Al/Co co-doped α-Ni（OH）2 samples were prepared by either ultrasonic co-precipitation method （Sample B） or co-precipitation method （Sample A）. The crystal structure and particle size distribution of the prepared...Al/Co co-doped α-Ni（OH）2 samples were prepared by either ultrasonic co-precipitation method （Sample B） or co-precipitation method （Sample A）. The crystal structure and particle size distribution of the prepared samples were examined by X-ray diffraction （XRD） and laser particle size analyzer, respectively. The results show that Sample B has more crystalline defects and smaller average diameter than Sample A. The cyclic voltammetry and electrochemical impedance spectroscopy measurements indicate that Sample B has better electrochemical performance than Sample A, such as better reaction reversibility, lower charge-transfer resistance and better cyclic stability. Proton diffusion coefficient of Sample B is 1.96×10-10cm2/s, which is two times as large as that （9.78×10-11cm2/s） of Sample A. The charge-discharge tests show that the discharge capacity （308 mA·h/g） of Sample B is 25 mA·h/g higher than that of Sample A （283 mA·h/g）.展开更多
Rational design of oxygen evolution reaction(OER)catalysts at low cost would greatly benefit the economy.Taking advantage of earth-abundant elements Si,Co and Ni,we produce a unique-structure where cobalt-nickel silic...Rational design of oxygen evolution reaction(OER)catalysts at low cost would greatly benefit the economy.Taking advantage of earth-abundant elements Si,Co and Ni,we produce a unique-structure where cobalt-nickel silicate hydroxide[Co_(2.5)Ni_(0.5)Si_(2)O_(5)(OH)_(4)]is vertically grown on a reduced graphene oxide(rGO)support(CNS@rGO).This is developed as a low-cost and prospective OER catalyst.Compared to cobalt or nickel silicate hydroxide@rGO(CS@rGO and NS@rGO,respectively)nanoarrays,the bimetal CNS@rGO nanoarray exhibits impressive OER performance with an overpotential of 307 mV@10 mA cm^(-2).This value is higher than that of CS@rGO and NS@rGO.The CNS@rGO nanoarray has an overpotential of 446 mV@100 mA cm^(-2),about 1.4 times that of the commercial RuO_(2)electrocatalyst.The achieved OER activity is superior to the state-of-the-art metal oxides/hydroxides and their derivatives.The vertically grown nanostructure and optimized metal-support electronic interactions play an indispensable role for OER performance improvement,including a fast electron transfer pathway,short proton/electron diffusion distance,more active metal centers,as well as optimized dualatomic electron density.Taking advantage of interlay chemical regulation and the in-situ growth method,the advanced-structural CNS@rGO nanoarrays provide a new horizon to the rational and flexible design of efficient and promising OER electrocatalysts.展开更多
The template effect controlling the structure and morphology of ultrafine particles was described. Ni(OH) 2 powders were prepared by NH 3 coordination precipitation method. The effects of SO 2- 4, NO - 3, Cl -, NH 3, ...The template effect controlling the structure and morphology of ultrafine particles was described. Ni(OH) 2 powders were prepared by NH 3 coordination precipitation method. The effects of SO 2- 4, NO - 3, Cl -, NH 3, pH value on Ni(OH) 2 structure and morphology were investigated experimentally, explained with the theoretical model that the growth units were the polyhedral structure of coordination anions. The results showed that the structure and morphology of Ni(OH) 2 were effectively controlled by the growth units, the dimensions and the linking patterns of the growth units vary with the changes of physical and chemical conditions in the aqueous solution.展开更多
Reaction of 2-pyridone, copper acetate and terbium(or yttrium) perchlorate in acetone with the mole ratio 6: 2: 1 results in the formation of heteronuclear complex Ln_2Cu_4L_8 (HL)_4 (OH)_2 (ClO_4)_4 (H_20)_(10) 2CH_3...Reaction of 2-pyridone, copper acetate and terbium(or yttrium) perchlorate in acetone with the mole ratio 6: 2: 1 results in the formation of heteronuclear complex Ln_2Cu_4L_8 (HL)_4 (OH)_2 (ClO_4)_4 (H_20)_(10) 2CH_3COCH_3(Ln = Tb (1), Y (2)). By recrystallizing (1) in CHCl_3 single crystals were obtained and the structure was determined by four-circle diffractometer. Data showed that the crystal is in space group C2/m with a=27. 454(9)A, b=13, 608A, c=30. 556(11)A, β=99. 89(3)°, v=11245. 7(7. 5)A^3. The structure was solved by a combination of Patterson method and Fourier technique. The final R value is 0. 103. In the structure, four copper and two terbium ions are bridged by 2-pyridone anions to form an essentially octahedral Cu_4Tb_2 core. The terbium atoms are each eight-coordinate and the copper atoms are five-coordinate.展开更多
The electronic structure and chemical bonding of the title comp- lexes have been studied by an unrestricted INDO program made applicable for the lanthanoid compounds.The results indicated:(1)In coordinated bonds O-Ln ...The electronic structure and chemical bonding of the title comp- lexes have been studied by an unrestricted INDO program made applicable for the lanthanoid compounds.The results indicated:(1)In coordinated bonds O-Ln and N-Ln,5d orbitals of Ln have large contribution in all valence orbitals of Ln and 4f orbitals have very small contribution.(2)The covalent chara- cter and ionic character are almost equal in the chemical bond which is comparatively weak between phen,C_2H_5OH and Ln are mainly ionic with some covalent character.展开更多
Two-dimensional (2D)Ni(OH)_(2) nanosheets can theoretically expose their active sites of 100%.Whereas,their intrinsic easy accumulation and low conductivity lead to weak and unsustainable reaction kinetics.Herein,we p...Two-dimensional (2D)Ni(OH)_(2) nanosheets can theoretically expose their active sites of 100%.Whereas,their intrinsic easy accumulation and low conductivity lead to weak and unsustainable reaction kinetics.Herein,we propose a novel halogen chlorine-triggered electrochemical etching strategy to controllably manage the reaction kinetics of 2D Ni(OH)_(2) nanosheets(EE/Cl-Ni(OH)_(2)).It is found that halogen chlorine doping can adjust the interlamellar spacing flexibly and promote the lattice oxygen activation to achieve controlled construction of superficial oxygen defects at the adjustable voltage.The optimal EE/Cl-Ni(OH)_(2) electrode exhibits a high rate capability and excellent specific capacity of 206.9 mA h g^(-1) at 1 A g^(-1) in a three-electrode system,which is more than twice as high as the pristine Ni(OH)_(2).Furthermore,EE/Cl-Ni(OH)_(2) cathode and FeOOH@rGO anode are employed for developing an aqueous Ni-Fe battery with an excellent energy density of 83 W h kg^(-1),a high power density of 17051 W kg^(-1),and robust durability over 20,000 cycles.This strategy exploits a fresh channel for the ingenious fabrication of highefficiency and stable nickel-based deficiency materials for energy storage.展开更多
Loading of cocatalysts can effectively inhibit the recombination of photogenerated carriers in photocatalysts and greatly improve the photocatalytic hydrogen production rate. Cocatalysts can be deposited at the outlet...Loading of cocatalysts can effectively inhibit the recombination of photogenerated carriers in photocatalysts and greatly improve the photocatalytic hydrogen production rate. Cocatalysts can be deposited at the outlet points of electrons using a photochemical method, which is beneficial for the following photocatalytic hydrogen production reaction. H2PO2^– has been used in the photochemical reduction of transition metals because of its special properties. However, the particles formed in the presence of H2PO2^– are very large and highly crystalline, which may inhibit the activity of photocatalysts. In this study, we designed a new method for synthesizing photocatalysts by photodeposition using some other phosphates, aiming to prepare controllable weakly crystalline and small-size cocatalysts to improve the hydrogen production activity. The cocatalyst prepared using H2PO3^– as an inorganic sacrificial agent has an amorphous structure and an average size of about 10 nm. The optimal photocatalytic hydrogen production rate of the obtained Ni(OH)2/g-C3N4(4.36 wt%) is 13707.86 μmol·g^-1·h^-1, which is even higher than the activity of Pt-4.36 wt%/g-C3N4(11210.93 μmol·g^-1·h^-1). Mechanistic studies show that loading of Ni(OH)2 can efficiently accelerate the separation and transfer efficiency of photogenerated charge carriers.展开更多
Spherical Ni（OH）2 particles were prepared by an aqueous solution precipitation route. The structure of spherical Ni（OH）2 was investigated by scanning electron microscopy and transmission electron microscopy and co...Spherical Ni（OH）2 particles were prepared by an aqueous solution precipitation route. The structure of spherical Ni（OH）2 was investigated by scanning electron microscopy and transmission electron microscopy and compared with that of traditional Ni（OH）2. The results show that the spherical nickel hydroxide consists of （Ni（OH）2） spheres with a reticulate structure of platelet-like, which is almost arranged radially and the crystalline grains intervene and connect with each other to form a three-dimensional net. The spherical Ni（OH）2 particle is full of pores, crannies between cleave planes. It is supposed that this structure is beneficial to the structural stability for the spherical particles during the charge/discharge processes and can improve the cycle life of the electrode; the pores and the crannies in spherical particles can shorten the proton diffusion distance and speed its velocity, which may result in that the local polarization is lowered. The electrochemical performances of the spherical Ni（OH）2 are improved by enhancing the conducting properties of the crystalline lattice due to its quick proton diffusion.展开更多
基金Project (10774030) supported by the National Natural Science Foundation of ChinaProject (2008J1-C161) supported by the Science and Technology Program of Guangzhou City of China
文摘Al/Co co-doped α-Ni（OH）2 samples were prepared by either ultrasonic co-precipitation method （Sample B） or co-precipitation method （Sample A）. The crystal structure and particle size distribution of the prepared samples were examined by X-ray diffraction （XRD） and laser particle size analyzer, respectively. The results show that Sample B has more crystalline defects and smaller average diameter than Sample A. The cyclic voltammetry and electrochemical impedance spectroscopy measurements indicate that Sample B has better electrochemical performance than Sample A, such as better reaction reversibility, lower charge-transfer resistance and better cyclic stability. Proton diffusion coefficient of Sample B is 1.96×10-10cm2/s, which is two times as large as that （9.78×10-11cm2/s） of Sample A. The charge-discharge tests show that the discharge capacity （308 mA·h/g） of Sample B is 25 mA·h/g higher than that of Sample A （283 mA·h/g）.
基金supported by the Fundamental Research Funds for the Central Universities(DUT21LK34)Natural Science Foundation of Liaoning Province(2020-MS-113).
文摘Rational design of oxygen evolution reaction(OER)catalysts at low cost would greatly benefit the economy.Taking advantage of earth-abundant elements Si,Co and Ni,we produce a unique-structure where cobalt-nickel silicate hydroxide[Co_(2.5)Ni_(0.5)Si_(2)O_(5)(OH)_(4)]is vertically grown on a reduced graphene oxide(rGO)support(CNS@rGO).This is developed as a low-cost and prospective OER catalyst.Compared to cobalt or nickel silicate hydroxide@rGO(CS@rGO and NS@rGO,respectively)nanoarrays,the bimetal CNS@rGO nanoarray exhibits impressive OER performance with an overpotential of 307 mV@10 mA cm^(-2).This value is higher than that of CS@rGO and NS@rGO.The CNS@rGO nanoarray has an overpotential of 446 mV@100 mA cm^(-2),about 1.4 times that of the commercial RuO_(2)electrocatalyst.The achieved OER activity is superior to the state-of-the-art metal oxides/hydroxides and their derivatives.The vertically grown nanostructure and optimized metal-support electronic interactions play an indispensable role for OER performance improvement,including a fast electron transfer pathway,short proton/electron diffusion distance,more active metal centers,as well as optimized dualatomic electron density.Taking advantage of interlay chemical regulation and the in-situ growth method,the advanced-structural CNS@rGO nanoarrays provide a new horizon to the rational and flexible design of efficient and promising OER electrocatalysts.
文摘The template effect controlling the structure and morphology of ultrafine particles was described. Ni(OH) 2 powders were prepared by NH 3 coordination precipitation method. The effects of SO 2- 4, NO - 3, Cl -, NH 3, pH value on Ni(OH) 2 structure and morphology were investigated experimentally, explained with the theoretical model that the growth units were the polyhedral structure of coordination anions. The results showed that the structure and morphology of Ni(OH) 2 were effectively controlled by the growth units, the dimensions and the linking patterns of the growth units vary with the changes of physical and chemical conditions in the aqueous solution.
基金Project supported by China National Climbing plan and National Nature Science Foundation
文摘Reaction of 2-pyridone, copper acetate and terbium(or yttrium) perchlorate in acetone with the mole ratio 6: 2: 1 results in the formation of heteronuclear complex Ln_2Cu_4L_8 (HL)_4 (OH)_2 (ClO_4)_4 (H_20)_(10) 2CH_3COCH_3(Ln = Tb (1), Y (2)). By recrystallizing (1) in CHCl_3 single crystals were obtained and the structure was determined by four-circle diffractometer. Data showed that the crystal is in space group C2/m with a=27. 454(9)A, b=13, 608A, c=30. 556(11)A, β=99. 89(3)°, v=11245. 7(7. 5)A^3. The structure was solved by a combination of Patterson method and Fourier technique. The final R value is 0. 103. In the structure, four copper and two terbium ions are bridged by 2-pyridone anions to form an essentially octahedral Cu_4Tb_2 core. The terbium atoms are each eight-coordinate and the copper atoms are five-coordinate.
文摘The electronic structure and chemical bonding of the title comp- lexes have been studied by an unrestricted INDO program made applicable for the lanthanoid compounds.The results indicated:(1)In coordinated bonds O-Ln and N-Ln,5d orbitals of Ln have large contribution in all valence orbitals of Ln and 4f orbitals have very small contribution.(2)The covalent chara- cter and ionic character are almost equal in the chemical bond which is comparatively weak between phen,C_2H_5OH and Ln are mainly ionic with some covalent character.
基金supported by the Opening Project of State Key Laboratory of Advanced Chemical Power Sourcesthe Guizhou Provincial Science and Technology Projects(QKHJC-ZK[2021]YB057)+1 种基金the Growth Project of Young Scientific and Technological Talents in Colleges and Universities of Guizhou Province(QKHJCKYZ[2021]252)the Reward and Subsidy Fund Project of Guizhou Education University(Z20210108)。
文摘Two-dimensional (2D)Ni(OH)_(2) nanosheets can theoretically expose their active sites of 100%.Whereas,their intrinsic easy accumulation and low conductivity lead to weak and unsustainable reaction kinetics.Herein,we propose a novel halogen chlorine-triggered electrochemical etching strategy to controllably manage the reaction kinetics of 2D Ni(OH)_(2) nanosheets(EE/Cl-Ni(OH)_(2)).It is found that halogen chlorine doping can adjust the interlamellar spacing flexibly and promote the lattice oxygen activation to achieve controlled construction of superficial oxygen defects at the adjustable voltage.The optimal EE/Cl-Ni(OH)_(2) electrode exhibits a high rate capability and excellent specific capacity of 206.9 mA h g^(-1) at 1 A g^(-1) in a three-electrode system,which is more than twice as high as the pristine Ni(OH)_(2).Furthermore,EE/Cl-Ni(OH)_(2) cathode and FeOOH@rGO anode are employed for developing an aqueous Ni-Fe battery with an excellent energy density of 83 W h kg^(-1),a high power density of 17051 W kg^(-1),and robust durability over 20,000 cycles.This strategy exploits a fresh channel for the ingenious fabrication of highefficiency and stable nickel-based deficiency materials for energy storage.
文摘Loading of cocatalysts can effectively inhibit the recombination of photogenerated carriers in photocatalysts and greatly improve the photocatalytic hydrogen production rate. Cocatalysts can be deposited at the outlet points of electrons using a photochemical method, which is beneficial for the following photocatalytic hydrogen production reaction. H2PO2^– has been used in the photochemical reduction of transition metals because of its special properties. However, the particles formed in the presence of H2PO2^– are very large and highly crystalline, which may inhibit the activity of photocatalysts. In this study, we designed a new method for synthesizing photocatalysts by photodeposition using some other phosphates, aiming to prepare controllable weakly crystalline and small-size cocatalysts to improve the hydrogen production activity. The cocatalyst prepared using H2PO3^– as an inorganic sacrificial agent has an amorphous structure and an average size of about 10 nm. The optimal photocatalytic hydrogen production rate of the obtained Ni(OH)2/g-C3N4(4.36 wt%) is 13707.86 μmol·g^-1·h^-1, which is even higher than the activity of Pt-4.36 wt%/g-C3N4(11210.93 μmol·g^-1·h^-1). Mechanistic studies show that loading of Ni(OH)2 can efficiently accelerate the separation and transfer efficiency of photogenerated charge carriers.
基金Project(50134020) supported by the National Natural Science Foundation of China
文摘Spherical Ni（OH）2 particles were prepared by an aqueous solution precipitation route. The structure of spherical Ni（OH）2 was investigated by scanning electron microscopy and transmission electron microscopy and compared with that of traditional Ni（OH）2. The results show that the spherical nickel hydroxide consists of （Ni（OH）2） spheres with a reticulate structure of platelet-like, which is almost arranged radially and the crystalline grains intervene and connect with each other to form a three-dimensional net. The spherical Ni（OH）2 particle is full of pores, crannies between cleave planes. It is supposed that this structure is beneficial to the structural stability for the spherical particles during the charge/discharge processes and can improve the cycle life of the electrode; the pores and the crannies in spherical particles can shorten the proton diffusion distance and speed its velocity, which may result in that the local polarization is lowered. The electrochemical performances of the spherical Ni（OH）2 are improved by enhancing the conducting properties of the crystalline lattice due to its quick proton diffusion.
