Chinese Journal of Catalysis 40 (2019) 1339–1344

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Communication (Special Issue on Celebrating the 100th Anniversary of Nankai University)

Development of a bismuth-based metal-organic framework for
photocatalytic hydrogen production
Yejun Xiao a,b, Xiangyang Guo a, Junxue Liu c, Lifang Liu a,b, Fuxiang Zhang a,*, Can Li a,#
a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy, the
Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian 116023, Liaoning, China
b University of Chinese Academy of Sciences, Beijing 100049, China

c State Key Laboratory of Molecular Reaction Dynamics, the Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute

of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

A R T I C L E I N F O A B S T R A C T

Article history: A novel 3D bismuth-organic framework (called Bi-TBAPy) single crystal was synthesized by em-
Received 20 December 2018 ploying 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H4TBAPy) as an organic linker. The study demon-
Accepted 8 February 2019 strates that the Bi-TBAPy not only possesses good chemical stability and suitable band edge posi-
Published 5 September 2019 tions for promising photocatalytic H2 evolution, but it also exhibits a typical ligand-to-metal charge
transfer for favorable charge separation. The photocatalytic H2 evolution rates on the as-obtained
Keywords: Bi-TBAPy with different cocatalysts modified were examined with triethanolamine as the sacrificial
Metal-organic framework reagent. Based on this, the hydrogen evolution rate of 140 μmol h1 g1 was obtained on the opti-
Photocatalysis mized sample with a loading of 2 wt% Pt as a cocatalyst. To the best of our knowledge, this is the
Water reduction first bismuth-based metal-organic framework (MOF) that functions as an effective photocatalyst for
Ligand-to-metal charge transfer photocatalytic water reduction. Our study not only adds a new member to the family of photocata-
Charge separation lyst materials, but also reveals the importance of cocatalyst modification in improving photocatalyt-
ic activity of MOFs.
© 2019, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
Published by Elsevier B.V. All rights reserved.

Metal-organic frameworks (MOFs) composed of metal-oxo from water provides an environmentally friendly and sustaina-
clusters and polydentate organic linkers represent an intri- ble alternative to fossil fuels [3].
guing class of porous crystalline material with many attractive To date, some MOF-based photocatalysts have been ex-
properties such as porosity, large surface area, and structural plored for hydrogen production. These contain UiO-66 [4],
and functional tunability [1]. Because of these unique ad- NH2-UiO-66 [4], NH2-MIL-125(Ti) [5], and Al-PMOF [6]. Alt-
vantages, MOFs have been widely investigated for gas storage hough major progress has been achieved, the selection of met-
and separation, sensors, drug delivery, and catalysis [2]. Some als is often confined based on the robustness and conduction
photo-responsive MOFs exhibiting semiconductor behavior band (CB) position of the as-obtained MOF material [7,8]. Con-
have been developed as photocatalysts for promising solar sequently, new photo-responsive MOFs composed of other
energy conversion. In particular, solar-driven water splitting is metals with good robustness and a suitable band structure are
of great significance when considering that hydrogen evolution desired. Bismuth, as a nontoxic and earth-abundant element, is

* Corresponding author. Tel: +86-411-82463370; E-mail: [email protected]

# Corresponding author. Tel: +86-411-84379070; Fax: +86-411-84694447; E-mail: [email protected]

This work was supported by the National Natural Science Foundation of China (21633009, 21522306, 21633010), DICP&QIBEBT (UN201805), and
the Dalian Science Foundation for Distinguished Young Scholars (2017RJ02).
DOI: S1872-2067(19)63329-2 | http://www.sciencedirect.com/science/journal/18722067 | Chin. J. Catal., Vol. 40, No. 9, September 2019
1340 Yejun Xiao et al. / Chinese Journal of Catalysis 40 (2019) 1339–1344

a promising candidate for the construction of stable MOFs, as it coordinated with eight oxygen atoms from four linkers with a
has a relatively high valence state and flexible coordination bond length of ~2.435 Å. A dimethylamine cation serving as the
geometry [9,10]. However, the synthesis of bismuth-based counter ion is also coordinated with the Bi atom to maintain
MOFs remains challenging because of their structural sensitiv- the charge balance, and the bond length of Bi–N is ~2.923 Å.
ity to the reaction conditions such as solvents, temperature, Each TBAPy4‒ linker coordinated to four bismuth centers
and reaction time. The complicated structural behavior of shapes the backbone of Bi-TBAPy into a 3D framework (Fig.
Bi3+ ions during the solvothermal synthesis makes controlling 1(b) and (c)). Two types of 1D channels with different shapes
the process of crystal growth difficult [11]. Consequently, re- exist along the a axis (Fig. 1(c)). One channel has a rhomboid
ports on the synthesis of bismuth-based MOFs with photocata- shape and is occupied by dioxane; the other has a quadrilateral
lytic activity are limited [12–14]. To the best of our knowledge, shape and is occupied by dimethylamine solvent molecules.
no bismuth-based MOFs have been synthesized for photocata- The length of the two sides of these two windows are both 7.37
lytic water reduction.  11.65 Å2, although their shapes are different. The total sol-
In this study, we report on a new stable bismuth-organic vent-accessible volume is approximately 8.4% upon solvent
framework (Bi-TBAPy) with a 3D framework structure by em- removal, which is calculated with PLATON software [15]. The
ploying 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H4TBAPy) as BET surface area of Bi-TBAPy is measured to be 594 m2 g‒1. The
the organic linker. The as-obtained Bi-TBAPy is demonstrated coordination effect between Bi ions and H4TBAPy linkers can
to possess good stability and suitable band edge positions for be further confirmed by the results of FT-IR measurement (Fig.
photocatalytic water reduction. Based on our optimization, S2), where the hydroxyl vibration peak of –COOH in the range
Bi-TBAPy exhibits the optimal H2 evolution rate of 140 μmol of 3000–3400 cm‒1 disappears during the shift of the carbonyl
h‒1 g‒1 when triethanolamine (TEOA) is used as the sacrificial vibration peak in the range of 1620–1750 cm‒1. The experi-
reagent, demonstrating its promising future in solar fuel pro- mental XRD pattern (Fig. 1(d)) of Bi-TBAPy conforms well with
duction. the simulated pattern, which is generated based on single crys-
The structure of a Bi-TBAPy single crystal was investigated tal structure analysis, thus demonstrating a good phase purity
by single-crystal X-ray diffraction (XRD) analysis, and details of of the bulk material.
the crystal structure and refinement data are provided in Table To examine the physical and/or chemical stability of
S1. As given in Fig. S1, the Bi-TBAPy is crystallized in mono- Bi-TBAPy, thermogravimetric analysis (TGA) was first con-
clinic space group C2/c to form a 3D rod-like structure. The ducted, with results given in Fig. S3. The results reveal that the
typical structure is introduced in Fig. 1(a), where the Bi atom is Bi-TBAPy exhibits good thermal stability with the framework

a) c)

b) d)

Bi-TBAPy
Intensity (a.u.)

Bi-TBAPy-simulated

5 10 15 20 25 30
Degree (2

Fig. 1. Structure and analysis of Bi-TBAPy. (a) Coordination mode of the Bi atom in Bi-TBAPy; (b) coordination mode of the TBAPy moiety in
Bi-TBAPy; (c) crystal structure of Bi-TBAPy viewed along the a axis; (d) XRD patterns of Bi-TBAPy and Bi-TBAPy-simulated. Color representations:
red, O; yellow, N; gray, C; green, Bi. H atoms are removed for clarity.
 Yejun Xiao et al. / Chinese Journal of Catalysis 40 (2019) 1339–1344 1341

collapsed at approximately 350 °C. Subsequently, the Bi-TBAPy potential was calculated to be ca. –0.15 V vs. RHE. As the bot-
sample was also demonstrated to have good solvent stability tom of the CB of an n-type semiconductor is generally more
when considering the fact that no obvious change of XRD pat- negative by ca. 0.1 eV than the flat band potential [16], the CB
terns could be observed in the samples before and after im- of Bi-TBAPy was estimated to be ca. –0.25 eV. Together with
pregnation in water, DMF, dioxane, acetonitrile, methylene the bandgap value estimated from the UV/vis DRS (Fig. 2(a)),
dichloride, or isopropanol for 12 h at room temperature (Fig. the valence band (VB) was thus determined to be located at
S4). On the whole, the as-obtained Bi-TBAPy sample has an 2.42 eV. The estimated band edge positions of Bi-TBAPy are
unexpected thermal and solvent stability, demonstrating its shown in the insert of Fig. 2(b), in which the CB exhibits suffi-
good potential as a photocatalyst. cient potential in the water reduction process.
Fig. 2(a) shows its typical UV/vis DRS, based on which the Encouraged by the good stability and suitable CB position of
Bi-TBAPy has a visible light response with an absorption edge Bi-TBAPy, we examined the performance of Bi-TBAPy for water
of ca. 465 nm. The band gap of Bi-TBAPy was then estimated to reduction by using TEOA as the hole scavenger. The photocata-
be ca. 2.67 eV from the Kubelka-Munk function. To evaluate lytic water reduction activity of the Bi-TBAPy sample free of a
further the band edge positions of Bi-TBAPy, a Mott-Schottky cocatalyst was very low (Fig. S5). As shown in Fig. 2(c), the
measurement was conducted. Fig. 2(b) clearly reveals the loading of a suitable cocatalyst is desired to promote the H2
n-type semiconductor property of Bi-TBAPy, and the flat band evolution rate, and the platinum modified sample appeared to

b)
(a) 12

C-2 X 10 (cm4F-2) 10
Absorbance (a.u.)

6
9

Bi-TBAPy 4
-0.15V
2

0
300 400 500 600 700 800 -0.2 0.0 0.2 0.4 0.6
Wavelength (nm) Potential (V vs.RHE)

160 d) 700
(c)
140
Amount of H2 evolution (mol h g )

600
 1 1

Amount of H2 evolution (mol g )



120 500
100
400
80
300
60
200
40
100
20
0
0
Pt Rh Ru Ir Pd 0 1 2 3 4 5
Reaction time (h)
Fig. 2. (a) UV/Vis diffuse reflectance spectra of Bi-TBAPy; (b) Mott-Schottky plot of the Bi-TBAPy electrode and the estimated band edge positions of
Bi-TBAPy (insert). Electrolyte: 0.05 mol/L phosphate buffer solution (PH = 6.0); (c) effect of typical reduction cocatalysts (2 wt%) on the photocata-
lytic H2 evolution rate of Bi-TBAPy; (d) time course of photocatalytic H2 evolution on 2 wt% Pt/Bi-TBAPy.
1342 Yejun Xiao et al. / Chinese Journal of Catalysis 40 (2019) 1339–1344

promote the H2 evolution rate most efficiently. The difference tic peaks of Bi3+ ions located at 164.2 and 158.9 eV, two new
in the promotion effect originating from the cocatalyst species peaks centered at 162.2 and 156.9 eV were deconvoluted after
may derive from their distinct ability at trapping electrons from 3 h of irradiation and were consistent with the characteristic
the CB of Bi-TBAPy and/or activating protons for H2 evolution peaks of the lower valence state of the Bi ion [19,20]. It should
[17]. A volcanic-type curve of H2 evolution dependence on the be noted that although the lower valence state of Bi ions was
Pt content was observed (Fig. S5), and the optimal H2 evolution generated, the framework of Bi-TBAPy was well maintained
rate of 140 μmol h‒1 g‒1 appeared for the sample with 2.0 wt% based on the XRD patterns shown in Fig. S7, indicating the ro-
Pt loaded. The XPS pattern of Bi-TBAPy after hydrogen evolu- bustness of Bi-TBAPy. Based on the XPS analysis, a lig-
tion verified the loading of metallic Pt based on the binding and-to-metal charge transfer (LMCT) process was observed to
energies of Pt 4f7/2 and Pt 4f5/2 peaks, as shown in Fig. S6 [18]. occur in Bi-TBAPy, where the photogenerated electrons trans-
The loading of a suitable amount of platinum could trap the ferred from the excited TBAPy group to Bi3+, resulting in partial
photogenerated electrons and accelerate the conversion of reduction of bismuth ions. The LMCT mechanism is always
water molecules, whereas an excess amount probably leads to observed for MOFs as photocatalysts because of the intrinsic
the shielded light absorption of MOFs, thus resulting in de- charge separation process. As a result, steady-state photolumi-
creased photocatalytic H2 evolution performance. For compar- nescence (PL) measurements were conducted to evaluate the
ison, the water reduction performance of 2 wt% Pt/H4TBAPy influence of this charge transfer process. The results are shown
was also examined under the same conditions as the 2 wt% in Fig. 3(b). H4TBAPy exhibits the strongest steady-state PL
Pt/Bi-TBAPy. The negligible hydrogen evolution indicates that intensity, revealing that a great carrier recombination process
the formation of a framework by incorporating Bi ions is vital occurs in organic linkers, and the construction of Bi-TBAPy
to the photocatalytic performance of Bi-TBAPy. The typical could suppress this process, thus resulting in decreased PL
time course of the photocatalytic water reduction on the opti- intensity of pristine Bi-TBAPy. Compared to the pristine sam-
mized sample is shown in Fig. 2(d), in which the linear increase ple, the considerably diminished steady-state PL intensity of
of H2 evolution as a function of the reaction time demonstrates Bi-TBAPy after irradiation confirmed the separation of pho-
the good photochemical stability of Bi-TBAPy. In addition, the toinduced carriers as a result of the LMCT process, which in
XRD patterns of Bi-TBAPy before and after H2 evolution were turn inhibited the process of charge recombination. The pro-
not obviously altered (Fig. S7), also indicating the good stability posed mechanism for photocatalytic H2 over Bi-TBAPy is illus-
of Bi-TBAPy during the photocatalytic reaction. Furthermore, trated in Fig. 4. First, the TBAPy groups in Bi-TBAPy absorb
the transient photocurrent response on the Bi-TBAPy photoe- light to generate electrons and holes. Then, the excited elec-
lectrode in a three-electrode setup was conducted by using a trons can be utilized through two pathways. In one pathway,
0.5-M sodium sulfate solution as an electrolyte solution. An electrons first transfer to the near Bi3+ ions by following the
obvious photocathode current could be observed from the LMCT mechanism and then transfer to the cocatalysts. In the
chopped photocurrent profile of Bi-TBAPy (Fig. S8), indicating other pathway, the excited electrons in TBAPy groups transfer
the generation of electron-hole pairs in Bi-TBAPy during light directly to Pt particles. Subsequently, the deposited Pt act as
irradiation and the capacity for photoelectrochemical water active sites to perform the catalytic reduction of water while
reduction by photoinduced electrons. the photogenerated holes are simultaneously consumed by the
To obtain insights into the mechanism of the charge transfer sacrificial reagent TEOA.
during the photocatalytic process, Bi 4f XPS patterns of In summary, we synthesized a novel 3D bismuth-organic
Bi-TBAPy before and after H2 evolution were measured and framework (Bi-TBAPy) with good stability and suitable band
compared. As shown in Fig. 3(a), in addition to the characteris- edge positions for promising photocatalytic H2 evolution. The

After H2 evolution (a) (b)

Bi 4f7/2
Bi 4f5/2 Bi-TBAPy
Bi-TBAPy-irradiated
H4TBAPy
Intensity (a.u.)
Intensity (a.u.)

Bi-TBAPy

166 164 162 160 158 156 400 440 480 520 560 600 640
Binding energy (eV) Wavelength (nm)

Fig. 3. Characterizations of typical samples. (a) Bi 4f XPS spectra of Bi-TBAPy and Bi-TBAPy after H2 evolution; (b) steady-state emission spectra of
Bi-TBAPy, Bi-TBAPy-irradiated, and H4TBAPy.
 Yejun Xiao et al. / Chinese Journal of Catalysis 40 (2019) 1339–1344 1343

Acknowledgments

This work was financially supported by National Natural

Science Foundation of China (21633009, 21522306,
21633010), jointed project between DICP and
QIBEBT(UN201805), and Dalian Science Foundation for Dis-
tinguished Young Scholars (2017RJ02). F. Zhang thanks the
priority support from the “Hundred Talents Program” of Chi-
nese Academy of Sciences.

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Graphical Abstract
Chin. J. Catal., 2019, 40: 1339–1344 doi: S1872-2067(19)63329-2
Development of a bismuth-based metal-organic framework for photocatalytic hydrogen production
Yejun Xiao, Xiangyang Guo, Junxue Liu, Lifang Liu, Fuxiang Zhang *, Can Li *
Dalian Institute of Chemical Physics, Chinese Academy of Sciences; University of Chinese Academy of Sciences

160
-1

140
Amount of H2 evolution / mol h-1g

120

100

80

60

40

20

0
Pt Rh Ru Ir Pd

A new 3D bismuth-organic framework (Bi-TBAPy) with ligand-to-metal charge transfer (LMCT) process was synthesized to exhibit for
the first time robust photocatalytic water reduction, demonstrating its promising future in solar energy conversion.
1344 Yejun Xiao et al. / Chinese Journal of Catalysis 40 (2019) 1339–1344

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新型铋基金属有机框架的合成及其光催化产氢性能
肖晔珺a,b, 郭向阳a, 刘俊学c, 刘利芳a,b, 章福祥a,*, 李 灿a,#
a
中国科学院大连化学物理研究所, 催化基础国家重点实验室, 洁净能源国家实验室,
能源材料化学协同创新中心, 辽宁大连116023
b
中国科学院大学, 北京100049
c
中国科学院大连化学物理研究所, 分子反应动力学国家重点实验室, 能源材料化学协同创新中心, 辽宁大连116023

摘要: 金属有机框架材料(MOFs)是由金属离子或团簇与多齿有机配体配位结合形成的一种结晶性材料. 因其具有三维孔

道结构, 以及比表面积大、结构和功能可调变等优点, 在气体的储存与分离、传感、药物传输和催化领域等方面具有广泛
的应用. 近年来, MOFs材料因其独特的结构和可调变性, 在太阳能转化领域逐渐崭露头角, 其中光催化水分解制氢作为一
种可行的太阳能光化学转化方法, 引起了人们的广泛关注. 目前, MOFs材料用于光催化水分解制氢的研究已经取得了一
定的进展, 但在合成新型具有光催化性能的MOFs材料时, 考虑到材料稳定性和能带位置的要求, 在金属离子选择上往往受
到限制. 铋元素无毒且储量丰富, 因其具有较高的价态和灵活的配位模式, 在构建MOFs材料时常常会表现出独特的优势.
然而, 铋基MOFs对于合成条件十分敏感, Bi3+离子复杂的配位模式也使晶体结晶的过程难以调控. 因此, 铋基MOFs在合成
方面具有一定的挑战. 目前已报道的具有光催化活性的铋基MOFs材料十分有限, 且能够实现光催化水还原的铋基MOFs
材料还未有报道. 本文利用1,3,6,8-四(4-羧基苯)芘(H4TBAPy)作为有机配体, 合成了一种新型的三维铋基MOFs单晶材料
(记为“Bi-TBAPy”), 并对其结构、稳定性、光催化水还原性能及电荷转移机理进行了研究.
单晶衍射结果表明, Bi-TBAPy中铋离子与来自四个不同配体的八个氧原子配位形成了立体的三维结构, 二甲胺阳离
子作为抗衡离子与铋离子配位使整个骨架保持电中性. 实验测得的XRD结果与模拟的一致, 表明Bi-TBAPy具有较高的相
纯度. TGA以及XRD测试分析也证明了Bi-TBAPy具有良好的热稳定性和化学稳定性. 结合UV/vis和莫特-肖特基的测试结
果可知, Bi-TBAPy具有n型半导体性质, 带隙宽度约为2.67 eV, 导带和价带位置分别位于–0.25和2.42 eV, 表明Bi-TBAPy在
热力学上能够满足光催化水还原的要求. 随后, 以三乙醇胺为牺牲试剂考察了Bi-TBAPy的光催化产氢性能. 研究发现助
催化剂的种类对催化剂性能具有重要影响, 担载2 wt% Pt时表现出最优的产氢速率, 达140 μmol h–1 g–1, 其为目前报道的首
个具有光催化水还原性能的铋基MOFs催化剂. 长时间的光催化水还原反应测试可以持续稳定的进行, 同时反应前后
Bi-TBAPy的XRD也不发生变化, 表明该材料具有很好的光化学稳定性. 反应后样品的Bi 4f XPS谱图表明反应过程中有低
价铋的生成, 这说明配体受激发产生的光生电荷能够转移到Bi3+上使其部分被还原. 因此, 该材料能够实现配体-金属电荷
转移(LMCT)的过程, 荧光光谱测试的结果证实了该过程有利于光生载流子的分离.
关键词: 金属有机框架; 光催化; 水还原; 配体到金属电荷转移; 电荷分离

收稿日期: 2018-12-20. 接受日期: 2019-02-08. 出版日期: 2019-09-05.

*通讯联系人. 电话: (0411)82463370; 电子信箱: [email protected]
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通讯联系人. 电话: (0411)84379070; 传真: (0411)84694447; 电子信箱: [email protected]
基金来源: 国家自然科学基金(21633009, 21522306, 21633010); 大连化物所与青岛能源所两所融合基金项目(UN201805); 大连杰
出青年科学基金(2017RJ02).
本文的电子版全文由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18722067).