A new mixed-metal sulfido incomplete cubane cluster [(MoCuS3) (O) (μ-dtp) (PPh3)3] Cdtp = S2P (OC2H5)2] has been prepared by reaction of (NH4)2MoOS3 with Cu(dtp) (PPh3)2 in dimethylformamide solution. It crystallizes...A new mixed-metal sulfido incomplete cubane cluster [(MoCuS3) (O) (μ-dtp) (PPh3)3] Cdtp = S2P (OC2H5)2] has been prepared by reaction of (NH4)2MoOS3 with Cu(dtp) (PPh3)2 in dimethylformamide solution. It crystallizes in the triclinic space group P1, a = 13.810(5), b = 19. 753(5), c=11. 719(4) A. α=99. 42(2), β=107. 24(3),γ=88. 05(3)°, V = 3012(2)A3, Dc = l. 51g/cm3and Z = 2. Final R=0. 046, Rw = 0. 056 for 7700 unique intensity data(I≥3σ(I)). The central unit [MoCu3S3]3+ can be described as a distorted incomplete cube with one missing corner. The Mo atom is tetrahedrally coordinated by three μ3-S atoms and one terminal O atom. Two Cu atoms are tetrahedrally coordinated whereas the third Cu atom has a highly distorted trigonal environment. The mean Mo - Cu bond length is 2. 752A. The Cu...Cu distances are in the range of 3. 200(1) -3. 740(1) A which are too long to form bonds.展开更多
A new heterometallic cluster W2Ag2S4(tdt)2(PPh3)2·CH2Cl2(H2tdt=H2CH3C6H3S2)(Ⅱ) has been prepared from the reaction of a well-defined molecular building block W2S4(tdt)22-(I) with Ag complex. The compound has bee...A new heterometallic cluster W2Ag2S4(tdt)2(PPh3)2·CH2Cl2(H2tdt=H2CH3C6H3S2)(Ⅱ) has been prepared from the reaction of a well-defined molecular building block W2S4(tdt)22-(I) with Ag complex. The compound has been characterized by X-ray diffraction study, IR., UV-Vis Spectroscopy and cyclic voltammetry.Crystallographic data for the compound are: space group P21/n,a=17.234(4), b=17.622(4), c=19. 094(4) A,β= 99. 22(2)°,V=5704(2) A3, Z=4,final R=0. 042 and Rw=0. 049 for 5983 independent reflections with I≥3σ(I) The structure analysis reveals that the cluster contains a cubane-like core [W2Ag2S4]4+ . The coordination geometry of each tungsten atom is a square pyramid just as that in the building block. Two types of metal-metal bonds of W-W bond and W-Ag bond exist in the core. The distance between two Ag atoms is out of the range of bonding.展开更多
High-entropy alloys(HEAs)contain multiple principal alloying elements,but usually with simple crystal structures.Quasicrystals are structurally complex phases,but are generally dominated by only one element.However,ne...High-entropy alloys(HEAs)contain multiple principal alloying elements,but usually with simple crystal structures.Quasicrystals are structurally complex phases,but are generally dominated by only one element.However,nearequiatomic high-entropy quasicrystals have rarely been reported because they are difficult to prepare experimentally and predict theoretically.Therefore,the preparation and crystal structures of near-equiatomic high-entropy quasicrystals have drawn much interest.We report a quinary decagonal quasicrystal(DQC)with near-equiatomic alloying elements in Al20Si20Mn20Fe20Ga20 melt-spun ribbons,which is the first to our knowledge.Meanwhile,the structural features of the DQC are characterized in detail.The configurational entropy of both the alloy and DQC satisfies the entropy-based criterion for HEAs,suggesting a high-entropy DQC.Our findings provide a new strategy to develop high-entropy quasicrystals.展开更多
The introduction of carbon interstitials into high-entropy alloys(HEAs)provides an effective way to improve their properties.However,all such HEA systems explored so far are limited to those with the face-centered-cub...The introduction of carbon interstitials into high-entropy alloys(HEAs)provides an effective way to improve their properties.However,all such HEA systems explored so far are limited to those with the face-centered-cubic(fcc)structure.Here we report the structural,mechanical and physical properties of the refractory(Nb_(0.375)Ta_(0.25)Mo_(0.125)W_(0.125)Re_(0.125))_(100−x)C_(x) HEAs over a wide x range of 0≤x≤20.It is found that,whereas the starting HEA(x=0)is composed of a major body-centered-cubic(bcc)phase with significant impurities,the bcc phase fraction increases with the C concentration and achieves almost 100%at x=20.Moreover,the increase of C content x results in an expansion of the bcc lattice,an enhancement of the microhardness,an increase in residual resistivity and a small variation of density of states at the Fermi level.All these features are consistent with the expectation that carbon atoms occupy the interstitial site.For x≥11.1,the X-ray photoelectron spectroscopy indicates the bond formation between the carbon and metal atoms,suggesting that some carbon atoms may also reside in the lattice site.In addition,a semiquantitative analysis shows that the enhanced mixing entropy caused by carbon addition plays a key role in stabilizing the(nearly)single solid-solution phase.Our study not only provides the first series of carbon interstitial HEAs with a bcc structure,but also helps to better understand the alloying behavior of carbon in refractory HEAs.展开更多
In this paper,13 kinds of transition metals are studied as catalysts for the hydrogen production from coal pyrolysis, and relationships between the catalytic activity of a transition metal and its outer electron confi...In this paper,13 kinds of transition metals are studied as catalysts for the hydrogen production from coal pyrolysis, and relationships between the catalytic activity of a transition metal and its outer electron configuration,d% of transition metals and geometric configuration are summarized.Experimental results show that the same group of transition metals show good similarity for hydrogen production from coal pyrolysis;the d%of transition metals which have activity for hydrogen production from coal pyrolysis is between 40%-50%;all transition metals which have catalytic activity possess either a face-centered cubic or a hexagonal crystal structure.Therefore,it is important to choose a transition metal with an appropriate d%and crystal structure as the catalyst for hydrogen production from coal pyrolysis.展开更多
文摘A new mixed-metal sulfido incomplete cubane cluster [(MoCuS3) (O) (μ-dtp) (PPh3)3] Cdtp = S2P (OC2H5)2] has been prepared by reaction of (NH4)2MoOS3 with Cu(dtp) (PPh3)2 in dimethylformamide solution. It crystallizes in the triclinic space group P1, a = 13.810(5), b = 19. 753(5), c=11. 719(4) A. α=99. 42(2), β=107. 24(3),γ=88. 05(3)°, V = 3012(2)A3, Dc = l. 51g/cm3and Z = 2. Final R=0. 046, Rw = 0. 056 for 7700 unique intensity data(I≥3σ(I)). The central unit [MoCu3S3]3+ can be described as a distorted incomplete cube with one missing corner. The Mo atom is tetrahedrally coordinated by three μ3-S atoms and one terminal O atom. Two Cu atoms are tetrahedrally coordinated whereas the third Cu atom has a highly distorted trigonal environment. The mean Mo - Cu bond length is 2. 752A. The Cu...Cu distances are in the range of 3. 200(1) -3. 740(1) A which are too long to form bonds.
文摘A new heterometallic cluster W2Ag2S4(tdt)2(PPh3)2·CH2Cl2(H2tdt=H2CH3C6H3S2)(Ⅱ) has been prepared from the reaction of a well-defined molecular building block W2S4(tdt)22-(I) with Ag complex. The compound has been characterized by X-ray diffraction study, IR., UV-Vis Spectroscopy and cyclic voltammetry.Crystallographic data for the compound are: space group P21/n,a=17.234(4), b=17.622(4), c=19. 094(4) A,β= 99. 22(2)°,V=5704(2) A3, Z=4,final R=0. 042 and Rw=0. 049 for 5983 independent reflections with I≥3σ(I) The structure analysis reveals that the cluster contains a cubane-like core [W2Ag2S4]4+ . The coordination geometry of each tungsten atom is a square pyramid just as that in the building block. Two types of metal-metal bonds of W-W bond and W-Ag bond exist in the core. The distance between two Ag atoms is out of the range of bonding.
基金the National Natural Science Foundation of China(51871015 and 51471024)the Selfdetermined Project of the State Key Laboratory for Advanced Metals and Materials(2016Z-13)。
文摘High-entropy alloys(HEAs)contain multiple principal alloying elements,but usually with simple crystal structures.Quasicrystals are structurally complex phases,but are generally dominated by only one element.However,nearequiatomic high-entropy quasicrystals have rarely been reported because they are difficult to prepare experimentally and predict theoretically.Therefore,the preparation and crystal structures of near-equiatomic high-entropy quasicrystals have drawn much interest.We report a quinary decagonal quasicrystal(DQC)with near-equiatomic alloying elements in Al20Si20Mn20Fe20Ga20 melt-spun ribbons,which is the first to our knowledge.Meanwhile,the structural features of the DQC are characterized in detail.The configurational entropy of both the alloy and DQC satisfies the entropy-based criterion for HEAs,suggesting a high-entropy DQC.Our findings provide a new strategy to develop high-entropy quasicrystals.
基金the foundation of Westlake University for financial supportThe work at Zhejiang University was supported by the National Key Research and Development Program of China(2017YFA0303002)。
文摘The introduction of carbon interstitials into high-entropy alloys(HEAs)provides an effective way to improve their properties.However,all such HEA systems explored so far are limited to those with the face-centered-cubic(fcc)structure.Here we report the structural,mechanical and physical properties of the refractory(Nb_(0.375)Ta_(0.25)Mo_(0.125)W_(0.125)Re_(0.125))_(100−x)C_(x) HEAs over a wide x range of 0≤x≤20.It is found that,whereas the starting HEA(x=0)is composed of a major body-centered-cubic(bcc)phase with significant impurities,the bcc phase fraction increases with the C concentration and achieves almost 100%at x=20.Moreover,the increase of C content x results in an expansion of the bcc lattice,an enhancement of the microhardness,an increase in residual resistivity and a small variation of density of states at the Fermi level.All these features are consistent with the expectation that carbon atoms occupy the interstitial site.For x≥11.1,the X-ray photoelectron spectroscopy indicates the bond formation between the carbon and metal atoms,suggesting that some carbon atoms may also reside in the lattice site.In addition,a semiquantitative analysis shows that the enhanced mixing entropy caused by carbon addition plays a key role in stabilizing the(nearly)single solid-solution phase.Our study not only provides the first series of carbon interstitial HEAs with a bcc structure,but also helps to better understand the alloying behavior of carbon in refractory HEAs.
文摘In this paper,13 kinds of transition metals are studied as catalysts for the hydrogen production from coal pyrolysis, and relationships between the catalytic activity of a transition metal and its outer electron configuration,d% of transition metals and geometric configuration are summarized.Experimental results show that the same group of transition metals show good similarity for hydrogen production from coal pyrolysis;the d%of transition metals which have activity for hydrogen production from coal pyrolysis is between 40%-50%;all transition metals which have catalytic activity possess either a face-centered cubic or a hexagonal crystal structure.Therefore,it is important to choose a transition metal with an appropriate d%and crystal structure as the catalyst for hydrogen production from coal pyrolysis.
