P-induced electron transfer interaction for enhanced selective hydrogenation rearrangement of furfural to cyclopentanone

Optimizing the intrinsic activity of non-noble metal by precisely tailoring electronic structure offers an appealing way to construct cost-effective catalysts for selective biomass valorization.Herein,we reported a P-doping bifunctional catalyst(Ni-P/mSiO_(2))that achieved 96.6%yield for the hydrogenation rearrangement of furfural to cyclopentanone at mild conditions(1 MPaH_(2),150°C).The turnover frequency of Ni-P/mSiO_(2)was 411.9 h^(-1),which was 3.2-fold than that of Ni/mSiO_(2)(127.2 h^(-1)).Detailed characterizations and differential charge density calculations revealed that the electron-deficient Niδ+species were generated by the electron transfer from Ni to P,which promoted the ring rearrangement reaction.Density functional theory calculations illustrated that the presence of P atoms endowed furfural tilted adsorb on the Ni surface by the C=O group and facilitated the desorption of cyclopentanone.This work unraveled the connection between the localized electronic structures and the catalytic properties,so as to provide a promising reference for designing advanced catalysts for biomass valorization.

Coupling ferromagnetic ordering electron transfer channels and surface reconstructed active species for spintronic electrocatalysis of water oxidation

Sluggish reaction kinetics of oxygen evolution reaction(OER), resulting from multistep proton-coupled electron transfer and spin constriction, limits overall efficiency for most reported catalysts. Herein, using modeled ZnFe_(2-x)Ni_xO_(4)(0 ≤ x ≤ 0.4) spinel oxides, we aim to develop better OER electrocatalyst through combining the construction of ferromagnetic(FM) ordering channels and generation of highly active reconstructed species. The number of symmetry-breaking Fe–O–Ni structure links to the formation of FM ordering electron transfer channels. Meanwhile, as the number of Ni^(3+)increases, more ligand holes are formed, beneficial for redirecting surface reconstruction. The electro-activated ZnFe_(1.6)Ni_(0.4)O_(4) shows the highest specific activity, which is 13 and 2.5 times higher than that of ZnFe_(2)O_(4) and unactivated ZnFe_(1.6)Ni_(0.4)O_(4), and even superior to the benchmark IrO_(2) under the overpotential of 350 mV. Applying external magnetic field can make electron spin more aligned, and the activity can be further improved to 39 times of ZnFe_(2)O_(4). We propose that intriguing FM exchange-field interaction at FM/paramagnetic interfaces can penetrate FM ordering channels into reconstructed oxyhydroxide layers, thereby activating oxyhydroxide layers as spin-filter to accelerate spin-selective electron transfer. This work provides a new guideline to develop highly efficient spintronic catalysts for water oxidation and other spin-forbidden reactions.

Promoting and controlling electron transfer of furfural oxidation efficiently harvest electricity,furoic acid,hydrogen gas and hydrogen peroxide

Conventional chemical oxidation of aldehydes such as furfural to corresponding acids by molecular oxygen usually needs high pressure to increase the solubility of oxygen in aqueous phase,while electrochemical oxidation needs input of external electric energy.Herein,we developed a liquid flow fuel cell(LFFC)system to achieve oxidation of furfural in anode for furoic acid production with co-production of hydrogen gas.By controlling the electron transfer in cathode for reduction of oxygen,efficient generation of electricity or production of H_(2)O_(2)were achieved.Metal oxides especially Ag_(2)O have been screened as the efficient catalyst to promote the oxidation of aldehydes,while liquid redox couples were used for promoting the kinetics of oxygen reduction.A novel alkaline-acidic asymmetric design was also used for anolyte and catholyte,respectively,to promote the efficiency of electron transfer.Such an LFFC system achieves efficient conversion of chemical energy of aldehyde oxidation to electric energy and makes full use the transferred electrons for high-value added products without input of external energy.With(VO_(2))_(2)SO_(4)as the electron carrier in catholyte for four-electron reduction of oxygen,the peak output power density(Pmax)at room temperature reached 261 mW/cm^(2)with furoic acid and H_(2)yields of 90%and 0.10 mol/mol furfural,respectively.With anthraquinone-2-sulfonate(AQS)as the cathodic electron carrier,Pmaxof 60 mW/cm^(2)and furoic acid,H_(2)and H_(2)O_(2)yields of 0.88,0.15 and 0.41 mol/mol furfural were achieved,respectively.A new reaction mechanism on furfural oxidation on Ag_(2)O anode was proposed,referring to one-electron and two-electron reaction pathways depending on the fate of adsorbed hydrogen atom transferred from furfural aldehyde group.

Activating coordinative conjugated polymer via interfacial electron transfer for efficient CO_(2) electroreduction

With tunable local electronic environment,high mass density of MN4sites,and ease of preparation,metal-organic conjugated coordinative polymer(CCP) with inherent electronic conductivity provides a promising alternative to the well-known M-N-C electrocatalysts.Herein,the coordination reaction between Cu^(2+)and 1,2,4,5-tetraaminobenzene(TAB) was conducted on the surface of metallic Cu nanowires,forming a thin layer of CuN4-based CCP(Cu-TAB) on the Cu nanowire.More importantly,interfacial transfer of electrons from Cu core to the CuN4-based CCP nanoshell was observed within the resulting CuTAB@Cu,which was found to enrich the local electronic density of the CuN4sites.As such,the CuTAB@Cu demonstrates much improved affinity to the*COOH intermediate formed from the rate determining step;the energy barrier for C-C coupling,which is critical to convert CO_(2)into C2products,is also decreased.Accordingly,it delivers a current density of-9.1 mA cm^(-2)at a potential as high as 0.558 V(vs.RHE) in H-type cell and a Faraday efficiency of 46.4% for ethanol.This work emphasizes the profound role of interfacial interaction in tuning the local electronic structure and activating the CuN4-based CCPs for efficient electroreduction of CO_(2).

Coupled intramolecular/heterointerfacial electron transfer in polyelectrolyte-shielded Iso-type black phosphorus hetero-structure boosts oxygen reduction kinetics

Searching new structured black phosphorus(BP)and exploring intriguing functions and applications have become a hot topic so far.Here,we introduce a novel Iso-type black phosphorus heterostructure guided by first principle calculation,which features unique heterointerface and electronic coupling interaction via stacking assembly of exfoliated black phosphorus(EBP)and amine-functionalized EBP(N-EBP).Inspired by the theoretical results,we constructed the Iso-type heterostructure comprising of ultrathin exfoliated few-layered EBP and N-EBP,both of which were derived from identical bulk BP.The purposive amine-functionalization not only creates positively-charged P atoms on N-EBP as effective active sites via N-induced intramolecular electron transfer(IET)but also endows N-EBP with lower work function relative to EBP,while the unique EBP/N-EBP Iso-type heterostructure engenders directional heterointerfacial electron transfer(HET).The coupled IET/HET effects optimize the charge redistribution to afford favorable O_(2)adsorption.In this case,our unique strategy for the first time exploits the inherent catalytic capability of BP toward the oxygen reduction reaction(ORR)and enables the first use of BP as metal-free ORR catalysts for Zn-air cells.The newly-designed heterostructure facilitates a 4-e^(-)transfer ORR relative to inactive EBP or N-EBP.Importantly,the polymer-shielded heterostructure acts as efficient air electrodes to endow a primary Zn-air cell with high stability,large capacity and high energy density—superior to the commercial Pt/C-enabled cell.This study as the first report on metal-free BP-based ORR catalysts and air electrodes not only extends BP's application scopes but also renders new insight toward design of electronically-coupled superstructures for energy-related applications.

Combined pretreatment using CaO and liquid fraction of digestate of rice straw: Anaerobic digestion performance and electron transfer

To improve anaerobic digestion(AD)efficiency of rice straw,solid alkaline CaO and the liquid fraction of digestate(LFD)were used as pretreatment agents of rice straw.The results showed that AD performance of rice straw with CaOLFD pretreatment was optimal in different pretreatment methods of the CaO+LFD,CaOLFD,LFD+CaO,CaO,and LFD.The maximum methane yield(314 ml(g VS)^(-1))and the highest VFAs concentration(14851 mg·L^(-1) on day 3)of the CaOLFD pretreatment group were 81%and 118%higher than that of the control group,respectively.Under the action of solid alkaline CaO,the bacteria of Clostridium,Atopostipes,Sphaerochaeta,Tissierella,Thiopseudomonas,Rikenellaceae,and Sedimentibacter could build up co-cultures with the archaeal of Methanosaeta,Methanobacterium,and Methanosarcina performing direct interspecies electron transfer(DIET)and improving AD performance of rice straw.Therefore,the combined pretreatment using CaO and LFD could not only pretreat rice straw but also stimulate co-cultures of microorganism to establish DIET enhancing AD efficiency.

Significant effect of electron transfer between current collector and active material on high rate performance of Li_4Ti_5O_(12)

The rate and cycling performances of the electrode materials are affected by many factors in a practical complicated electrode process. Learning about the limiting step in a practical electrochemical reaction is very important to effectively improve the electrochemical performances of the electrode materials. Li4Ti5O12, as a zero-strain material, has been considered as a promising anode material for long life Li-ion batteries. In this study, our results show that the Li4Ti5O12 pasted on Cu or graphite felt current collector exhibits unexpectedly higher rate performance than on A1 current collector. For Li4Ti5O12, the electron transfer between current collector and active material is the critical factor that affects its rate and cycling performances.

Photo-induced intramolecular electron transfer and intramolecular vibrational relaxation of rhodamine 6G in DMSO revealed by multiplex transient grating spectroscopy

Photo-induced intramolecular electron transfer （PIET） and intramolecular vibrational relaxation （IVR） dynamics of the excited state of rhodamine 6G （Rh6G＋） in DMSO are investigated by multiplex transient grating. Two major compo- nents are resolved in the dynamics of Rh6G＋. The first component, with a lifetime τTPIET = 140 fs-260 fs, is attributed to PIET from the phenyl ring to the xanthene plane. The IVR process occurring in the range ZIVR = 3.3 ps-5.2 ps is much slower than the first component. The PIET and IVR processes occurring in the excited state of Rh6G＋ are quantitatively determined, and a better understanding of the relationship between these processes is obtained.

Effect of SDBS on interfacial electron transfer at the liquid/liquid interface by thin layer method

The effect of an adsorbed anionic surfactant sodium dodecyl benzene sulfonate （SDBS） on electron transfer （ET） reaction between ferricyanide aqueous solution and decamethylferrocene （DMFc） located on the adjacent organic phase was investigated for the first time by thin layer method. The adsorption of SDBS at the interface resulted in a decay in the cathodic plateau current of bimolecular reaction with increasing concentrations of SDBS in aqueous phase. However, the rate constant of electron transfer （ket） increased monotonically as the SDBS concentrations increased from 0 to 200 p, moFL. The experimental results showed that SDBS formed patches on the interface and influenced the structure of electrical double layer. 2009 Xiao Quan Lu. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Study of Electron Transfer Reactions Between a Water/1,2-Dichloroethane Interface by Scanning Electrochemical Microscopy

Electron transfer (ET) from ascorbic acid (AA) in aqueous to ferrocene (Fc) in1,2-dichloroethane (DCE) was probed by the scanning electrochemical microscopy (SECM). Therate constants were extracted from the dependence of the steady-state current at ultramicro-electrode(UME, tip) on the distance between the tip and the phase boundary by comparison to theoreticalworking cures.

Enhancing the dynamic electron transfer of Au species on wormhole-like TS-1 for boosting propene epoxidation performance with H_(2) and O_(2)

Engineering unique electronic structure of catalyst to boost catalytic performance is of prime scientific and industrial importance.Herein,the identification of intrinsic electronic sensitivity for direct propene epoxidation was first achieved over highly stable Au/wormhole-like TS-1 catalyst.Results show that the electron transfer of Au species can be regulated by manipulating the dynamic evolutions and contents of Au valence states,thus resulting in different catalytic performance in 100 h time-on-stream.By DFT calculations,kinetic analysis and multicharacterizations,it is found that the Au^(0) species with higher electronic population can easily transfer more electrons to activate surface O_(2) compared with Au^(1+) and Au^(3+) species.Moreover,there is a positive correlation between Au^(0) content and activity.Based on this correlation,a facile strategy is further proposed to boost Au^(0) percentage,resulting in the reported highest PO formation rate without adding promoters.This work harbors tremendous guiding significance to the design of highly efficient Au/Ti-containing catalyst for propene epoxidation with H_(2) and O_(2).

Carbon dots regulate the interface electron transfer and catalytic kinetics of Pt-based alloys catalyst for highly efficient hydrogen oxidation

The regulation of interface electron-transfer and catalytic kinetics is very important to design the efficient electrocatalyst for alkaline hydrogen oxidation reaction(HOR).Here,we show the Pt-Ni alloy nanoparticles(PtNi_(2))have an enhanced HOR activity compared with single component Pt catalyst.While,the interface electron-transfer kinetics of PtNi_(2)catalyst exhibits a very wide electron-transfer speed distribution.When combined with carbon dots(CDs),the interface charge transfer of PtNi_(2)-CDs composite is optimized,and then the PtNi_(2)-5 mg CDs exhibits about 2.67 times and 4.04 times higher mass and specific activity in 0.1 M KOH than that of 20%commercial Pt/C.In this system,CDs also contribute to trapping H^(+)and H_(2)O generated during HOR,tuning hydrogen binding energy(HBE),and regulating interface electron transfer.This work provides a deep understanding of the interface catalytic kinetics of Pt-based alloys towards highly efficient HOR catalysts design.

Evaluation of Transient Absorption Spectra of N, N, N, N- Tetra - ( p -methylphenyl ) - 4, 4- diamino - 1, 1- diphenyl Ether ( TPDAE ) for Electron Transfer from TPDAE to Fullerenes ( C_(60) / C_(70) ) by Laser Flash Photolysis

Photoinduced electron transfer processes between fullerenes (C60 / C70) and N, N, N, N tetra - ( p-methylphenyl ) - 4, 4 diamino - 1, 1- diphenyl ether ( TPDAE ) have been studied by nanosecond laser flash photolysis. Quantum yields and rate constants of electron transfer from TPDAE to excited triplet state of fullerenes (C60 / C70 ) in benzonitrile have been evaluated by observing the transient absorption bands in the near-IR region where the excited triplet state, radical anion of fullerenes ( C60 / C70 ) and radical cations of TPDAE appear.

Synthesis and Cation-Mediated Electron Transfer in Fluorescence Quenching of Donor-Acceptor Podands

Reduced rate constants of photoinduced electron transfer in intramolecular fluorescence quenching of donor-acceptor podands induced by cation-complexation are observed in the highly exothermic reactions.

Salt-induced Electron Transfer Photooxidation of Cholesterol in Nonpolar Solvents

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Photoinduced Electron Transfer in Host-Guest Complexes of Naphthalene Derivatives with p-NBCD and m-NBCD

A number of naphthalene derivatives containing adamantanamine binding moiety and an （CH2）. （n = 2, 3, 4, 5, 6） spacer were prepared as electron donor. A supramolecular assembly was fabricated by the inclusion complexation of the donor substrates with the host molecules, mono-6-O-p-nitrobenzoyl-β-cyclodextrin （p-NBCD） and mono-6-O-m-nitrobenzoyl-β-cyclodextrin （m-NBCD）, in water. The fluorescence quenching in these systems was studied and detailed Stern-Volmer constants were measured. It revealed that an efficient photoinduced electron transfers （PET） between the naphthalene donors and the cyclodextrin acceptors occurred.

The Electron Transfer Reaction between ρ-Nitrobenzoates and β-N, N-Dimethylaminonaphthalene

A few of p-nitrobenzoates were synthesized, and the electron transfer of them with b-N, N-dimethylaminonaphthalene (DMAN) in methanol solution was studied. Steady-state fluore-scence results showed the cyclodextrin moiety in p-nitrobenzoyl-b-cyclodextrin would block the electron transfer pathway from DMAN compared with other electron acceptors, thus, reduced the electron transfer efficiency.

Photoinduced Electron Transfer (PET) between C_(60) and Amines in Micelle Solution A Kinetic ESR Study

As indicated by kinetic ESR measurements, the key factor to affect electron recombination in the process of PET between C60 and amines is the space between donor and C60. To increase solubility of C60 in water, it was incorporated into micelle of surfactants. ]

Room Temperature Phosphorescence pH Switch Based on Photo-induced Electron Transfer

In this paper, photoinduced electron transfer(PET) phosphoroionophore, N-(1-bromo- 2-naphthylmethyl)-diethanolamine (BND) was synthesized and its phosphorescent characteristics were studied. The experimental results showed that strong phosphorescence could be observed in b-cyclodextrin aqueous solution only at low pH value. This system combined AND and NOT function to produce a three-input inhibit (INH) logic gate.

Electron Transfer Reaction Between Desoxyadenosine and Triplet 2-Methyl-1,4-naphthaquinone:A Laser Photolysis Study

Introduction Electron transfer oxidation of DNA by triplet artificial photonuclease reveals a bright prospect of its application in biology and medicine. Both molecular orbital calculation and laser experiments have indicated that the homo guanine sequence should be the final localization site of photoexcited hole via long range migration within DNA. However, the direct observation of the produced ion pairs of biomolecules especially the stabilized radical cation DNA or its components is hampered by the overwhelming transient absorption of protonated radical anion of photosensitizers, such as 2-methyl-1,4-naphthaguinonel （MQ）.