General

Siquan Feng, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Associate Professor

E-mail: siquan@dicp.ac.cn

Address: No. 457, Zhongshan Road, Shahekou District, Dalian, Liaoning

Zip: 116023


Research Areas

  1. Atomic dispersion of transitional metal particles.
  2. Construction of atomically dispersed single-site, and dual-sites metal catalysis.
  3. Determination of structure-activity relationship in heterogeneous catalysis.
  4. Sulfur tolerance of nanoparticles, clusters, and single-atom catalysts.
  5. Carbonylation of alcohol, ester, alkenes, alkynes, and amine by single-site catalysis.
  6. Preparation of environmental-friendly polyester monomer, EG, PGA, 1,3-PDO, 1,4-BDO,  CBDO.
  7. Activation of methane, ethane, propane, butane, and carbon dioxide.
  8. Transformation of syngas to high-carbon alcohols, paraffin, and valuable alkenes.
  9. Basic research + theoretical exploration + engineering simulation.
  10.  Laboratory trial → pilot test (single  tube or kettle) → industrial model test → demonstration.

Education

2019-2014

Doctorate in Industrial   Catalysis, Dalian Institute of Chemical Physicals, Chinese Academy of Science

2014-2013

Department of   Chemical Science and Engineering, University of Chinese Academy of Science   (Guaranteed acceptance)

2013-2009

BSc in Chemical   Science and Engineering, Yunnan University

Experience

In situ FT-IR ; In situ XPS; In situ QXAFS; In situ XRD; In situ FEL TOF MS

EXAFS/XANES analysis; HR-TEM/HAADF-STEM; 

Raman ; EPR-ESR; Chem Adsorption; Phyiscal Adsorption; NMR; FEL TOF MS; GC MS; GC

C4D; Chem Draw; PS; 3d MAX; Maya; Auto CAD; Origin; Xmind; Diamond; Crystal maker; Gaussian 09; Materials Studio; Metlab 2019; VESTA; VASP; Digtal micrograph; Solid works; Sigmal plot 

Preparation of varieties of single atom catalysts

Evaluation of the activity of heterogeneous catalyst in fix-bed reactor, pilot test (single tube or kettle)

Experience in the pilot test in single-tube of 3m, 7m

Work Experience

2023- 2022

Associate Professor   II, Master's Supervisor, Dalian Institute of Chemical Physicals, Chinese   Academy of Science

2022-2020

Associate Professor   III, Master's Supervisor, Dalian Institute of Chemical Physicals, Chinese   Academy of Science (Special Talents Program)


Publications

   
Papers

 Main Publications:

[22Siquan Feng#, Miao Jiang#, Tao Wu#, Panzhe Qiao, Siyue Liu, Xiangen Song*, Li Yan, Cunyao Li, Bin Li, Yutong Cai, Weiqing Zhang, Guorong Wu, Jiayue, Yang, Wenrui Dong*, Xueming Yang, Jingwei Li, Zheng Jiang, Yunjie Ding*H2S Poisoning and Self-recovery of Single-site Rh1/POPs for Heterogeneous Hydroformylation of OlefinsAngew. Chem. Int. Ed. 2023, e202304282.

https://doi.org/10.1002/anie.202304282

[21] Siquan Feng#; Jiali Mu#; Xiangsong Lin#; Xiangen Song; Siyue Liu; Wen Shi; Weiqing Zhang; Guorong Wu; Jiayue Yang; Wenrui Dong; Xueming Yang; Jingwei Li; Zheng Jiang; Yunjie DingSulfur-Poisoning on Rh NP but Sulfur-Promotion on single-Rh1-site for Methanol Carbonylation. Applied Catalysis B – Environmental, 2023, 325, 122318.

https://doi.org/10.1016/j.apcatb.2022.122318

[20] Xingju Li, Siquan Feng, Xiangen Song*, Qiao Yuan, Bin Li, Lili Ning, Weimiao Chen, Jingwei Li, Yunjie Ding*, The Evolution of Single-Site Pd1/AC Catalyst During the Process of Acetylene Dialkoxycarbonylation, Journal of Catalysis, 2022, 413, 762-768.

https://doi.org/10.1016/j.jcat.2022.07.026.

[19] Yuan Qiao#; Gu Yating#Feng, Siquan; Song, Xiangen*; Jiali, Mu; Li, Bin; Li, Xingju; Cai, Yutong; Jiang, Miao; Yan, Li; Jingwei, Li; Jiang, Zheng; Wei, Yingxu; Ding, Yunjie*Sulfur-Promoted Hydrocarboxylation of Olefins on Heterogeneous Single-Rh-Site CatalystsACS Catalysis 2022, 12, 7, 4203-4215.

https://doi.org/10.1021/acscatal.1c06039.

[18] Xingju, Li#Feng, Siquan#; Patrick, Hemberger; Andras, Bodi; Song, Xiangen*; Qiao, Yuan; Jiali, Mu; Li, Bin; Jiang, Zheng; Ding, Yunjie* Iodide-Coordinated Single-Site Pd Catalysts for Alkyne DialkoxycarbonylationACS Catalysis 2021, 11, 9243-9251.

https://doi.org/10.1021/acscatal.1c01579.

 [17Feng, Siquan#; Lin, Xiangsong#; Song, Xiangen*; Binbao, Mei; Jiali, Mu; Jingwei, Li; Yang, Liu; Jiang, Zheng*; Ding, Yunjie*Constructing Efficient Single-Rh-Sites on Activated Carbon via Surface Carbonyl Groups for Methanol CarbonylationACS Catalysis 2021, 11(2), 682-690.

https://doi.org/10.1021/acscatal.0c03933.

[16] Yu, Zhipeng#; Xu, Junyuan#Feng, Siquan#; Song, Xiangen; Bondarchuk, Oleksandr; Faria, Joaqim L.; Ding, Yunjie*; Liu, Lifeng*; Rhodium Single-atom Catalysts with Enhanced Electrocatalytic Hydrogen Evolution PerformanceNew Journal of Chemistry 2021, 45, 5770-5774.

https://doi.org/10.1039/D1NJ00210D.

[15] Li, Bin; Song, Xiangen*; Feng, Siquan; Yuan, Qiao; Jiang, Miao; Yan, Li; Ding, Yunjie*; Direct Conversion of Methane to Oxygenates on Porous Organic Polymers Supported Rh Mononuclear Complex Catalyst under Mild ConditionsApplied Catalysis B: Environmental 2021293, 120208. 

https://doi.org/10.1016/j.apcatb.2021.120208.

[14] Yuan, Qiao; Song, Xiangen*; Feng, Siquan; Jiang, Miao; Yan, Li; Ding, Yunjie*; An Efficient and Ultrastable Single-Rh-Site Catalyst on a Porous Organic Polymer for Heterogeneous Hydrocarboxylation of Olefins. Chemical Communication 202157(4), 472-475. 

https://doi.org/10.1039/D0CC06863B.

[13Feng, Siquan; Hemberger, Patrick; Bodi, Andras; Song, Xiangen; Yu, Tongpo; Jiang, Zheng; Liu, Yang;  Ding, Yunjie*Preparation and Regeneration of Supported Single-Ir-site Catalysts by Nanoparticle Dispersion via Nascent I RadicalsJournal of Catalysis 2020382, 347-357.

https://doi.org/10.1016/j.jcat.2019.12.040.

[12Feng, Siquan#; Lin, Xiangsong#; Song, Xiangen*; Liu, Yang; Jiang, Zheng; Hemberger,   Patrick; Bodi, Andras; Ding, Yunjie*; The Role of H2 on the Stability of the Single-Metal-Site Ir1/AC Catalyst for Heterogeneous Methanol CarbonylationJournal of Catalysis 2020, 381, 193-203.

https://doi.org/10.1016/j.jcat.2019.10.032.

[11] Li, Jinlei; Li, Cunyao; Feng, Siquan; Zhao, Ziang; Zhu, Hejun; Ding, Yunjie*; Atomically Dispersed Zn-Nx Sites in N-Doped Carbon for Reductive N-formylation of Nitroarenes with Formic Acid. ChemCataChem 202012 (6), 1546-1550. 

https://doi.org/10.1002/cctc.201902109.

[10Feng, Siquan#; Song, Xiangen#*; Liu, Yang#; Lin, Xiangsong*; Yan, Li; Liu, Siyue; Dong, Wenrui; Yang, Xueming; Jiang, Zheng*; Ding, Yunjie*; In situ formation of mononuclear complexes by reaction-induced atomic dispersion of supported noble metal nanoparticles. Nature Communication 201910 (1), 5281.

https://doi.org/10.6084/m9.figshare.9948161.

[9Feng, Siquan#; Lin, Xiansong#; Song, Xiangen; Liu, Yang; Jiang, Zheng; Ding, Yunjie;  Insight into the stability of binuclear Ir–La catalysts for efficient heterogeneous methanol carbonylationJournal of Catalysis 2019, 377, 400-408.

https://doi.org/10.1016/j.jcat.2019.06.050.

[8Feng, Siquan; Song, Xiangen; Ren, Zhou; Ding, Yunjie; La-stabilized, single-atom Ir/AC catalyst for heterogeneous methanol carbonylation to methyl acetateIndustrial & Engineering Chemical Research 2019, 58 (12), 4755-4763.

https://doi.org/10.1021/acs.iecr.8b05402.

[7] Zheng, Changyong; Feng, Siquan; Song, Xiangen*; Ding, Yunjie*; Activated Carbon Supported Au-Cu Binary Catalyst for Heterogeneous Methanol Carbonylation. Shiyou Huagong/Petrochemical Technology, 2019, 48(12), 1191-1198.

[6] Ren, Zhou; Liu, Yang; Lyu, Yuan*; Song, Xiangen; Zheng, Changyong; Feng, Siquan; Jiang, Zhen; Ding, Yunjie*; Sing-Atom Rh Based Bipyridine Framework Porous Organic Polymer: A High Active and Suprerb Stable Catalyst for Heterogeneous Methanol Carbonylation.  Journal of Catalysis, 2019, 369, 249-256.

https://doi.org/10.1016/j.jcat.2018.11.015.

[5] Ren, Zhou; Lyu, Yuan*; Feng, Siquan; Song, Xiangen; Ding, Yunjie*; Acid-Promoted Ir-La-S/AC Catalyzed Methanol  Carbonylation on Single Atomic Active Sites. Chines Journal of Catalysis 2018, 39 (6), 1060-1069.

https://doi.org/10.1016/S1872-2067(18)63019-0.

[4] Ren, Zhou.; Lyu, Yuan*; Feng, Siquan; Song, Xiangen; Ding, Yunjie*; A Highly Efficient Single Site Rh-POL-PPh3 Catalyst for  Heterogeneous Methanol Carbonylation. Molecular  Catalysis 2017, 442, 83-88.

https://doi.org/10.1016/j.mcat.2017.09.007.

[3] Li, Cuiping;* Wang, Jiaqiang; Feng, Siquan; Liu, Zhan, Low-Temperature Synthesis of Crystalline  Inorganic/Metallic Nanocr-Halloysite Composite Nanotubes. Chinese Journal Chemistry 2014, 32 (7), 599-606.

https://doi.org/10.1002/cjoc.201400154.

[2] Li, Cuiping;* Wang, Jiaqiang; Feng, Siquan; Yang, Zhan; Ding, Sujiang, Low-Temperature Synthesis of Heterogeneous Crystalline TiO2-Halloysite Nanotubes and Their Visible Light Photocatalytic Activity. Journal of Materials Chemistry A 2013, 1 (27), 8045-8054.

https://doi.org/10.1039/C3TA11176H.

[1] Liu, Chuanshui; Tai, Zhigang; Feng, Siquan; Fang, Yunshan; Cai, Le*; Ding, Zhongtao, Chemical Constituents from the Seed Coat of Juglans Regia. China J. Chin. Mater. Med. 2012,   37 (10), 1417-1421.


Patents

 Patents (41, including PCT 3, Authorized 12)

(1) PCT Patents (2)

[1] Ding Yunjie; Feng Siquan; Song Xiangen; Li Xingju, Palladium-based catalyst, preparation, method therefore and use thereof. WO2022105199A1, PCT, 20220527/20210609

[2] Ding Yunjie; Song Xiangen; Li Bin; Feng Siquan; Jiang Miao, Catalyst, and preparation method and use, WO2022105047A1, PCT, 20220527/20210108

[3] Ding Yunjie; Feng Siquan; Song Xiangen; Li Xingju, Monatomically dispersed palladium-based catalyst, preparation method and application thereof. WO2022257025A1, PCT, 20221215/20210608

(2) Authorized (12)

[12] Ding Yunjie; Feng Siquan; Song Xiangen, The invention discloses a catalyst for preparing methyl acetate by methanol gas-phase carbonylation, and preparation and application thereof, CN109759084B, China, 20220510/20171109

[11] Ding Yunjie; Feng Siquan; Song Xiangen; Activated carbon supported sulfur-containing iridium-based catalyst as well as preparation and application thereof, CN109759055B, China, 20220415/20171109

[10] Ding Yunjie; Feng Siquan; Song Xiangen, Activated carbon supported iron sulfide-based catalyst as well as preparation method and application thereof, CN109759085B, China, 20211130/20171109

[9] Ding Yunjie; Feng Siquan; Song Xiangen, Activated carbon supported iron sulfide-based catalyst containing auxiliary agent as well as preparation and application of activated carbon supported iron sulfide-based catalyst, CN109759086B, China, 20211130/20171109

[8] Ding Yunjie; Feng Siquan; Song Xiangen, Activated carbon supported iridium-based catalyst containing iron-nickel sulfide as well as preparation and application of activated carbon supported iridium-based catalyst, CN109759090B, China, 20211123/20171109

[7] Ding Yunjie; Feng Siquan; Song Xiangen, Rhodium-based catalyst, preparation method thereof and application of rhodium-based catalyst in methanol vapor phase carbonylation reaction, CN111195529B, China, 20210525/20181120

[6] Ding Yunjie; Feng Siquan; Song Xiangen, Atomic-scale monodispersed iridium-based catalyst, preparation method thereof and application of atomic-scale monodispersed iridium-based catalyst in preparation of methyl acetate through methanol gas-phase carbonylation, CN111195532B, China, 20210525/20181120

[5] Ding Yunjie; Feng Siquan; Song Xiangen, Atomic-scale monodispersed iridium-based catalyst and preparation method and application thereof. CN111195530B, China, 20210423/20181120

[4] Yunjie Ding; Feng Siquan; Song Xiangen, Atomic scale monodisperse rhodium-based catalyst, preparation method thereof and application of catalyst in methyl acetate preparation through methanol vapor phase carbonylation, CN111195516B, China 20210423/20181120

[3] Yunjie Ding; Feng Siquan; Song Xiangen, Monoatomic disperse precious metal catalyst as well as preparation method and application thereof, CN111195515B, China, 20210423/20181120

[2] Ding Yunjie; Feng Siquan; Song Xiangen; Li Bin, Monoatomically dispersed rhodium-based catalyst, preparation method thereof and application thereof in methane low-temperature oxidation reaction, CN111195514B, China, 20210330/20181120

[1] Song Xiangen; Ding Yunjie; Lyu Yuan; Feng Siquan; Ren Zhou, Ultrahigh loading monatomic noble metal catalyst and preparation method thereof, CN109126774B, China, 20210209/20170615

 

Open and un-authorized yet (20)

[20] Ding Yunjie; Song Xiangen; Li Bin; Feng Siquan; Jiang Miao, Quaternary phosphonium salt polymer supported bimetallic monoatomic catalyst and preparation method and application thereof, CN114515604A, China, 20220520/20201211

[19] Feng Siquan; Ding Yunjie; Song Xiangen; Li Xingju; The invention relates to an application of a carbon-supported monoatomic Pd catalyst in alkyne carbonylation reaction, CN114524729A, China, 20220524/20221123

[18] Ding Yunjie; Song Xiangen; Feng Siquan; The invention relates to a supported sulfonium anchoring monoatomic catalyst and a preparation method thereof, CN114534780A, China, 20220527/20221124

[17] Song Xiangen; Ding Yunjie; Feng Siquan, Active carbon-loaded rhodium-based catalyst and its preparation method and use, CN106140156A, China, 20161123/20150420

[16] Ding Yunjie; Feng Siquan; Ren Zhou; Song Xiangen; Chen Weimiao, Activated carbon supported iridium-based catalyst for preparing methyl acetate through methanol vapor-phase carbonylation and application of catalyst, CN108069857A, China, 20180525/20161115

[15] Yunjie Ding; Song Xiangen; Feng Siquan; The invention relates to a method for preparing 1, 4-diaceoxy-2-butene, CN115466177A, China, 20221213/20210611

[14] Ding yunjie; Feng siquan; Song xiangen; Li xingju; Monoatomic dispersed palladium-based catalyst and preparation method and application thereof, CN115445636A, China, 20221209/20210608

[13] Ding Yunjie; Xingju Li; Song Xiangen; Feng Siquan, Application of quaternary phosphonate ionic polymer supported palladium Catalyst in Carbonylation of alkynes, CN115463694A, China, 20221213/20210610

[12] Ding Yunjie; Xingju Li; Song Xiangen; Feng Siquan, The invention relates to a phosphate-containing organic polymer/activated carbon composite carrier and its preparation and application, CN115463648A, China, 20221213/20210610

[11] Feng Siquan; Ding Yunjie; Song Xiangen; Li Xingju; The invention discloses a carbon-supported Pd-M bimetallic monoatomic catalyst and an application thereof in a C2H2 dicarbonylation reaction, CN114522683A, China, 20220524/20201123

[10] Ding Yunjie; Yuan Qiao; Song Xiangen; Feng Siquan, The invention relates to a method for preparing acetic acid and acetic ester by halogen-free gas-phase carbonylation of methanol, CN114534724A, China, 20220527/20201124

[9] Ding Yunjie; Feng Siquan; Song Xiangen, Porous organic ion polymer, supported monatomic Rh catalyst thereof, and preparation method and application thereof, CN114534782A, China, 20220527/20220117

[8] Ding Yunjie; Yuan Qiao; Song Xiangen; Feng Siquan, The invention relates to a preparation method and application of a catalyst for preparing acetic acid and acetic ester through halogen-free gas-phase carbonylation of methanol, CN113941329A, China, 20220118/20200706

[7] Ding Yunjie; Song Xiangen; Feng Siquan, The invention relates to a method for preparing methyl acetate through carbonylation of methanol, CN114539056A, China, 20220527/20201124

[6] Ding Yunjie; Yuan Qiao; Song Xiangen; Feng Siquan, A process for preparing organic carboxylic acids by hydrocarboxylation of olefins, CN114534792A, China, 20220527/20201124

[5] Ding Yunjie; Li Xingju; Song Xiangen; Feng Siquan; Yuan Qiao; Ning Lili, Method for preparing acetaldehyde, ethanol and ethyl acetate by reduction carbonylation of methanol, CN114524719A, 20220524/20201123

[4] Ding Yunjie; Lee Sung-Kuk; Song Xiangen; Feng Siquan; Yuan Qiao; Ning Lili, The invention relates to a carbon-supported bimetallic monoatomic catalyst and a preparation method thereof. CN114522682A, China, 20220524/20201123

[3] Ding Yunjie; Feng Siquan; Ren Zhou; Song Xiangen; Chen Weimiao, Activated carbon supported Ir-based catalyst as well as preparation and application thereof, CN108067226A, China, 20180525/20161115

[2] Song Xiangen; Ding Yunjie; Feng Siquan; Chen Weimiao, Iridium-based catalyst loaded by carbon-based material and preparation method and application of iridium-based catalyst, CN106807367A, China, 20170609/20151202

[1] Song Xiangen; Ding Yunjie; Feng Siquan; Chen Weimiao; Activated carbon-supported iridium-based catalyst, as well as preparation method and application thereof, CN106807368A, China, 20170609/20151202


Conferences

[1] Feng Siquan; Song  Xiangen; Ding Yunjie; Ir1-La1/AC catalyzed carbonylation of methanol to methyl acetate. The 16#   International Congress on Catalysis, Beijing, 2016, Poster.

Collaboration

(1) University of Science and Technology of China; Heifei Synchrotron Radiation Facitity;

(2) University of Chinese Academy of Scienses;

(3) Dalian University of Technology, China;

(4) Jiaxing University;

(5) Institute of Advanced Studies, Zhejiang Normal University;

(6) Institute of Applied Physics, CAS;  Shanghai Advanced Research Institute, CAS;

(7) Shanghai Synchrotron Radiation Facitity;

(8) Beijing Institute of High Energy; Beijing Synchrotron Radiation Facitity;

(9) Yunnan University;

(10) Paul Scherrer Institute (PSI), Switzerland;

Students in Recent 3 Years

(1) Bin Li, PhD, Industrial Catalysis, University of Chinese Academy of Sciences, 2017.09

(2) Qiao Yuan, Master, Industrial Catalysis, University of Chinese Academy of Sciences, 2018.09

(3) Xingju Li, PhD, Physical Chemistry, University of Science and Technology of China, 2019.09

Honors & Distinctions

(12) Member of Youth Innovation Promotion Association, Chinese Academy of Sciences, 2022

(11) Top 100 Excellent Doctoral Dissertation Award, Chinese Academy of Sciences, 2021  

(10) Excellent Doctoral Graduates of Chinese Academy of Science University, Institute (School), 2021

(9) Excellent Doctoral Graduates of Beijing, Municipal and Prefecture-level, 2020

(8) Outstanding young doctoral talents of Dalian Institute of Chemical Physicals, CAS, 2019

(7) National Scholarship, National Level, 2019

(6) Tang Lixin Scholarship, Institute (School), 2019

(5) Lin Liwu Outstanding Doctoral Scholarship, Institute (School), 2019

(4) Excellent Communist of Chinese Communist Party, Institute (School), 2019

(3) Merit Student Model of University of Chinese Academy of Sciences, Institute (School), 2018

(2) Excellent Student Cadre of University of Chinese Academy of Sciences, Institute (School), 2015

(1) Outstanding Student Cadre of Yunnan Province, Provincial, 2012



Key Job Performance

(1) MTE (methanol to ethanol) technology by methyl acetate

Considering the national energy security of fuel ethanol and the reality of the shortage of bioethanol, our team designed several paths to produce ethanol.

(a) Syngas to oxygenated chemicals, and further hydrogenated to ethanol; (Lab test finalize, single tube pilot test verification);

(b) Methanol carbonylation to acetic acid, and further hydrogenated to ethanol; (30,000 tons industrialization);

(c) Dimethyl ester carbonylation to methyl acetate, and further hydrogenated to ethanol; (500,000 tons industrial demonstration, Liu Zhongming team);

(d) Esterification of ethylene and acetate acid to acetic esters, and further hydrogenated to ethanol. (Two sets of 300,000 tons of industrial equipment);

Based on the above technologies, we proposed a new way of MTE via methanol carbonylation to methyl acetate, and hydrogenated to ethanol in a fix-bed reactor.

Figure 1  MTE by methanol carbonylation to methyl acetate and hydrogenation.

As the core member, I participated in the key research project of coal to ethanol via syngas and methanol carbonylation to methyl acetate and hydrogenation technologies, and the national key research and development plan of "Direct production of ethanol from coal by syngas" (2017YFB0602203/06). Recently, the technology has been licensed to four chemical enterprises (Two sets of 300,000 tons of industrial equipment to ethanol, and one set of 300,000 tons of industrial equipment to ethyl acetate).

For this technology, an adjustment of the product from acetate acid (99%) at homogeneous to methyl acetate (96%) at heterogeneous was achieved. Our heterogeneous single-atom Ir-La/AC catalyst demonstrated higher activity than the homogeneous Cartiva TM [Ir(CO)2I2]-  catalyst. The related work is published in Industrial & Engineering Chemistry Research 2019, 58, 4755−4763. (First author)

(2) Atomic dispersion of noble nanoparticles supported on activated carbon

Figure 2.1  Atomic dispersion of Rh metal nanoparticles supported on activated carbon.

During the process of heterogeneous methanol carbonylation, it is interesting to find that the nanoparticles Rh or Ir catalyst supported on activated carbon could atomic dispersing into the level of a single atom. Further investigation suggested that CO and CH3I are the most important promoter for the atomic dispersing of nanoparticles.

XRD, EDS, EXAFS, HAADF-STEM, and other characterization methods were used to characterize the catalyst‘s geometrical structure before and after dispersion. The atomically dispersed single-Rh-atom catalysts did not contain Rh-Rh metallic bond basically, and there was no loss of Rh metal. The characterization results of CO-TPD, ATR-FTIR, EPR, LDI/TOF MS further proved that the atomically dispersed Rh was mainly composed of Rh(CO)2I3(O=AC) mono complex. In addition, it is found that the appropriate temperature, CO, CH3I, and the oxygen-containing functional groups on the surface of supported activated carbon are necessary to fulfill the atomic dispersion of Rh nanoparticles. LDI/TOF MS test showed that during the dispersive process, CH3I would homogenize and produce a large amount of iodine-free radical (I·), which has a strong oxidation ability to the metal atoms on the surface of nanoparticles. Meanwhile, the synergistic effect of I· and CO can synergetically promote the breaking of the Rh-Rh bond on the surface of Rh nanoparticles and the formation of Rh(CO)2I3(O=AC) mononuclear complex, so as to realize the gradual single-atomic dispersion of Rh nanoparticles. The oxygen functional group on the carrier surface provides a stable anchoring site for Rh mononuclear complex.

Figure 2.2  Atomic dispersion of Rh metal nanoparticles supported by activated carbon.

The technique is also effective for the atomic dispersion of other 5% (wt.) carbon-supported Ir, Pt, Pd, Ru, Ag, and other noble metal nanoparticles, indicating that the method has good universality and can be used for the large-scale preparation of single atomic catalysts. At the same time, the method provides a very good way for the regeneration of deactivated catalysts due to sintering agglomeration. The related work is published in Nature Communication 2019, 10 (1), 5281 (First author).

(3) Regeneration of Ir catalyst and their size effect in atomic dispersion

Since the Ir-Ir metal bond is the strongest in precious metals, investigating the atomic dispersion of Ir nanoparticles has significance for other metal nanoparticles. It was found that CO/CH3I synergetic interaction was also effective for the atomic dispersion of small Ir nanoparticles (1~3nm) supported by activated carbon. However, when the size of Ir nanoparticles increased and was larger than 6 nm, it could not be atomically dispersed, and on the contrary, aggregated into larger nanoparticles, it is different from the theory of Ostwald Ripening. This is attributed to the size effect during the dispersion of Ir nanoparticles. It is found that when Ir nanoparticles grow larger, surface potential energy and surface defects will be greatly reduced. At the same time, the surface atoms are strengthened by metal bonds in the metal bulk phase, which is greater than the pulling of CO and CH3I on surface atoms. As a result, it becomes very difficult to peel the surface atoms of large Ir nanoparticles until they cannot be dispersed. The related work is published in the Journal of Catalysis 2020, 382, 347-357 (First author).

Figure 3 Preparation and regeneration of single-site Ir1 supported on activated carbon (AC) for methanol gas-phase carbonylation.


(4) Investigation of homogeneous and heterogeneous metal catalysis.

 

 

Figure 4 Homogeneous and heterogeneous catalyzed methanol carbonylation over single-site Rh1 catalyst ([Rh(CO)2I2]- and Rh1/AC).

The single-site Rh1/AC catalyst was prepared by CO/CH3I treatment as above mentioned, and the bridge relationship between homogeneous catalysis and heterogeneous catalysis was investigated. It was found that the single-site Rh1 catalyst Rh(CO)2I3(O=AC) showed better catalytic activity of methanol carbonylation than the homogeneous [Rh(CO)2I2]- system. It is found that the oxidation addition of CH3I is the rate-determining step of the reaction, and the single-site Rh1/AC catalyst demonstrated lower apparent activation energy and reaction energy barrier than the homogeneous catalyst. It was found that the strong interaction of metal-supported electrons enhances the nucleophilic attack of the single-site Rh1 against CH3I. The related work is published in ACS Catalysis 2021, 11(2), 682-690 (First Author).


  (5) H2 and the stability of single-site Ir1/AC for methanol carbonylation

Figure 5 Mechanism of methanol carbonylation over Ir1/AC catalyst.

H2 was evidenced vital to guarantee the stability of single-site Ir1/AC catalyst for methanol carbonylation. Single-site Ir1/AC catalyst would gradually be inactivated without H2 due to carbon deposition and metal loss, which came from the resident species of the acetyl iodine reduction step, which has very high energy barrier. H2 sacrifice part of the active site to convert single-site Ir1 atoms into Ir0 clusters, which return activated H2 to produce active H, which is the excellent promoter inhibiting and alleviating the acetyl iodine reduction step carbon of the catalyst. The nanoclusters will atomic dispersed again under the action of CO and CH3I. Therefore, H2 maintains the structure-activity equilibrium between the aggregation and single-atom dispersion of Ir.

Besides, metal loss of catalyst was confirmed mainly from the volatilization of Ir(CO)3I species. The presence of Ir191(CO)3I and Ir193(CO)3I species was detected for the first time using the PEPICO-UVU spectra of the Swiss light source. The existence of H2 inhibits the formation of the volatilizative Ir(CO)3I species. The related study was published in the Journal of Catalysis 2020, 381, 193-203 (First Author).


 (6) Single-site dual-core Ir1-La1/AC, indirect metal support strong interaction.

Figure 6.1 (a) single-site Ir1/AC and (b) single-site dual-core Ir1-La1/AC.

Catalysts often have a seesaw effect between catalytic activity and stability, that is, the higher the catalytic activity, the worse the stability of the catalyst. To solve this problem, we prepared a single-site dual-core Ir1-La1/AC catalyst for methanol carbonylation, and found that the Ir1-La1/AC catalyst performed better catalytic activity than the traditional nanoparticle catalyst. Moreover, compared with the single-site Ir1/AC catalyst, Ir1-La1/AC catalyst still showed higher catalytic activity, which achieved the unity of high activity and high catalytic stability of methanol carbonylation under harsh reaction conditions.

 

Figure 6.2 Comparison of Ir1/AC and Ir1-La1/AC for methanol carbonylation.

Figure 6.3 Scheme of Ir1-La1/AC catalyzing methanol carbonylation.

 By using HAADF-STEM and EXAFS et al., it has been found that there is an Ir-La and Ir-I-La interaction for Ir1-La1/AC catalyst in a single-site dual-core Ir1-La1/AC catalyst. In the carbonylation reaction, the apparent activation energy of the Ir1-La1/AC catalyst is much lower than that of the Ir1/AC catalyst. The presence of La promotes Ir3+ reduction to Ir+ but inhibits Ir+ reduction to Ir0.  Ir0 is the inactive state of Ir. The interaction of Ir-La enhanced the stability of Ird+ in response. In addition, Ir-La interaction changes the rate-determining step of the reaction, significantly reduces the energy barrier of the CH3COI reduction elimination step, inhibits the carbon deposition of the catalyst, and improves the catalytic activity and stability. In addition, further research found that in the single-site dual-core Ir1-La1/AC catalyst, the presence of La promoted the reduction of Ir3+ to Ir+ but inhibited the reduction of Ir+ to Ir0. The catalytic process of the active metal Ir would cycle between +1 and +3. Therefore, the presence of La not only promoted the reaction but also increased the stability of the single-site dual-core Ir1-La1/AC catalyst. The stability of the electronic state of the catalytic active Ird+ was maintained. The related research was published in the Journal of Catalysis 2019, 377, 400-408 (First Author).

 

 (7)   Expanding of the single-atom dispersion strategy of nanoparticles

 

Figure 7 Scheme of preparation of hetero-bimetallic monatomic catalyst by single-atomic dispersion of bimetallic nanoparticles.

The single-atomic dispersion strategy of single-metal nanoparticles was extended to the bimetallic or multi-metallic nanoparticles, and it was found that the CO/CH3I treatment was still effective for the single-atomic dispersion of bimetallic or multi-metallic nanoparticles. Currently, it has been found that CO/CH3I treatment is also effective for the single-atomic dispersion of the Rh-Ru/AC, Rh-Pd/AC, Rh-Ru-Pd/AC, Rh-Ru-Pd-Au/AC nanoparticles, which can be easily realized and preparing the atomic dispersion of two-sites or multi-sites Rh1-Ru1/AC, Rh1-Pd1/AC, Rh1-Ru1-Pd1/AC, and Rh1-Ru1-Pd1-Au1/AC catalyst. It is further proved that this method opens a new direction for the preparation and application of double single-atom metal active site catalysts, especially hetero-metallic single-atomic catalysts. The related work was supported by the National Natural Science Foundation of China (NSF 22002156). (Project leader).

 

(8) Acetylene single-carbonylation to acrylic acid, methyl acrylate, and acrylamide

With the maturation of methane to acetylene industrial technology (cost 6200 /ton), and the gradual rise of the price of ethylene (8400 /ton), propylene (7600 /ton), the development of high-value utilization and conversion of acetylene is of great significance to guarantee the energy security and economic development of China. Acrylic acid (12000 /ton), acrylic ester (18000 /ton), and acrylamide (14000 /ton) are the ordinary chemicals, in which acrylamide is known as "Versatile additives" and is huge shorted. The previous technology required the use of toxic and harmful acrylonitrile to hydrolyze amination, the cost is higher. The conversion of acetylene carbonyl to acrylic acid methyl acrylate and acrylamide by single-atom catalysis is an important breakthrough point.

Figure 8 Scheme of acetylene carbonylation catalyzed by single atom Pd1 to to acrylic acid, methyl acrylate, and acrylamide.

Through the single-atomic dispersion strategy of nanoparticles and the bottom-to-top strategy, the unit Pd1 catalyst was constructed to achieve the synthesis of methyl acrylate (71% conversion, 85% selectivity) and acrylamide (60% conversion, 99% selectivity) by acetylene single carbonylation. This project is supported by the Independent Deployment Innovation Fund (DICPI 202237) of the Dalian Institute of Chemical Sciences, Chinese Academy of Sciences. (Project leader).

 

 (9) Dicarbonylation of acetylene catalyzed by single atom Pd1.

With the deployment of the 14th Five-Year Plan and the implementation of the national "plastic restriction" policy of China, degradable plastics ushered in a development opportunity. Dimethyl butenediate is the direct monomer of biodegradable plastics PBS and the upstream raw material of biodegradable plastics PBT and PBAT intermediate monomer BDO (1, 4-butanediol). Limited by the shortage of technology and raw materials, the price of BDO soared from 12,000 /ton to 38,000 /ton in 2021. In this context, the single-atomic Pd1/AC catalyst was prepared in-situ from Pd nanoparticles by the single-atomic dispersive method, and consequently, the dimethyl butenediate was produced with high activity and high selectivity by acetylene dicarbonylation under moderate conditions of 80 and system pressure of 3.5MPa (both conversion rate and selectivity > 90%). It is also proved that Pd is different from Ir metal nanoparticles in that there is no size effect in its single-atomic dispersion, which is due to the weaker Pd-Pd metal bond than Ir-Ir metal bond, the strong oxidation of I∙ to Pd, and the lower HOMO-LUMO potential energy difference of I-Pd and I-Ir. In addition, the importance of the ligand coordination environment of the single-atom Pd1 catalyst was verified. The associated work was published in ACS Catalysis 2021, 11, 9243-9251 (Contribute equally, conceived, implemented, and the supervisor).

Figure 9 Dicarbonylation of acetylene catalyzed by single-atom Pd1.

 

(10)         Sulfur poisoning, promotion, and reversible recovery of supported metal catalysts.

Metal-catalyzed sulfur poisoning has been an unsolved industrial problem for centuries. We used single-site Rh1 catalyst as the model, methanol carbonylation, ethylene/acetylene hydrocarboxyl hydroformylation, and iodobenoxycarbonylation as the probe reactions, and found an interesting phenomenon that sulfur poisoning on Rh nanoparticles but promoted on its single-atomic Rh1 catalyst. The sulfur reversal effect between nanoparticle and single-atom catalyst was addressed and highlighted. Meanwhile, the sulfur effect can be extended to other single-atomic catalysts such as Pd1, Pt1, Ir1, Au1, and so on, revealing that the conversion of inorganic sulfur (H2S) to organic sulfur (CH3SCH3, CH3SH) can greatly improve the sulfur resistance of single-atomic catalysts. The related work submissions are in ACS Catalysis, 2022, 12(7) (First providing academic idea): 4203-4215, Applied Catalysis B-Environmental November 17, 2022 (Accepted) (First Author). In addition, an in-depth study on the sulfur-resistance performance of the hydro-formylation industrialized single-atom Rh1/POPs catalyst, which has been scaled up by our research group, revealed for the first time that the single-site Rh1/POPs catalyst can be recovered from sulfur poisoning reversibly just withdrawal of the sulfur species and without any additional operation. The dynamic evolution of the geometric molecular configuration of Rh1/POPs, the sulfur poisoning process, and its reversible regeneration process during hydro-formylation were all carefully revealed. The above research plays an important role in promoting the development of sulfur-resistant and sulfur-promoted single-atomic catalysts. The related work was contributed by Nature Catalysis, November 8, 2022 (Submitted, First Author).

Figure 10 Scheme of Rh nanoparticle sulfur poisoning and Rh single-atom sulfur promotion.