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Abbreviation (ISO4): Prog Chem      Editor in chief: Jincai ZHAO

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Progress in Chemistry >

2023 , Vol. 35 >Issue 6: 940 - 953

DOI: https://doi.org/10.7536/PC221216

Review

Nano-State Layered Double Hydroxides Based Materials for Photo-Driven C1 Chemical Conversion

  • Chi Duan 1 ,
  • Zhenhua Li , 1, * ,
  • Tierui Zhang , 1, 2, *
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  • 1 Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences,Beijing 100190, China
  • 2 Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences,Beijing 100049, China
*Corresponding authore-mail: (Zhenhua Li);
(Tierui Zhang)

Received date: 2022-12-28

  Revised date: 2023-05-19

  Online published: 2023-05-25

Supported by

The National Natural Science Foundation of China(51825205)

The National Natural Science Foundation of China(52120105002)

The National Natural Science Foundation of China(22088102)

The National Natural Science Foundation of China(22209190)

The Postdoctoral Science Foundation of China(2021M703288)

The Postdoctoral Science Foundation of China(2022T150665)

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Abstract

Energy is the basic guarantee for human survival. As an important reaction in field of energy, C1 chemical conversion has safeguarded the development of human society. With the proposal of "double carbon" goal, energy saving-emission reduction and environmental friendliness have been the new pursuit of C1 catalytic conversion researchers. Recently, photo-driven C1 chemical conversion has attracted researchers’ attention through which C1 small molecules can be transformed into various value-added products under ambient condition. Layered double hydroxides (LDH) have gained wide application in photo-driven C1 chemical conversion for their distinctive two-dimensional layered structure. Herein, we review the latest progress achieved in nano-state LDH based materials for photo-driven C1 chemical conversion from three aspects containing LDH precursors acting as catalyst, LDH derivatives acting as catalyst and LDH acting as catalyst carrier, and conclude the challenges this field may face in the future. Through analyzing and discussing above-mentioned work, we hope to offer researchers some inspiration on photo-driven C1 chemistry.

Contents

1 Introduction

2 A brief introduction of LDH

2.1 Structural composition of LDH

2.2 Basic properties of LDH

3 Application of LDH based materials in photo-driven C1conversion

3.1 LDH precursors as catalyst

3.2 LDH derivatives as catalyst

3.3 LDH as catalyst carrier

4 Conclusion and outlook

Key words： C1 chemical conversion; LDH; photo-driven; valve-added chemicals

Cite this article

Chi Duan , Zhenhua Li , Tierui Zhang . Nano-State Layered Double Hydroxides Based Materials for Photo-Driven C1 Chemical Conversion[J]. Progress in Chemistry, 2023 , 35(6) : 940 -953 . DOI: 10.7536/PC221216

1 Introduction

With the rapid growth of global population, the demand for energy in human society is increasing day by day. In recent years, the reserves of traditional energy represented by oil are decreasing day by day. In order to alleviate the excessive dependence on oil, it is necessary to seek new energy conversion paths. C1 catalytic conversion based on small C1 molecules such as carbon monoxide (CO), carbon dioxide (CO2), methane (CH4), methanol (CH3OH), and formic acid (HCOOH) offers great potential for the sustainable production of high-value chemicals[1⇓⇓⇓⇓~6]. However, the traditional thermal catalytic conversion of C1 usually requires high temperature and high pressure reaction conditions, accompanied by a large amount of energy consumption, and also causes secondary pollution to the environment. Based on this, there is an urgent need for researchers to find a sustainable and clean energy conversion path. Solar energy, as an "inexhaustible" energy, has attracted more and more attention from researchers. Compared with the traditional thermal catalysis, the chemical catalytic conversion of C1 driven by sunlight is cleaner, which is expected to make the catalytic reaction conditions milder, further reduce the dependence on fossil energy, and achieve green and efficient chemical conversion of C1[7⇓⇓⇓⇓~12].
Materials are the basis of catalytic reactions.Layered Double Hydroxides (LDH) have been a hot material in the field of light-driven chemical conversion of Layered Double Hydroxides in recent years because of their multi-metal sites and highly dispersed sites[13]. In this paper, we will review the research progress of nano-LDH-based materials in the field of light-driven chemical conversion of C1 from three aspects of LDH precursors, LDH derivatives and LDH as catalyst supports.

2 Introduction to LDH

2.1 Structure and composition of LDH

LDH is a layered bimetallic inorganic nanomaterial whose chemical formula can be written as [ M 1 - x 2 + M x 3 + (OH)2]x+(An- ) x / n ·mH2O,Wherein M2+ and M3+ represent divalent and trivalent metal ions, respectively, and the molar ratio X of M3+ to total metal cations is generally between 0.20 and 0.33,The common M2+ in LDH are Ca2+, Mg2+, Zn2+,Fe2+ 、UCu2+ UNCo2+ NKNi2+Common M3+ are Al3+, U Fe3+, UN Cr3+[14][15][16] The [MO6] octahedra formed by metal ions and O2- constitute the main layer plate in the intercalation structure, because the M3+ occupies a part of the M2+ sites in the lattice,The main lamina is positively charged, and the interlayer anion An- can usually be C O 3 2 -, N O 3 -, Cl-[17][18]. In addition to the binary LDH mentioned above, some researchers have also introduced a third metal ion into the main layer to obtain ternary LDH such as NiMgAl-LDH and CoFeAl-LDH[19,20][21,22].

2.2 Basic properties of LDH.

The combination of the two valence metal elements on the LDH main layer plate is various, the proportion of the metal ions with different valence States is flexible and adjustable, and the metal ions are highly dispersed on the main layer plate[23,24][25]. The interlayer anions of LDH can be exchanged, and the type of interlayer anions can be adjusted by impregnation[26]. As early as 1995, Rives et al. Of Spain used the ion exchange property of LDH to impregnate the N O 3 - intercalated NiAl-LDH in the aqueous solution containing VO 3 -, and finally obtained the V O 3 - intercalated LDH which is difficult to synthesize by general coprecipitation or hydrothermal method[27].
LDH has a topological transition effect, that is, in the process of calcination heat treatment, the H2O adsorbed on the LDH, the H2O and anions intercalated between the layers, and the hydroxyl on the main layer plate are successively removed, the LDH intercalation structure is gradually collapsed, and at the same time, the metal ions on the main layer plate can migrate directionally.As a result, some crystal planes of the calcined product have a certain topological relationship with the crystal planes of the LDH precursor, so a variety of topological transformation products including Mixed Metal Oxides (MMO) and spinel can be formed at different temperatures[28][29][30][31].
LDH has a certain memory effect. If the topological transition product MMO obtained at a lower temperature is immersed in an aqueous solution containing anions for a period of time, the intercalation structure can be gradually restored, and the MMO can be restored to LDH again, which is the "memory effect" of LDH[32]. Wiercioch et al. Confirmed that CuZnAl-LDH was restored to the original LDH structure after calcination at 400 ~ 600 ℃ through the hydration process, and the "memory effect" of LDH disappeared when the calcination temperature exceeded 600 ℃[33].

3 Application of LDH-based materials in light-driven C1 conversion

3.1 LDH precursor material as catalyst

Although LDH precursor is not a typical semiconductor material, it has a certain response under UV-visible light conditions[34⇓~36]. Based on this, researchers mainly use it for photocatalytic CO2 reduction to produce value-added chemicals, including CO, CH3OH, CH4 and C2+ products[37⇓⇓~40].
As early as 2012, Tanaka et al. Of Kyoto University in Japan reported that several different kinds of LDH achieved the conversion of CO2 to CO under illumination[37]. Because that metal element of the LDH main lamina are flexible and adjustable, and the adsorption sites and reaction active site required by the reduction of the CO2 to different products are different, a specific reduction product can be obtained by selecte the LDH containing the potential metal active sites[41⇓~43]. Recently, our group synthesized ZnTi-LDH, ZnFe-LDH, ZnCo-LDH, ZnGa-LDH and ZnAl-LDH respectively by changing the trivalent metal ions of ZnM-LDH[43]. The experimental results show that different LDH corresponds to different reduction products, in which the product of ZnTi-LDH is mainly CH4, while the product of ZnGa-LDH and ZnAl-LDH is CO (selectivity is 70% and 90%, respectively); ZnFe-LDH and ZnCo-LDH have 100% H2 selectivity (Figure 1A). The theoretical calculation results show that the adsorption capacity of ZnFe-LDH and ZnCo-LDH for CO2 is poor, so the corresponding product is H2. Then we carried out DFT calculations on the transition States of different product transformation paths on ZnTi, ZnAl and ZnFe-LDH, and further revealed the reasons for the different product selectivities of the three CO2 photoreduction. ZnTi-LDH has a low energy barrier for hydrogen production and a low energy barrier for CH4, so the selectivity of CH4 in the product is high. ZnAl-LDH has the highest energy barrier for both hydrogen production and CH4, so it is not conducive to the production of H2 and CH4, but tends to produce CO; ZnFe-LDH has the lowest energy barrier for hydrogen production, and the energy barriers for both CO production and CH4 are higher, so it has higher H2 selectivity (Fig. 1b-d).
图1 (a) ZnM-LDH结构示意图及相应的光催化CO2还原产物; ZnM-LDH上(b) 产氢, (c) 光催化CO2还原至CO和(d) 光催化CO2还原至CH4的Gibbs自由能图[43]

Fig.1 (a) Scheme of ZnM-LDH structure and corresponding photocatalytic CO2 reduction product; The Gibbs free energy diagram of (b) H2 evolution, (c) photocatalytic CO2 reduction to CO and (d) photocatalytic CO2 reduction to CH4 over ZnM-LDH[43].Copyright 2020, Elsevier

The composition of metal elements in LDH components not only has a certain influence on the reaction path of CO2, but also affects the adsorption state of CO2. Zhong et al. Synthesized a series of Ni-based LDHs, such as NiTi, NiCo, NiFe, NiMn, and NiAl, and analyzed the chemisorption state of CO2 on these LDHs by means of in situ infrared characterization[44]. The results showed that the CO2 adsorbed on NiCo, NiFe, NiMn and NiAl-LDH were converted to B- C O 3 2 - or c-   C O 3 2 -, while most of the CO2 adsorbed on NiTi-LDH was converted to the intermediate · C O 2 - of CO product. The photocatalytic performance test results showed that NiTi-LDH had the highest CO formation rate and selectivity.
The morphology and particle size of catalytic materials are important factors affecting the catalytic reaction, and different morphology and size often lead to different catalytic activity and product selectivity[45⇓~47]. As a layered two-dimensional material, the morphology and size of LDH are affected by many factors, such as the synthesis method, crystallization time, pH value, crystallization temperature and so on[48][49][50][51]. In recent years, researchers have obtained more defects and larger specific surface area by controlling the morphology and size of LDH, and then achieved the improvement of catalytic performance[52,53][56]. Based on this, our group synthesized ZnAl-LDH with different morphologies by different methods (Figure 2A)[54]. The characterization results show that the thickness of ZnAl-LDH obtained by reverse microemulsion method is only 2. 74 nm. Compared with bulk ZnAl-LDH synthesized by coprecipitation method, ultrathin ZnAl-LDH has abundant oxygen vacancies. Subsequently, its photocatalytic CO2 reduction performance was tested, and the results showed that the corresponding CO generation rate of the ultrathin ZnAl-LDH was 7.6μmol·g-1·h-1, while the bulk ZnAl-LDH had almost no performance, and the cycling experiment showed that the ultrathin ZnAl-LDH had good stability (Figure 2B). Furthermore, 13CO2 isotope experiments showed that the product originated from the reactant rather than other impurities. The DFT calculation results show that the defect structure composed of oxygen vacancies and unsaturated coordinated Zn can promote the adsorption of both CO2 and H2O, thus contributing to the improvement of photocatalytic CO2 activity (Fig. 2C).
图2 (a) 体相和超薄ZnAl-LDH合成示意图; (b) 超薄ZnAl-LDH光催化CO2还原循环实验; (c) CO2和H2O在a) 超薄ZnAl-LDH和b) 体相ZnAl-LDH上的吸附能[54]

Fig.2 (a) Synthesis scheme of bulk and ultrathin ZnAl-LDH; (b) Photocatalytic CO2 reduction cycling studies of ultrathin ZnAl-LDH; (c) Adsorption energies of CO2 and H2O molecules on a) ultrathin ZnAl-LDH system and b) bulk ZnAl-LDH[54].Copyright 2015, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Song Yufei et al. Prepared m-NiAl-LDH (1 nm), f-NiAl-LDH (5 nm) and b-NiAlLDH (27 nm) with different thicknesses by double-drop method, hydrothermal method and urea method, respectively[55]. The photocatalytic CO2 reduction performance test with [Ru(bpy)3]Cl2·6H2O as photosensitizer and TEOA as sacrificial agent under λ > 400 nm illumination showed that m-NiAl-LDH had the lowest selectivity for hydrogen production and the highest selectivity for CH4 (6. 54%). Then they switched to a light source with a wavelength of more than 600 nm for testing, and found that the CH4 selectivity of m-NiAl-LDH was increased to 70. 3%, and the side reaction of hydrogen production was inhibited. The structural characterization and DFT theoretical calculation results confirm that the high CH4 selectivity of m-NiAl-LDH at λ > 600 nm is due to the abundant VOH, VAl and VNi. Subsequently, they further investigated the photocatalytic CO2 reduction performance of multilayer b-NiFe-LDH and monolayer m-NiFe-LDH in another work. The experimental results show that the corresponding CO2 reduction product of multilayer b-NiFe-LDH is H2, while m-NiFe-LDH has better CH4 selectivity[56].
Abundant CO2 adsorption sites can be constructed by manipulating the morphology and size of LDH. Tokudome and Teramura et al. Have successfully synthesized nanocrystalline NNiAl-LDH in ethanol medium in a supersaturated alkaline environment provided by propylene oxide, and the rate of photocatalytic reduction of CO2 to CO is much higher than that of NiAl-LDH obtained by conventional coprecipitation method[57]. The grain size of NNiAl-LDH is 20 nm, and the specific surface area is nearly twice that of NiAl-LDH. Further experiments show that the higher performance of NNiAl-LDH is not only due to its larger specific surface area. They found that the CO production performance of NNiAl-LDH treated with different concentrations of NaOH solution decreased significantly under the same conditions. They believed that propylene oxide made the pH value of the solution rise sharply, and the obtained NNiAl-LDH was in a thermodynamic metastable state, so it contained abundant unsaturated coordination metal sites and had a stronger adsorption capacity for CO2. However, the treatment of NaOH solution will change the thermodynamic metastable state into the thermodynamic steady state, and the original CO2 adsorption sites will disappear, resulting in the decline of performance.
In addition to regulating the catalytic activity of LDH by changing its own properties through various means, some researchers have recently compounded LDH with other materials to construct core-shell structures, heterojunctions and other structures to optimize the photocatalytic CO2 reduction performance[58]. Recently, Song Yufei et al. Grew a layer of NiMn-LDH on the surface of MIL-100 molecular sieve in situ to obtain MIL-100 @ NiMn-LDH (Figure 3A)[59]. The catalyst exhibited superior photocatalytic CO2 reduction performance under visible light, and the generation rate of CH4 could reach 284μmol·g-1·h-1 with a selectivity of 88%. A series of characterizations and theoretical calculations confirmed that the high activity of MIL-100 @ NiMn-LDH can be attributed to the large number of CO2 adsorption activation sites exposed by its layered structure. In addition, the large amount of VO in the in-situ grown LDH also plays a role in optimizing the band gap and promoting the electron-hole separation (Fig. 3 B, C).
图3 (a) MIL-100@NiMn-LDH的合成示意图[59]; (b) NiMn-LDH和MIL-100@NiMn-LDH的电子顺磁共振谱图[59]; (c) MIL-100@NiMn-LDH上的缺陷示意图(M = Ni, Mn)[59]; (d) g-C3N4/Ti3C2T/CoAlLa-LDH上的S型光催化DRM机理[60]

Fig.3 (a) Scheme of MIL-100@NiMn-LDH synthesis[59]; (b) EPR spectra of NiMn-LDH and MIL-100@NiMn-LDH[59]; (c) Illustration for defects on MIL-100@NiMn-LDH(M = Ni, Mn)[59]; (d) S-scheme photocatalytic DRM mechanism over g-C3N4/Ti3C2T/CoAlLa-LDH[60].Copyright 2022, American Chemical Society

A similar LDH composite idea has also been used for photocatalytic CH4 reforming. Tahir et al. Used electrostatic assembly strategy to successfully construct g-C3N4/Ti3C2T/CoAlLa-LDH multi-element heterostructure (Ti3C2T refers to Ti3C2 with in-situ growth of TiO2)[60]. The CoAlLa-LDH, the g-C3N4 and the TiO2 form a 2D/2D interface structure, photogenerated electrons are stored by the Ti3C2 and then conducted to the CoAlLa-LDH and the g-C3N4,For photocatalytic CO2 reduction, while holes are enriched in the TiO2 valence band for the oxidation of CH4 (Figure 3D). A series of characterizations confirmed that g-C3N4/Ti3C2T/CoAlLa-LDH also has a strong adsorption capacity for both CH4 and H2O. The researchers tested the dry reforming performance of CH4 with different CO2/CH4 ratios and found that when CO2/CH4=1,The H2/CO ratio of syngas obtained by g-C3N4/Ti3C2T/Co2Al0.95La0.05-LDH is 1. 04, and the proportion of H2 in the product gradually increases with the increase of the CH4 ratio. By adding the same amount of water as the CO2 during feeding, not only the synthesis gas with a H2/CO of 1 was obtained, but also the generation rate of H2 was increased by 24%.

3.2 LDH-based derivative material as catalyst

Under certain temperature conditions, LDH has a topological transformation effect, and a series of LDH derivatives, including MMO, MMO supported metal elements or alloys, can be obtained, which are widely used in light-driven C1 chemical conversion, such as photothermal Fischer-Tropsch Synthesis (FTS), CO2 hydrogenation, and CH4 coupling and reforming[29][30][61].

3.2.1 Photothermal catalytic FTS

FTS is a kind of traditional thermal catalytic reaction. The commonly used catalysts are metal Fe, Co, Ni or the corresponding carbides and precious metals Ru, Rh, etc., which generally need to be carried out under high temperature and high pressure reaction conditions[62,63][64][65,66]. Solar energy, as a clean and renewable energy, is widely used in various fields, especially in the field of catalysis, which shows its unique advantages[67⇓⇓~70].
In 2015, our research group obtained a series of Ni-based catalysts with different phases by calcining and reducing NiAl-LDH at different temperatures[71]. The phase was characterized by XPS, XAS and other characterization methods, and it was found that with the gradual increase of reduction temperature, metal Ni gradually appeared, and the Ni/NiOx interface structure was formed at 500 ℃ (Fig. 4A). Subsequently, the FTS performance of Ni-x (X represents the reduction temperature) under illumination was investigated, in which the CO conversion of Ni-525 could reach 60.1% 27.7%,C2+ selectivity. The DFT calculation results further confirm that the Ni/NiOx interfacial structure effectively suppresses the methanation of CO while promoting the C-C coupling (Fig. 4 B, C). We further extended it to Co-based catalysts and also achieved highly selective synthesis of C2+ under illumination[72].
图4 (a) Ni-x的XPS Ni 2p谱图[71]; Ni(111)和4O/Ni(111)上的(b) CH4生成势能图[71]及(c) C-C偶联势能图[71]; (d) Co-x的Co K边EXAFS谱图[73]; Co(111)/Co3O4(220)和Co(111)上的(e) CO解离势能图[73]及(f) CH2偶联与C2H4加氢势能图[73]

Fig.4 (a) Ni 2p XPS spectra of Ni-x[71]; The potential energy profile of (b) CH4 formation and (c) C-C coupling on Ni(111) and 4O/Ni(111)[71]; (d) Co K-edge EXAFS spectra for Co-x[73]; The potential energy profile of (e) CO dissociation and (f) CH2 coupling and C2H4 hydrogenation on Co(111)/Co3O4(220) and Co(111)[73]. Copyright 2016&2018, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

As an important industrial raw material, the preparation of light olefins ( C 2 ~ 4 =) is more important than that of some short-chain alkanes. To improve the selectivity of C 2 ~ 4 = in photothermal FTS products, the researchers optimized the structure of the catalyst. ZnCoAl-LDH was reduced at different temperatures to obtain Co-based catalysts with different phases for photothermal FTS[73]. Synchrotron radiation characterization results showed that elemental Co was gradually reduced with the increase of reduction temperature, and the peak of metallic Co became stronger with the increase of reduction temperature (Fig. 4D). The FTS performance of Co-based catalysts obtained at different temperatures was further tested. The FTS products of Co-350 and Co-650 obtained by reduction at 350 ℃ and 650 ℃ had only a small amount of C 2 ~ 4 =, while the FTS products of Co-450 obtained by reduction at 450 ℃ had a significant increase in the proportion of olefins in the C 2 ~ 4 = products, and the ratio of olefins to paraffins reached 6. 1. The characterization results show that the Co0/Co3O4 interfacial structure is formed in Co-450, which is beneficial to the formation of light olefins. Further DFT calculation results show that compared with the single metal CO or Co3O4,Co0/Co3O4 interface structure, on the one hand, it can reduce the Co dissociation energy (Fig. 4E), on the other hand, it can effectively inhibit the further hydrogenation of olefin products, resulting in higher C 2 ~ 4 = selectivity (Fig. 4F). However, the price of metal Co is relatively expensive, and the reserves of metal Co in China are limited, mainly relying on imports, so it is necessary to seek cheaper metal to replace Co in order to achieve further industrialization. Based on this, Co in the LDH precursor was replaced by Fe, and the Fe0/FeOx interface structure was obtained by reduction treatment at 500 ℃, and the C 2 ~ 4 = selectivity of 42.4% was obtained under the same experimental conditions[74].

3.2.2 Photothermal catalytic CO2 hydrogenation

CO2 hydrogenation mainly includes two reaction mechanisms: FTS-like and methanol intermediate pathways. In the former, Reverse Water-Gas Shift (RWGS) occurs first to produce CO, followed by FTS to produce high value-added products such as CH4, CH3OH, HCOOH and C2+[75][76⇓⇓~79]. Although the product distribution of the latter can break through the limitation of Anderson-Schulz-Flory distribution, the by-product CO selectivity of this path is higher[80][81]. In recent years, many photothermal catalysts have been developed around CO2 hydrogenation, which have successfully realized the efficient conversion of CO2 to CO, CH4, CH3OH, C2+ and other products[82⇓⇓~85].
Ye et al. Irradiated MgAl-LDH impregnated with Cu2+ and Fe3+ with a Xe lamp under CO2/H2 atmosphere, and the Cu and Fe metal nanoparticles produced by reduction caused a local photothermal effect under illumination, so that the LDH region near them collapsed into porous MgAl-MMO (MAO), and finally a CuOx&FeOx/MAO structure was etched on the MgAl-LDH precursor (Figure 5A)[86]. Through a series of performance comparison experiments, they found that the FeOx distributed around the CuOx particles and the MAO etching structure played a protective role on the Cu sites, which could effectively prevent the aggregation of CuOx (Fig. 5B).
图5 (a) CuOx&FeOx/MAO的合成机理; CuOx&FeOx/MAO上的(b) 空间限域效应和(c) CO2与H2的活化机理[86]

Fig.5 (a) Synthetic mechanism of CuOx&FeOx/MAO; (b) Space confined effect and (c) Activation mechanism of CO2 and H2 on CuOx&FeOx/MAO[86]

Further characterization results also show that the interface between CuOx and FeOx provides more sites than single metal for the dissociation activation of H2, and the MAO substrate rich in alkali sites can effectively promote the adsorption activation of CO2 (Figure 5C).The two cooperate with each other, so that the CuOx&FeOx/MAO has a CO2 conversion rate of 41.3% and a CO selectivity of 100% under ultraviolet-visible light irradiation.
In our group, Ni-based LDH derivatives were used to realize the high selectivity preparation of CO2 hydrogenation to CH4[87]. A series of Ni-based supported nanocatalysts were obtained by H2 reduction of NiAl-LDH at different temperatures. The results of CO2 hydrogenation test under ultraviolet-visible-near infrared irradiation showed that the metal Ni nanoparticle-supported catalyst obtained by reduction at 600 ℃ had a CO2 conversion of 78.4%,CH4 selectivity of 99.7%, and the formation rate of CH4 was 278.8 mmol·g-1·h-1. The performance of the catalyst remained unchanged under mobile phase conditions for 100 H.
To further increase the product added value, researchers have improved the C2+ product selectivity by introducing noble metals or forming alloys to inhibit the methanation reaction[88,89][90,91]. In our group, CoFeAl-LDH was synthesized by hydrothermal method, and then a series of bimetallic supported nanocatalysts were obtained by reduction treatment at different temperatures[22]. The study showed that the CoOx supported catalyst was synthesized at low temperature, the FeOx/CoOx supported catalyst was synthesized at medium temperature, and the CoFe alloy nano-supported catalyst is synthesized at high temperature (Fig. 6a). Subsequently, the photothermal CO2 hydrogenation performance of the above reduction products was investigated, and the results showed that the CoFe-alloyed nanocatalysts obtained at high temperature exhibited excellent CO2 hydrogenation performance under UV-visible light irradiation, and the CoFe-650 obtained at 650 ° C exhibited a 2 h CO2 conversion of 35% with a 78.6%,C2+ selectivity. However, the catalytic performance test of this work was completed in the closed tank reactor, because the closed tank reactor can not discharge the product in real time, so it is very easy to cause further hydrogenation of olefins in the C2+ product to produce alkanes. Based on this, our research group compared the photothermal CO2 hydrogenation performance of CoFeAl-LDH, NiFeAl-LDH and NiCoAl-LDH reduced at 650 ℃ to obtain CoFe-650, NiFe-650 and NiCo-650 supported catalysts under mobile phase conditions, and found that under ultraviolet-visible light irradiation, when the reaction gas flow rate was controlled at 15 mL·min-1 and the temperature was 250 ℃, the C2+ selectivity of NiFe-650 and NiCo-650 was almost zero, and only CoFe-650 showed 21. 01%[92].
图6 (a) CoFe-x的形成和相应CO2加氢产物示意图[22]; (b) Fe-x的XRD谱图[93]; (c) Fe-500的HRTEM图片[93]; (d) Fe-500的CO2加氢流动相性能[93]; (e) 3O/Fe(110)和Fe(110)上CH4形成(上图)和C-C偶联(下图)的势能图[93]

Fig.6 (a) Illustration of CoFe-x catalysts formation and corresponding CO2 hydrogenation products[22]; (b) XRD spectra for Fe-x[93]; (c) HRTEM image for Fe-500[93]; (d) CO2 hydrogenation performance of Fe-500 using a flow system[93]; (e) The potential energy profile of CH4 formation (up) and C-C coupling (down) on 3O/Fe(110) and Fe(110)[93]. Copyright 2017&2021, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

In order to further improve the C2+ selectivity of CO2 hydrogenation and reduce the catalyst cost, our research group successfully prepared Fe-500 catalyst with MgAl-MMO supported Fe0/FeOx interface structure by reducing MgFeAl-LDH at 500 ℃[93]. The formation of this interfacial structure was demonstrated by XRD and HRTEM characterization (Fig. 6 B, C). The results of CO2 hydrogenation performance test under UV-visible light irradiation showed that the CO2 conversion of Fe-500 was 52.9% for 50.1%,C2+ selectivity, and the catalyst showed good stability under mobile phase conditions (Fig. 6d). The energy barriers of methanation and C-C coupling reactions on the (110) plane of 3O/Fe and Fe models were compared by DFT calculation, and 3O/Fe has a higher methanation energy barrier and a lower C-C coupling energy barrier, so it can effectively suppress the formation of CH4 and obtain a higher C2+ selectivity (Fig. 6e).

3.2.3 Photothermal catalytic CH4 reforming and coupling

CH4 is the main component of natural gas, which is of great significance to human production and life. At present, its conversion and utilization are mainly through CO2 dry reforming (DRM), H2O wet reforming (SRM) or partial oxidation of O2.And then separate that H2 or taking the synthesis gas as a raw material to continuously carry out chemical conversion of other C1 such as FTS and the like[94⇓~96]. Ni-based catalysts have been widely studied in thermal catalytic CH4 reforming, but the high temperature conditions required to activate C — H bonds can easily lead to catalyst sintering or carbon deposition[97⇓⇓~100][101⇓⇓~104]. Recently, photocatalytic and photothermal catalytic CH4 reforming has become a major research focus because of its mild reaction conditions, low energy consumption, and easy to break the thermodynamic limit[105,106]. Based on the uniform dispersion of LDH metal sites and the characteristics of thermally induced topological transformation in reducing atmosphere, which is easy to form alloys, researchers reported the application of a series of LDH derivatives supported Ni-based alloy catalysts in photothermal catalytic CH4 reforming.
A series of NiFe-LDH derivative NixFey containing NiFe alloy were obtained by calcining and reducing NiFeAl-LDH at 650 ℃ while changing the ratio of Ni to Fe[107]. Among them, the DRM performance of Ni3Fe1 is the best, and the syngas generation rate can reach 46.69 mmol·g-1·h-1 and remain stable within 20 H under UV-visible light irradiation at 100 ° C (Fig. 7 a). Under the same reaction temperature, the activation energy is lower under UV-Vis illumination than under pure thermal conditions (Fig. 7B, C). The relationship between catalytic activity and light intensity at different temperatures was then compared, and the results showed that the relationship was linear at low light intensity and superlinear at high light intensity (Fig. 7 d, e). In addition, after NiFe alloy absorbs ultraviolet light, Localized Surface Plasmon Resonance (LSPR) occurs, and the generated hot electrons are injected into the antibonding orbitals of the reactant molecules, which is beneficial to the activation of the reactant, and this LSPR effect is more obvious at low temperatures. The finite-difference time-domain simulation results further confirm that the LSPR effect under 330 nm UV irradiation has the strongest promotion effect on the photothermal catalytic DRM performance of Ni3Fe1.
图7 (a) Ni3Fe1在紫外-可见光照下的DRM稳定性测试; (b) Ni3Fe1光驱动DRM机理示意图; (c) Ni3Fe1在光照和黑暗条件下的DRM活化能; (d) 300℃和 (e) 400℃时Ni3Fe1不同光强下的DRM催化性能[107]

Fig.7 (a) DRM stability test for Ni3Fe1 under UV-vis irradiation; (b) Schematic illustration for the photo-driven DRM reaction over Ni3Fe1; (c) DRM activation energy under light and dark conditions for Ni3Fe1, respectively; Catalytic performance of Ni3Fe1 for DRM at (d) 300℃ and (e) 400℃ under different light intensities[107].Copyright 2022, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Noble metals such as Pd and Pt are the classical active phases for alkane dehydrogenation. A large number of studies have shown that these noble metal sites can not only effectively activate alkane molecules to promote the cleavage of C — H bonds, but also inhibit carbon deposition and prolong the life of catalysts[108⇓~110][111,112]. Based on this, researchers have tried to introduce precious metals such as Pd and Pt into Ni-based LDH to activate the C-H bond of CH4 with the help of precious metals. Our research group doped Pd into NiAl-LDH, and obtained Pd/NiAl of amorphous Al2O3 supported PdNi bimetallic alloy after reduction at 600 ℃ (Fig. 8 a)[113]. The hydrogen production rate of Pd/NiAl can reach 82.9 mmol·g-1·h-1 when the surface temperature of the catalyst is 300 ℃ under UV-Vis irradiation, which is 2.6 times that of the catalyst without Pd. Under sunlight, the hydrogen production rate of Pd/NiAl reached 260.9 mmol·g-1·h-1. A series of characterization and DFT calculation results such as CH4-TPD confirm that the high activity of Pd/NiAl can be attributed to the promotion of CH4 adsorption by Pd doping (Fig. 8 B, C).
图8 (a) Pd/NiAl的合成示意图; NiAl和Pd/NiAl的(b) CH4-TPD谱图和(c) CH4吸附能[113]

Fig.8 (a) Scheme for the synthesis of Pd/NiAl; (b) CH4-TPD spectra and (c) CH4 adsorption energy of NiAl and Pd/NiAl[113].Copyright 2022, American Chemical Society

As another way to transform CH4, CH4 coupling is also of great significance, which is mainly divided into aerobic coupling and anaerobic coupling[114]. Our research group compared the photothermal catalytic CH4 oxygen-free coupling performance of the derivatives Ni-650R, Co-650R and NiCo-alloy obtained from NiAl, CoAl and NiCoAl-LDH calcined and reduced at 650 ° C[115]. Although the three catalysts have similar light absorption properties (Fig. 9a), in terms of catalytic performance, both Ni-650R and NiCo-alloy have millimolar hydrogen production rates, while Co-650R has a lower hydrogen production rate, and the amount of liquid hydrocarbon products produced by Ni-650R and NiCo-alloy is much higher than that of Co-650R (Fig. 9b). Subsequently, we analyzed the adsorption energy of CH4 on the three catalysts by DFT calculation, and the results showed that the CH4 adsorption energy on Co-650R was positive and that on Ni-650R was negative, but after Ni was introduced to Co-650R (NiCo-alloy), the CH4 adsorption energy on Co sites also became negative, indicating that the introduction of Ni promoted the adsorption of CH4 (Fig. 9c).
图9 (a) 催化剂和LDH前体的漫反射谱图[115]; CoAl-650R、NiAl-650R和NiCo-alloy的(b)H2与液态产物生成速率, (c) CH4吸附能[115]; (d) 流动相条件下Au-ZnO/TiO2的光催化CH4有氧偶联稳定性测试[116]; (e) CH4有氧偶联至C2H6或CO2的势能图[116]

Fig.9 (a) Diffuse reflection spectra of the catalysts and LDH precursors; (b) H2 and liquid products yield rate and (c) CH4 adsorption energy for CoAl-650R, NiAl-650R and NiCo-alloy, respectively[115]; (d) Continuous stability test of the photocatalytic OCM over Au-ZnO/TiO2 in a gas flow reactor[116]; (e) Potential energy diagrams for OCM to C2H6 or CO2 on Au-ZnO/TiO2[116]. Copyright 2022, IOP Publishing Ltd

To further activate CH4, researchers introduced O2 into the reaction to achieve efficient activation of CH4. Recently, Ye et al. Designed a Au-ZnO/TiO2 composite structure with ZnTi-LDH as the precursor based on TiO2 and ZnO, two typical photocatalysts[116]. The study shows that, on the one hand, ZnO acts as an adsorption and dissociation active phase of CH4 and O2, and the heterojunction formed by TiO2 and ZnO also effectively inhibits the separation of photogenerated electron-hole pairs.On the other hand, after the ·CH3 generated by the dissociation of the CH4 is transferred to the Au cluster, a higher energy barrier is required for overoxidation, and the interaction with Au greatly reduces the desorption energy, thus avoiding the overoxidation of the ·CH3 to the CO2 and greatly promoting the coupling of the ·CH3 in the next step (Fig. 9e). Subsequently, they further tested the aerobic coupling performance of their CH4 under mobile phase conditions, and the results showed that the generation rate of C2H6 reached an astonishing 5000μmol·g-1·h-1, with a selectivity of 90%, and remained stable within 12 H (Fig. 9d).

3.3 Hydrotalcite-based material as catalyst carrier

Catalysts generally include a catalytically active phase and a support. A suitable support can disperse the reaction active sites, inhibit agglomeration and sintering, and thus prolong the life of the catalyst. If the support has intrinsic activity, it can also induce the adsorption and activation of reactant molecules[117][118,119][120]. In addition, with the help of appropriate synthesis methods, the carrier and the active phase can also form a nanoscale interface structure, which can realize the rapid transmission of electrons between different active sites, and the catalytic performance is also improved[121].
Two-dimensional materials are regarded as ideal catalyst supports because of their large specific surface area, easy control of structural characteristics, and easy formation of interfacial contact[122,123]. Compared with other two-dimensional materials, the unique intercalation structure of LDH, the abundant hydroxyl groups on the lamina, and the flexible and adjustable metal sites make it easier to introduce the active phase[23⇓~25]. Recently, LDH supports have been widely used in a variety of photo/photothermal catalytic CO2 conversion systems, and researchers have loaded various metals/metal oxides on LDH to achieve performance improvement. Although LDH has certain photoresponse properties, the electron-hole pairs generated by photoexcitation are very easy to recombine, resulting in low photocatalytic activity[124]. In order to improve the separation rate of photogenerated carriers, researchers have tried to control the band structure of LDH by loading transition metal oxides.
Katsumata et al. Used ascorbic acid to reduce the wet sample of ZnCr-LDH doped with a small amount of Cu, and obtained ZnCr-LDH loaded with Cu2O[125]. A series of characterization and comparison experiments confirmed that ZnCr-LDH mainly acts as a photosensitizer, while the Cu2O undergoes auto-oxidation under UV irradiation and transforms into a mixed-valence CuOx, and the resulting 3D unoccupied orbital potential of Cu is corrected, so the electrons excited by UV light in the conduction band of ZnCr-LDH can be transferred and enriched on the CuOx, and the recombination of photogenerated electron-hole pairs is inhibited. The photocatalytic CO2 reduction test results showed that the CO production activity of 0.1Cu2O@ZnCr-LDH was much higher than that of ZnCuCr-LDH and ZnCr-LDH. Using the same strategy, Wang et al. Loaded Fe3O4 on ultrathin MgAl-LDH for photocatalytic CO2 reduction[126]. It has been shown that, on the one hand, the strong interaction between Fe3O4 and the support LDH promotes the CO2 adsorption, and on the other hand, because the band gap of Fe3O4 is only 0.1 eV,The photogenerated electrons transported to the surface of LDH can be quickly transferred from the loaded Fe3O4 to the adsorbed CO2, which is beneficial to the further activation of the CO2. The CO2 photoreduction performance of Fe3O4/MgAl-LDH was significantly improved compared with that of MgAl-LDH, and the CO and CH4 formation rates reached 442.2 mmol·g-1·h-1 and 223.9 mmol·g-1·h-1, respectively.
In addition to loading transition metal oxides on LDH, in recent years, many researchers have also achieved efficient conversion of CO2 under light irradiation by using LDH loaded noble metal active phases. Yufei Song et al. Constructed a group of Pd/CoAl-x (X = 0.55, 2.46, 7.57) with different Pd loadings (X wt%) by adding PdCl2 in the synthesis of CoAl-LDH[127]. They found that as the Pd content rises, the Co3+/Co2+ ratio becomes larger, while the valence of Pd gradually decreases, which indicates that Pd2+ abstracts the electron of Co2+ to produce Pd(2-n)+ (Fig. 10 a, B). The photocatalytic CO2 reduction test results under UV – vis illumination showed that the ratio of the product syngas H2 was positively correlated with the Pd loading (Fig. 10 C).
图10 Pd/CoAl-x的 (a) Co 2p, (b) Pd 3d XPS谱图[127]; (c) Pd/CoAl-x光催化CO2还原产物合成气的CO/H2比例[127]; (d) Pt单原子结构随光强的演化[128]; 不同光强下的Pt单原子驱动光催化CO2还原的(e) 选择性和(f) 反应机理[128]

Fig.10 (a) Co 2p, (b) Pd 3d XPS spectra of Pd/CoAl-x[127]; (c) CO/H2 ratio of photocatalytic CO2 reduction products for Pd/CoAl-x[127]; (d) Illustration of Pt SA structure evolution vs light intensity[128]; (e) Selectivity and (f) Reaction mechanism of photocatalytic CO2 reduction driven by Pt SA under different light intensity[128].Copyright 2022, American Chemical Society

Heterogeneous nanocatalytic system is composed of catalyst, reactant and microenvironment, and the interaction among them determines the performance of the whole system. In general, the interaction between the catalyst and the reactant is more concerned by researchers, while the influence of the microenvironment of the system is often ignored. For the LDH-based photocatalytic C1 conversion process, light intensity is an important part of the microenvironment of the system. It is generally believed that the change of light intensity will only increase or decrease the number of photogenerated carriers in LDH, but will not change the intrinsic properties of the catalyst. However, recent studies have shown that light intensity can also change the state of noble metal active sites on LDH carriers, thereby changing the conversion path of the same reactant, and ultimately affecting the product selectivity.
Feng et al. Utilized the carrier defect anchoring mechanism to introduce noble metal Pt onto ZnNiTi-LDH rich in VZn to construct a ZnNiTi-LDH supported Pt single-atom structure[128]. Subsequently, they explored the coordination structure of monatomic Pt under different light intensities, and found that with the increase of light intensity, the coordination number of Pt-O decreased, and the PtIV also accepted the photogenerated electrons to change to a lower valence state (PtIV;500 mW·cm-2 for 200 mW·cm-2, Ptδ+ for PtII;1000 mW·cm-2) (Fig. 10d). The results of photocatalytic CO2 reduction showed that the selectivity of CO was close to 99% when the light intensity was 200 mW·cm-2. When the light intensity increased to the 500 mW·cm-2, the product showed a C2H6 (selectivity 20.49%), which indicated that the single atom of the PtII had a certain C — C coupling activity. When the light intensity is further increased to 1000 mW·cm-2,CH4, the selectivity increases to 8.83%, indicating that the Ptδ+ is beneficial to the hydrogenation path (Fig. 10e, f).
Ye et al. Loaded RuO2 on ultrathin MgAl-LDH by impregnation method and used it for photothermal catalytic CO2 hydrogenation[129]. After a period of pre-activation in the reactant atmosphere, the formed Ru nanoparticles were supported on ultrathin LDH (Ru @ FL-LDH). The ultrathin LDH exposes more hydroxyl sites and has a stronger basicity, thus promoting the adsorption of CO2 (fig. 11A). They further compared the photothermal catalytic CO2 hydrogenation performance of Ru @ FL-LDH and Ru @ LDH, Ru@SiO2, FL-LDH, as shown in Fig. 11 B, C, when FL-LDH was not loaded with Ru,The CO2 conversion is always 0, which indicates that the Ru nanoparticles are the active phase of the reaction, while when the common MgAl-LDH or SiO2 is used as the catalyst support, both the CO2 conversion and the CH4 yield decrease significantly. Therefore, the excellent performance of Ru @ FL-LDH is due to the synergistic effect between Ru nanoparticles and ultrathin MgAl-LDH support. The results of mobile phase performance test under UV-visible-NIR illumination showed that the CO2 conversion rate of Ru @ FL-LDH was over 95%, and the CH4 selectivity was 100% (Fig. 11d).
图11 (a) 富含表面羟基的超薄LDH结构形成示意图; 负载Ru的催化剂和FL-LDH在流动相测试时(b) CO2和(c) CH4 浓度的变化(S1, Ru@FL-LDH; S2, Ru@LDH; S3, Ru@SiO2; S4, FL-LDH); (d) Ru@FL-LDH的CO2加氢稳定性测试[129]

Fig.11 (a) Scheme of formation of ultrathin LDH structure with abundant surface hydroxyl groups; The concentration change of (b) CO2 and (c) CH4 over Ru loaded catalysts and FL@LDH using a flow system (S1, Ru@FL-LDH; S2, Ru@LDH; S3, Ru@SiO2; S4, FL-LDH); (d) Stability test of CO2 hydrogenation over Ru@FL-LDH[129].Copyright 2017, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

4 Conclusion and prospect

In summary, we summarize the latest research progress in light-driven catalytic C1 conversion from three aspects: LDH precursors, LDH-based derivatives, and LDH as catalyst supports.The structure-activity relationship of catalysts is discussed in detail in order to provide readers with a clear and complete perspective, so as to have a deeper understanding of the current frontier research progress of C1 chemistry.
Although there have been many reports on the study of nano-state LDH-based photocatalytic C1 conversion, there are still some challenges in this field.
(1) At present, most of the reported studies on photocatalytic C1 conversion driven by nano-LDH-based materials focus on the light/photothermal catalytic conversion of CO, CO2 and CH4, which are three C1 molecules.There are few studies using LDH and its derivatives to catalyze the transformation of polar C1 molecules with characteristic functional groups, such as CH3OH, HCHO, HCOOH. Researchers can try to apply nano-LDH-based materials to the photocatalytic conversion of these C1 molecules, and further expand the application of LDH-based materials in C1 chemistry.
Recently, our group realized the photothermal catalytic CH3OH reforming to H 2 by using the topological transformation effect of CuAl-LDH[130]. At present, little attention has been paid to the types and selectivity of carbon-containing products in the reaction of CH3OH reforming to H2. Carbonaceous products are generally CO and CO2 with low added value, so it is necessary to further increase the added value of products. With the help of LDH-based materials containing specific metal components, the preparation of high-value carbon-containing products can be achieved by further regulating the reaction path of intermediates (—CH2) while obtaining higher yield of H2. HCHO and HCOOH face the same problem.
(2) The light-driven C1 conversion of nano-LDH-based materials reported at present often only completes the one-step conversion of C1 molecules, and the research on the tandem reaction system of C1 conversion is still in the exploratory stage. It is hoped that a series of nano-LDH-based catalysts driving the conversion of different C1 will be used in the future to further enhance the added value of products. However, in the tandem reaction system, there are often two different types of reactions, two different active sites, and their reaction conditions are generally different. How to make the reaction conditions more matched requires a challenge in the design of catalysts and the construction of bifunctional active sites, which will be the focus and difficulty of future research in this field.
(3) At present, the understanding of nano-LDH-based light-driven C1 conversion reaction system generally stays at the gas-liquid and gas-solid two-phase level, ignoring the influence of the third phase reaction system. In the future, the reaction system containing liquid products should be understood from the perspective of gas-liquid-solid three phases, and the role of mass transfer in the reaction system should be considered to achieve further regulation of the selectivity of target products. However, the biggest challenge in the three-phase system is the stability problem, which is easy to destroy the catalytic interface during the reaction, thus affecting the formation of products, and this problem remains to be solved.
(4) At present, the reaction mechanism of light-driven C1 chemical conversion is still unclear, and the role of light is highly controversial, especially in some complex C1 conversion reactions, such as FTS and CO2 hydrogenation to multi-carbon products. How to quantify the contribution of photothermal and photocatalysis more accurately in the process of photothermal synergistic catalysis will be of great significance and a major challenge in the future. In addition, in a series of light-driven C1 chemical reactions, some calculation formulas are controversial, such as the calculation formula of solar energy conversion efficiency.

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