites.This research provides a new route to activate carbon catalysts toward highly active and selective O_(2)-to-H_(2)O_(2) conversion.展开更多
In spite of the numerous advances in the development of H_(2)and O_(2)evolutions upon water splitting,the separation of H_(2)from O_(2)still remains a severe challenge.Herein,the novel dual-functional nanocatalysts Pd...In spite of the numerous advances in the development of H_(2)and O_(2)evolutions upon water splitting,the separation of H_(2)from O_(2)still remains a severe challenge.Herein,the novel dual-functional nanocatalysts Pd/carbon nanosphere(CNS),obtained via immobilization of ultrafine Pd nanoparticles onto CNS,are developed and employed for both selective H_(2)generation from HCOOH dehydrogenation and O_(2)evolution from H_(2)O_(2)decomposition.In these reactions,the highest activities for Pd/CNS-800(i.e.,calcinated at 800℃)are 2478 h−1 and 993 min^(−1)for H_(2)and O_(2)evolution,respectively.The highly efficient and selective“on-off”switch for selective H_(2)generation from HCOOH is successfully realized by pH adjustment.This novel and highly efficient nanocatalyst Pd/CNS-800 not only provides new approaches for the promising application of HCOOH and H_(2)O_(2)as economic and safe H_(2)and O_(2)carriers,respectively,for fuel cells,but also promotes the development of“on-off”switch for on-demand H_(2)evolution.展开更多
In this work,La-doped Mg-Ni multiphase alloys were prepared by resistance melting furnace(RMF)and then modified by high-energy ball milling(HEBM).The hydrolysis H_(2) generation kinetics/thermodynamics of prepared all...In this work,La-doped Mg-Ni multiphase alloys were prepared by resistance melting furnace(RMF)and then modified by high-energy ball milling(HEBM).The hydrolysis H_(2) generation kinetics/thermodynamics of prepared alloys in Na Cl solutions have been investigated with the help of nonlinear and linear fitting by Avrami-Erofeev and Arrhenius equations.Combining the microstructure information before and after hydrolysis and thermodynamics fitting results,the hydrolysis H_(2) generation mechanism based on nucleation&growth has been elaborated.The final H_(2) generation capacities of 0La,5La,10La and 15 La alloys are 677,653,641 and 770 m L·g^(-1)H_(2) in 240 min at291 K,respectively.While,the final H_(2) generation capacities of HEBM 0La,5La,10La and 15 La alloys are 632,824,611 and 653 m L·g^(-1)H_(2) in 20 min at 291 K,respectively.The as-cast 15La alloy and HEMB 5La alloy present the best H_(2) production rates and final H_(2) production capacities,especially the HEBM 5La can rapidly achieve high H_(2) generation capacity(670 and 824 m L·g^(-1)H_(2) )at low temperature(291 K)within short time(5 and 20 min).The difference between the H_(2) generation capacities is mainly originated from the initial nucleation rate of Mg(OH)_(2) and the subsequent processes affected by the microstructures and phase compositions of the hydrolysis alloys.Relative low initial nucleation rate and fully growth of Mg(OH)_(2) nucleus are the premise of high H_(2) generation capacity due to the hydrolysis H_(2) generation process consisted by the nucleation,growth and contacting of Mg(OH)_(2) nucleus.To utilization H_(2) by designing solid state H_(2) generators using optimized Mg-based alloys is expected to be a feasible H_(2) generation strategy at the moment.展开更多
Anchoring molecular cocatalysts on semiconductors has been recognized as a general strategy to boost the charge separation efficiency required for efficient photocatalysis.However,the effect of molecular cocatalysts o...Anchoring molecular cocatalysts on semiconductors has been recognized as a general strategy to boost the charge separation efficiency required for efficient photocatalysis.However,the effect of molecular cocatalysts on energy funneling(i.e.,directional energy transfer)inside semiconductor photocatalysts has not been demonstrated yet.Here we prepared CdS nanorods with both thin and thick rods and anchored the conjugated molecules 2‐mercaptobenzimidazole(MBI)and cobalt molecular catalysts(MCoA)sequentially onto the surface of nanorods.Transient absorption measurements revealed that MBI molecules facilitated energy funneling from thin to thick rods by the electronic coupling between thin and thick nanorods,which is essentially a light‐harvesting antenna approach to enhance the charge generation efficiency in the reaction center(here the thick rods).Moreover,MBI and MCoA molecules selectively extracted photogenerated holes and electrons of CdS nanorods rapidly,leading to efficient charge separation.Consequently,CdS/MBI/MCoA displayed 15 times enhanced photocatalytic H_(2) evolution(1.65 mL)than pure CdS(0.11 mL)over 3 h of illumination.The amount of H_(2) evolution reached 60 mL over 48 h of illumination with a high turnover number of 26294 and an apparent quantum efficiency of 71%at 420 nm.This study demonstrates a novel design principle for next‐generation photocatalysts.展开更多
Two kinds of different mechanistic oscillations can be displayed in the H_2O_2-KSCN-CuSO_4-NaOH system. One discovered by this study is the pH oscillation in a continuous flow stirred tank reactor(CSTR) resulting from...Two kinds of different mechanistic oscillations can be displayed in the H_2O_2-KSCN-CuSO_4-NaOH system. One discovered by this study is the pH oscillation in a continuous flow stirred tank reactor(CSTR) resulting from the oxidation of KSCN. The other is the oscillation of H_2O_2 decomposition in both CSTR and batch reactors(reported by Orbáin in 1986). Under appropriate experimental conditions, the system exhibits a birhythmicity in a CSTR. Two different pH oscillations are reported here. The pH oscillations which accompany the decomposition of H_2O_2 exist in the batch reactor and the CSTR at a high flowrate, but the pH oscillations in a CSTR at a low flowrate originates from proton positive and negative feedback in the oxidation of KSCN. The oscillation of non-catalyzed oxidation of KSCN by hydrogen peroxide in a CSTR can be found. Also we have observed whether Cu^(2+) exists or not in the batch system, the pH increases to near neutral ultimately after pH drops twice.展开更多
基金supported by the National Natural Science Foundation of China(NSFC) awarded to Tang Zhao-xin(grant number:30671550)
文摘The present experiment was performed with the objective of examining the effects of copper sources and levels on hydrogen peroxide(H_2O_2) generation by mitochondria from broiler hepatocytes. Treatments were applied to compare sources of copper(CuSO_4 versus Cu-Met) and 4 levels of dietary Cu (11,110,220 and 330 mg/kg).Day-old broilers(Cobb 500,Gallus domesticus,n=288) were randomly divided into 8 groups of 36 each and fed diets as follows:Controls(Cu 11 mg/kg) and high copper(Cu 110, 220,and 330 mg/kg),for 60 days under normal conditions.Sample collections were made at 12,36 and 60 days of age to investigate the changes in H_2O_2 generation by mitochondria from hepatocytes.Compared with those of the control diets,H_2O_2 generation by mitochondria in the high copper groups(110 to 330 mg/kg) of the two copper sources were increased(P<0.05 or P<0.01);At days 36 and 60,H_2O_2 generation by hepatic mitochondria from Cu-Met supplementation exceeded that from birds supplemented with CuSO_4 (P<0.05 or P<0.01).In addition,H_2O_2 generation by mitochondria from broilers fed with high dietary copper appeared to be associated with altered function of mitochondrial complexⅣ.The results indicated that dietary supplementation with copper induced oxidative stress damage in liver.At each level of copper supplementation,the organic Cu-Met led to more rapid H_2O_2 generation than did inorganic CuSO_4.The results also suggest that mitochondrial complexⅣmay be targeted under conditions of high dietary copper supplementation.
基金supported by Shanxi Province Science Foundation (20210302124446202102070301018)+1 种基金the National Natural Science Joint Foundation (U1710112)Basic Research Project from the Institute of Coal Chemistry, CAS (SCJC-HN-2022-17)。
文摘Hydrogen peroxide(H_(2)O_(2)) is a high-demand organic chemical reagent and has been widely used in various modern industrial applications. Currently,the prominent method for the preparation of H_(2)O_(2) is the anthraquinone oxidation.Unfortunately, it is not conducive to economic and sustainable development since it is a complex process and involves unfriendly environment and potential hazards. In this context, numerous approaches have been developed to synthesize H_(2)O_(2). Among them, photo/electro-catalytic ones are considered as two of the most promising manners for on-site synthesis of H_(2)O_(2). These alternatives are sustainable in that only water or O_(2) is required. Namely, water oxidation(WOR) or oxygen reduction(ORR)reactions can be further coupled with clean and sustainable energy. For photo/electro-catalytic reactions for H_(2)O_(2) generation, the design of the catalysts is extremely important and has been extensively conducted with an aim to obtain ultimate catalytic performance. This article overviews the basic principles of WOR and ORR,followed by the summary of recent progresses and achievements on the design and performance of various photo/electro-catalysts for H_(2)O_(2) generation. The related mechanisms for these approaches are highlighted from theoretical and experimental aspects. Scientific challenges and opportunities of engineering photo/electro-catalysts for H_(2)O_(2) generation are also outlined and discussed.
基金supported by the“National Natural Science Foundation of China (Nos.51902162,21901154)”the FoundationResearch Project of Jiangsu Province (BK20221338)+1 种基金Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources,International Innovation Center for Forest Chemicals and Materials,Nanjing Forestry University,merit-based funding for Nanjing innovation and technology projects,Shanghai Pujiang Program (21PJD022)the Foundation of Jiangsu Key Lab of Biomass Energy and Material (JSBEM-S-202101).
文摘Compared with the traditional heteroatom doping,employing heterostructure is a new modulating approach for carbon-based electrocatalysts.Herein,a facile ball milling-assisted route is proposed to synthesize porous carbon materials composed of abundant graphene/hexagonal boron nitride(G/h-BN)heterostructures.Metal Ni powder and nanoscale h-BN sheets are used as a catalytic substrate/hard template and“nucleation seed”for the formation of the heterostructure,respectively.As-prepared G/h-BN heterostructures exhibit enhanced electrocatalytic activity toward H_(2)O_(2) generation with 86%-95%selectivity at the range of 0.45-0.75 V versus reversible hydrogen electrode(RHE)and a positive onset potential of 0.79 versus RHE(defined at a ring current density of 0.3 mA cm^(-2))in the alkaline solution.In a flow cell,G/h-BN heterostructured electrocatalyst has a H_(2)O_(2) production rate of up to 762 mmol g_(catalyst)^(-1) h^(-1) and Faradaic efficiency of over 75%during 12 h testing,superior to the reported carbon-based electrocatalysts.The density functional theory simulation suggests that the B atoms at the interface of the G/h-BN heterostructure are the key active sites.This research provides a new route to activate carbon catalysts toward highly active and selective O_(2)-to-H_(2)O_(2) conversion.
基金National Natural Science Foundation of China,Grant/Award Number:21805166111 Project of China,Grant/Award Number:D20015+1 种基金Ministryof Education,Hubei province,China,Grant/Award Number:T2020004Foundation of Science and Technology Bureau of Yichang City,Grant/Award Number:A21‐3‐012。
文摘In spite of the numerous advances in the development of H_(2)and O_(2)evolutions upon water splitting,the separation of H_(2)from O_(2)still remains a severe challenge.Herein,the novel dual-functional nanocatalysts Pd/carbon nanosphere(CNS),obtained via immobilization of ultrafine Pd nanoparticles onto CNS,are developed and employed for both selective H_(2)generation from HCOOH dehydrogenation and O_(2)evolution from H_(2)O_(2)decomposition.In these reactions,the highest activities for Pd/CNS-800(i.e.,calcinated at 800℃)are 2478 h−1 and 993 min^(−1)for H_(2)and O_(2)evolution,respectively.The highly efficient and selective“on-off”switch for selective H_(2)generation from HCOOH is successfully realized by pH adjustment.This novel and highly efficient nanocatalyst Pd/CNS-800 not only provides new approaches for the promising application of HCOOH and H_(2)O_(2)as economic and safe H_(2)and O_(2)carriers,respectively,for fuel cells,but also promotes the development of“on-off”switch for on-demand H_(2)evolution.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.51704188,51702199,61705125,51802181)the State Key Laboratory of Solidification Processing in NWPU(Grant No.SKLSP201809)+2 种基金Natural Science Foundation of Shaanxi Province(Grant No.2019JQ-099)Research Starting Foundation from Shaanxi University of Science and Technology(Grant No.2016GBJ-04)the financial support of China Scholarship Council(Grant No.201808610089)。
文摘In this work,La-doped Mg-Ni multiphase alloys were prepared by resistance melting furnace(RMF)and then modified by high-energy ball milling(HEBM).The hydrolysis H_(2) generation kinetics/thermodynamics of prepared alloys in Na Cl solutions have been investigated with the help of nonlinear and linear fitting by Avrami-Erofeev and Arrhenius equations.Combining the microstructure information before and after hydrolysis and thermodynamics fitting results,the hydrolysis H_(2) generation mechanism based on nucleation&growth has been elaborated.The final H_(2) generation capacities of 0La,5La,10La and 15 La alloys are 677,653,641 and 770 m L·g^(-1)H_(2) in 240 min at291 K,respectively.While,the final H_(2) generation capacities of HEBM 0La,5La,10La and 15 La alloys are 632,824,611 and 653 m L·g^(-1)H_(2) in 20 min at 291 K,respectively.The as-cast 15La alloy and HEMB 5La alloy present the best H_(2) production rates and final H_(2) production capacities,especially the HEBM 5La can rapidly achieve high H_(2) generation capacity(670 and 824 m L·g^(-1)H_(2) )at low temperature(291 K)within short time(5 and 20 min).The difference between the H_(2) generation capacities is mainly originated from the initial nucleation rate of Mg(OH)_(2) and the subsequent processes affected by the microstructures and phase compositions of the hydrolysis alloys.Relative low initial nucleation rate and fully growth of Mg(OH)_(2) nucleus are the premise of high H_(2) generation capacity due to the hydrolysis H_(2) generation process consisted by the nucleation,growth and contacting of Mg(OH)_(2) nucleus.To utilization H_(2) by designing solid state H_(2) generators using optimized Mg-based alloys is expected to be a feasible H_(2) generation strategy at the moment.
文摘Anchoring molecular cocatalysts on semiconductors has been recognized as a general strategy to boost the charge separation efficiency required for efficient photocatalysis.However,the effect of molecular cocatalysts on energy funneling(i.e.,directional energy transfer)inside semiconductor photocatalysts has not been demonstrated yet.Here we prepared CdS nanorods with both thin and thick rods and anchored the conjugated molecules 2‐mercaptobenzimidazole(MBI)and cobalt molecular catalysts(MCoA)sequentially onto the surface of nanorods.Transient absorption measurements revealed that MBI molecules facilitated energy funneling from thin to thick rods by the electronic coupling between thin and thick nanorods,which is essentially a light‐harvesting antenna approach to enhance the charge generation efficiency in the reaction center(here the thick rods).Moreover,MBI and MCoA molecules selectively extracted photogenerated holes and electrons of CdS nanorods rapidly,leading to efficient charge separation.Consequently,CdS/MBI/MCoA displayed 15 times enhanced photocatalytic H_(2) evolution(1.65 mL)than pure CdS(0.11 mL)over 3 h of illumination.The amount of H_(2) evolution reached 60 mL over 48 h of illumination with a high turnover number of 26294 and an apparent quantum efficiency of 71%at 420 nm.This study demonstrates a novel design principle for next‐generation photocatalysts.
基金Supported by NSFC(29573109) and Research fund of CUMT.
文摘Two kinds of different mechanistic oscillations can be displayed in the H_2O_2-KSCN-CuSO_4-NaOH system. One discovered by this study is the pH oscillation in a continuous flow stirred tank reactor(CSTR) resulting from the oxidation of KSCN. The other is the oscillation of H_2O_2 decomposition in both CSTR and batch reactors(reported by Orbáin in 1986). Under appropriate experimental conditions, the system exhibits a birhythmicity in a CSTR. Two different pH oscillations are reported here. The pH oscillations which accompany the decomposition of H_2O_2 exist in the batch reactor and the CSTR at a high flowrate, but the pH oscillations in a CSTR at a low flowrate originates from proton positive and negative feedback in the oxidation of KSCN. The oscillation of non-catalyzed oxidation of KSCN by hydrogen peroxide in a CSTR can be found. Also we have observed whether Cu^(2+) exists or not in the batch system, the pH increases to near neutral ultimately after pH drops twice.
