氮化硼纳米片负载纳米Cu2O及其催化还原对硝基苯酚

doi:10.15541/jim20180487

摘要/Abstract

摘要：

纳米级氧化亚铜具有高效的催化性能, 但较差的稳定性使其应用受限。本研究采用简单可控的抗坏血酸液相还原及气氛焙烧法, 制备了一种兼具高催化活性与催化稳定性的Cu₂O/BNNSs-OH负载型催化剂, 其中以聚乙烯吡咯烷酮(PVP)与水相变提供的“推-拉”作用剥离的氮化硼纳米片(BNNSs)为载体, 液相还原反应体系pH=11时, 抗坏血酸向Cu ²⁺滴定制备的Cu₂O纳米颗粒(2~7 nm)为活性组分。通过扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)、原子力显微镜(AFM)、X射线衍射仪(XRD)、X射线光电子能谱仪(XPS)、傅里叶变换红外光谱仪(FT-IR)及拉曼(Raman)光谱仪等对样品的形貌和结构进行表征, 结果表明: Cu₂O纳米粒子不但高度分散于载体表面, BNNSs对Cu₂O还有一定的稳定作用, 避免其被氧化成CuO。将Cu₂O/BNNSs-OH应用于对硝基苯酚催化还原反应中, 该催化剂表现出同贵金属类似的高催化活性, 5次重复利用后的转化率仍高达90%。

关键词: 氮化硼纳米片, 冻融法, PVP, Cu₂O纳米粒子, 对硝基苯酚, 对氨基苯酚

Abstract:

Despite excellent catalytic capability, Cu₂O nanomaterial exhibits weak stability which limits its application. In this study, a novel kind of Cu₂O, Cu₂O/BNNSs-OH, supported catalyst with highly catalytic efficiency and stability, was facilely fabricated via a controllable liquid phase reduction of ascorbic acid and combining with an annealing process. Cu₂O/BNNSs-OH catalyst was synthesized by using boron nitride nanosheets (BNNSs), prepared by the “push-pull” effect of polyvinylpyrrolidone (PVP) and water phase change, as a supporter and spherical Cu₂O nanoparticles (2-7 nm) prepared by forward titration (ascorbic acid→Cu ²⁺, solution with a pH 11) as active components. Morphology and structure of as-obtained samples were characterized by scanning electron microscopy (SEM), high resolution transmission electronic microscopy (HRTEM), atomic force microscopy (AFM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), and Raman spectroscopy. The results of the synthetic method showed that spherical Cu₂O nanoparticles were uniformly dispersed on the carrier surface and BNNSs displayed some stabilization effect on Cu₂O which could be prevented from being oxidized into CuO. Moreover, the catalytic activity was investigated by catalytic reduction reaction of 4-nitrophenol to 4-aminophenol. Cu₂O/BNNSs-OH with high catalytic activity similar to the noble metal catalyst for the reduction of 4-nitrophenol is highly reusable for five successive cycles without significant degradation and activity loss.

Key words: boron nitride nanosheets, freeze-thaw method, PVP, Cu₂O nanoparticles, 4-nitrophenol

中图分类号:

TQ174

朱萌萌, 李国华, 张雪明, 翟佳欣, 甘思平, 宋潇. 氮化硼纳米片负载纳米Cu₂O及其催化还原对硝基苯酚[J]. 无机材料学报, 2019, 34(8): 817-826.

ZHU Meng-Meng, LI Guo-Hua, ZHANG Xue-Ming, ZHAI Jia-Xin, GAN Si-Ping, SONG Xiao. Boron Nitride Nanosheets Supported Cu₂O Nanoparticles: Synthesis and Catalytic Reduction for 4-nitrophenol[J]. Journal of Inorganic Materials, 2019, 34(8): 817-826.

图/表 11

图1 冻融法剥离的机理示意图

Fig. 1 Gentle water freezing-thawing exfoliation of h-BN triggered by freezing expansion force and against reaggregation by PVP coating

图2 不同表面活性剂剥离的BNNSs紫外-可见吸收光谱图(a), BNNSs、PVP/ BNNSs、纯PVP的TGA曲线(b)

Fig. 2 Absorption spectra for h-BN dispersions stabilized with various surfactants (a), TGA curves of washed BNNSs, PVP stabilized BNNSs, and pure PVP (b)

图3 BNNSs的SEM ((a)右上角为块状h-BN放大图片), TEM (b)和HRTEM照片((c)左上角为SEAD图案), 及其AFM图(d)、高度轮廓图(e)和厚度统计图(f)

Fig. 3 SEM image (a) with inset showing bulk h-BN, TEM image (b), HRTEM image (c) with inset showing corresponding SAED pattern, AFM image (d), and the corresponding height profile of random nanosheet along the red trace (e) and statistical analyse on the number of monolayers per sheet (f) of BNNSs

图4 氮化硼剥离前后的XRD图谱(a)和Raman谱图(b)

Fig. 4 XRD patterns (a) and Raman spectra (b) of h-BN and BNNSs

图5 加入抗坏血酸前混合溶液不同pH(a: pH 5-7, b: pH 9-11)下得到前驱体的XRD谱(A), 抗坏血酸还原反应体系不同pH下制备的样品的XRD图谱(B), Cu2O/BNNSs-OH的红外光谱图(C, pH11)

Fig. 5 XRD patterns of precursors (A) before adding VC at pH 5-7 (a) and pH 9-11 (b), specimens (B) in ascorbic acid solution reduction system at different pH, and FT-IR spectra of the as-obtained samples at pH 11 (C)

图6 Cu2O/BNNSs-OH的的XPS谱图

Fig. 6 XPS of B1s, N1s, O1s, Cu2p of the sample Cu2O/BNNSs-OH

图7 羟基化氮化硼纳米片(a), CuO/BNNSs-OH(b)在不同pH抗坏血酸还原反应体系下制备样品的SEM照片((c) pH 3, (d) pH 5, (e) pH 7, (f) pH 9, (g) pH 11), Cu2O/BNNSs-OH的HRTEM照片(h~i) (h)右上角为Cu2O NPs粒径统计图, (i)左下角为SEAD图案及晶格条纹图案, pH 11

Fig. 7 SEM images of BNNSs-OH (a), CuO/BNNSs-OH (b), products prepared in ascorbic acid solution reduction system at different pH((c) pH 3, (d) pH 5, (e) pH 7, (f) pH 9, (g) pH 11), HRTEM images of Cu2O/BNNSs-OH (h-i) with inset in (h) showing the corresponding size distributions of Cu2O NPs with inset in (i) showing the corresponding selected SAED pattern and lattice fringe pattern at pH 11

图8 不同混合方式下制备Cu2O/BNNSs-OH的SEM照片

Fig. 8 SEM images of products under different mixing ways (a) VC→Cu2+; (b) Cu2+→VC

图9 Cu/BNNSs-OH(a)、CuO/BNNSs-OH(b)、Cu2O/BNNSs-OH(c)、Cu2O-Cu/BNNSs-OH(d)以及Cu2O/BNNSs(e)催化还原4-NP紫外-可见吸收光谱图, At/A0与化学反应时间T的关系图(f)

Fig. 9 UV-Vis absorption spectra of Cu/BNNSs-OH (a), CuO/BNNSs-OH (b), Cu2O/BNNSs-OH (c), Cu2O-Cu/BNNSs-OH (d), and Cu2O/BNNSs (e) in contrast to the reduction of 4-NP as a function of reaction time with excess amount of NaBH4 over various catalysts (f)

图10 加入NaBH4(a)、BNNSs-OH(b)前后4-NP的紫外-可见光谱图, 及Cu2O/BNNSs-OH催化还原4-NP的机理示意图

Fig. 10 UV-Vis absorption spectra of 4-NP solution before and after NaBH4 (a) and BNNSs-OH (b) additions, and schematic of the reduction of 4-NP to 4-AP over the Cu2O/ BNNSs-OH (c)

图11 Cu2O/BNNSs-OH催化还原4-NP循环利用图(A), 5次循环前后Cu2O/BNNSs-OH催化剂XRD图谱(B)

Fig. 11 Reusability of Cu2O/BNNSs-OH catalyst for the reduction of 4-NP with NaBH4 (A), XRD patterns of Cu2O/BNNSs- OH catalyst before and after five usages (B)

参考文献 31

[1]	RATH P C, SAIKIA D, MISHRA M , et al. Exceptional catalytic performance of ultrafine Cu₂O nanoparticles confined in cubic mesoporous carbon for 4-nitrophenol reduction. Applied Surface Science, 2018,427:1217-1226.
[2]	NIU H, LIU S, CAI Y , et al. MOF derived porous carbon supported Cu/Cu₂O composite as high performance non-noble catalyst. Microporous and Mesoporous Materials, 2016,219:48-53.
[3]	ROCHA M, COSTA P, PEREIRA C , et al. L-serine-functionalized montmorillonite decorated with Au nanoparticles: a new highly efficient catalyst for the reduction of 4-nitrophenol. Journal of Catalysis, 2018,361:143-155.
[4]	MAHAM M, NASROLLAHZADEH M, SAJADI S M , et al. Biosynthesis of Ag/reduced graphene oxide/Fe₃O₄ using Lotus garcinii leaf extract and its application as a recyclable nanocatalyst for the reduction of 4-nitrophenol and organic dyes. Journal of Colloid & Interface Science, 2017,497:33-42.
[5]	ZOU P P, WANG M S, ZHAO L , et al. One-step synthesis of Pt@three-dimensional graphene composite hydrogel: an efficient recyclable catalyst for reduction of 4-nitrophenol. Applied Organometallic Chemistry, 2016,30(8):722-725.
[6]	COCCIA F, TNUCCI L, BOSCO D , et al. One-pot synthesis of lignin-stabilised platinum and palladium nanoparticles and their catalytic behaviour in oxidation and reduction reaction. Green Chemistry, 2012,14(4):1073-1078.
[7]	GACEM N, DIAO P . Effect of solvent polarity on the assembly behavior of PVP coated rhodium nanoparticles. Colloids and Surfaces A, 2013,417:32-38. DOI URL
[8]	YANG X F, WANG A, QIAO B , et al. Single-atom catalysts: a new frontier in heterogeneous catalysis. Accounts of Chemical Research, 2013,46(8):1740-1748.
[9]	OH S D, KIM M R, CHOI S H , et al. Radiolytic synthesis of Pd-M (M=Ag, Au, Cu, Ni and Pt) alloy nanoparticles and their use in reduction of 4-nitrophenol. Journal of Industrial and Engineering Chemistry, 2008,14(5):687-692.
[10]	MUNNIK P, DE JONGH P E, DE JONG K P . Recent developments in the synthesis of supported catalysts. Chemical Reviews, 2015,46(38):6687-6714.
[11]	YAN X, WANG X, TANG Y , et al. Unusual loading-dependent sintering-resistant properties of gold nanoparticles supported within extra-large mesopores. Chemistry of Materials, 2013,25(9):1556-1563.
[12]	NAG A, RAIDOGIA K, HEMBRAM K P , et al. Graphene analogues of BN: novel synthesis and properties. ACS Nano, 2010,4(3):1539-1544.
[13]	LASKOWSKI R, BLAHA P, SCHWARZ K . Bonding of hexagonal BN to transition metal surfaces: an ab initio density-functional theory study. Physical Review B Condensed Matter, 2008,78(78):1436-1446.
[14]	HUANG C, CHEN C, YE X , et al. Stable colloidal boron nitride nanosheet dispersion and its potential application in catalysis. Journal of Materials Chemistry A, 2013,1(39):12192-12197.
[15]	ZHENG M, LIU Y, GU Y , et al. Synthesis and characterization of boron nitride sponges as a novel support for metal nanoparticles. Science in China Series B: Chemistry, 2008,51(3):205-210.
[16]	LIANG H L . Research on the physical properties of fully hydrogenated boron nitride films. Jinan: Shandong University. 2012:1-24.
[17]	LI C, WANG T L, WU Y Z , et al. Fabrication of two-dimensional nanosheets via water freezing expansion exfoliation. Nanotechnology, 2014,25(49):1-6.
[18]	GUARDIA L, PAREDES J I, ROZADA R , et al. Production of aqueous dispersions of inorganic graphene analogues by exfoliation and stabilization with non-ionic surfactants. RSC Advances, 2014,4(27):14115-14127.
[19]	LIU Q, KAZUAKI N, KENSUKE K , et al. Effects of reaction parameters on the preparation of submicron Cu particles by liquid phase reduction method and the study of reaction mechanism. Powder Technology, 2013,241(3):98-104.
[20]	SONG H, LI T, ZHANG J , et al. Highly anisotropic Sb₂Se₃ nanosheets: gentle exfoliation from the bulk precursors possessing 1D crystal structurep. Advanced Materials, 2017,29(29):1-7.
[21]	SMITH R J, KIBG P J, LOTYA M , et al. Large-scale exfoliation of inorganic layered compounds in aqueous surfactant solutions. Advanced Materials, 2011,23(34):3944-3948.
[22]	MA P, SPENCER J T . Non-covalent stabilization and functionalization of boron nitride nanosheets (BNNSs) by organic polymers: formation of complex BNNSs-containing structures. Journal of Materials Science, 2015,50(1):313-323. DOI URL
[23]	GAO W, ZHAO Y, YIN H . Lateral size selection of liquid exfoliated hexagonal boron nitride nanosheets. RSC Advances, 2018,8:5976-5983. DOI URL
[24]	HUMINIC G, HUMINIC A . Application of nanofluids in heat exchangers: a review. Renewable & Sustainable Energy Reviews, 2012,16(8):5625-5638.
[25]	PARK K S, LEE D Y, KIM K J , et al. Observation of a hexagonal BN surface layer on the cubic BN film grown by dual ion beam sputter deposition. Applied Physics Letters, 1997,70(3):315-317.
[26]	WAGNER C D, RIGGS W M, Davis L E , et al. Muilenber, handbook of X-ray Photoelectron Spectroscopy. erkin Elmer Corporation Physical Electronics Division, USA, 1979: 1-190.
[27]	ESPINOS J P, MORALES J, BARRANCO A , et al. Interface effects for Cu, CuO, and Cu₂O deposited on SiO₂ and ZrO₂. XPS determination of the valence state of copper in Cu/SiO₂ and Cu/ZrO₂ Catalysts. Journal of Physical Chemistry B, 2002,106(27):6921-6929.
[28]	SUN Q, LI Y, SUN X , et al. Improved photoelectrical performance of single-crystal TiO₂ nanorod arrays by surface sensitization with copper quantum dots. ACS Sustainable Chemistry & Engineering, 2013,1(7):798-804.
[29]	YAN X Y, TONG X L, ZHANG Y F , et al. Cuprous oxide nanoparticles dispersed on reduced graphene oxide as an efficient electrocatalyst for oxygen reduction reaction. Chemical Communications, 2012,48(13):1892-1894.
[30]	MICHIKAZU H, TAKESHI K, MUTSUKO K , et al. Cu₂O as a photocatalyst for overall water splitting under visible light irradiation. Chemical Communication, 1998,3:357-358.
[31]	HUANG J, VOGEHR S, TANG S , et al. Highly catalytic Pd-Ag bimetallic dendrites. Journal of Physical Chemistry C, 2010,114(35):15005-15010.

氮化硼纳米片负载纳米Cu₂O及其催化还原对硝基苯酚

Boron Nitride Nanosheets Supported Cu₂O Nanoparticles: Synthesis and Catalytic Reduction for 4-nitrophenol

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