CN110862126B - 一种含磷酸银/磷酸钙的水凝胶电催化电极的制备方法 - Google Patents
一种含磷酸银/磷酸钙的水凝胶电催化电极的制备方法 Download PDFInfo
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- CN110862126B CN110862126B CN201911169631.5A CN201911169631A CN110862126B CN 110862126 B CN110862126 B CN 110862126B CN 201911169631 A CN201911169631 A CN 201911169631A CN 110862126 B CN110862126 B CN 110862126B
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- phosphate
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 81
- 229940019931 silver phosphate Drugs 0.000 title claims abstract description 53
- 229910000161 silver phosphate Inorganic materials 0.000 title claims abstract description 53
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 title claims abstract description 52
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 title claims abstract description 42
- 229910000389 calcium phosphate Inorganic materials 0.000 title claims abstract description 41
- 239000001506 calcium phosphate Substances 0.000 title claims abstract description 35
- 235000011010 calcium phosphates Nutrition 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 39
- 239000000648 calcium alginate Substances 0.000 claims abstract description 34
- 235000010410 calcium alginate Nutrition 0.000 claims abstract description 34
- 229960002681 calcium alginate Drugs 0.000 claims abstract description 34
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims abstract description 34
- 239000007864 aqueous solution Substances 0.000 claims abstract description 32
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 16
- 238000005266 casting Methods 0.000 claims abstract description 16
- 239000010452 phosphate Substances 0.000 claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 16
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 14
- 239000000661 sodium alginate Substances 0.000 claims abstract description 14
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 14
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 14
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229960001714 calcium phosphate Drugs 0.000 claims description 31
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 24
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 12
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 12
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 12
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 11
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 11
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- 239000001110 calcium chloride Substances 0.000 claims description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 8
- 229940072056 alginate Drugs 0.000 claims description 8
- 235000010443 alginic acid Nutrition 0.000 claims description 8
- 229920000615 alginic acid Polymers 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005696 Diammonium phosphate Substances 0.000 claims description 6
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 6
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 6
- 239000004227 calcium gluconate Substances 0.000 claims description 6
- 229960004494 calcium gluconate Drugs 0.000 claims description 6
- 235000013927 calcium gluconate Nutrition 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 6
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 claims description 6
- 230000001112 coagulating effect Effects 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 6
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- OWKFQWAGPHVFRF-UHFFFAOYSA-N n-(diethylaminosilyl)-n-ethylethanamine Chemical compound CCN(CC)[SiH2]N(CC)CC OWKFQWAGPHVFRF-UHFFFAOYSA-N 0.000 claims description 3
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims 1
- 235000019800 disodium phosphate Nutrition 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- 239000012528 membrane Substances 0.000 abstract description 4
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 239000002105 nanoparticle Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- CZIMGECIMULZMS-UHFFFAOYSA-N [W].[Na] Chemical compound [W].[Na] CZIMGECIMULZMS-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
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- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- B01J13/0052—Preparation of gels
- B01J13/0056—Preparation of gels containing inorganic material and water
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0065—Preparation of gels containing an organic phase
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
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- B01J35/33—Electric or magnetic properties
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
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Abstract
本发明公开了一种含磷酸银/磷酸钙的水凝胶电催化电极的制备方法。首先将过量可溶性磷酸盐与硝酸银反应，生成磷酸银和可溶性磷酸盐的混合物水溶液，然后在该混合物水溶液中溶解海藻酸钠，得到铸膜液。将铸膜液涂覆到经过氨基硅烷处理的裸碳电极表面，在含过量的可溶性钙盐水溶液中充分交联，在生成海藻酸钙水凝胶的同时，在水凝胶中生成磷酸钙盐，且磷酸钙将磷酸银包裹起来避免了其在水凝胶中的流失。磷酸银赋予海藻酸钙水凝胶良好的抗菌性能。本发明制备的一种含磷酸银/磷酸钙的水凝胶电催化电极具有制备简单、成本低、制备过程绿色环保、操作方便、可多次使用等优点，在有机物电催化降解领域具有广阔的应用前景。
Description
技术领域
本发明涉及一种含磷酸银/磷酸钙的水凝胶电催化电极的制备方法，属于功能材料和催化领域。
本发明涉及电催化电极、水凝胶、磷酸银等技术领域。具体涉及一种含磷酸银/磷酸钙的水凝胶电催化电极的制备方法。
背景技术
世界各国现代工业发展迅猛，对能源的需求量也随之急剧增加，但二十世纪末以来，我们却面临巨大的能源危机，以及日益严重的环境污染问题，节约有限能源、治理污染是当务之急。电催化科学的研究恰好适应了这种要求【Appl.Catal.B，2009，88：323-330】。电催化是使电极、电解质界面上的电荷转移加速反应的一种催化作用。电极催化剂的范围仅限于金属和半导体等的电性材料。电催化研究较多的有骨架镍、硼化镍、碳化钨、钠钨青铜、尖晶石型等半导体氧化物，以及各种金属化物及酞菁一类的催化剂【Appl.Catal.B，2009，88：323-330】。电极材料主要有金属电极、碳素电极、金属氧化物电极和非金属化合物电极。
在众多应用于光催化降解的半导体材料中，TiO2由于其高活性，高化学稳定性，光稳定性，无毒和低价等优良性能被认为是最合适的光催化剂。在传统的废水处理过程中，TiO2纳米粒子通常以悬浮系统的形式被利用，因为其粒子具有较大的表面积。然而，废水中悬浮的TiO2纳米粒子的分离必然会增加营运成本并且造成二次污染，因而大大限制了其实际应用。传统的光催化剂TiO2由于其禁带宽度较宽，只对紫外光响应，而这部分光占比不到太阳光的5％，对可见光利用率低，并且电子-空穴对复合率高且具有量子效率低等缺点，因此，寻找一种新型的、对可见光利用率高、光催化降解效率高的光催化剂成为必然趋势。
磷酸银常温下为淡黄色固体粉末，微溶于水和醋酸，在加热或光照条件下会变为棕色。磷酸银以高活性著称，但存在光腐蚀、稳定性差的问题，通过对其进行表面修饰可以提高光稳定性。目前制备磷酸银的方法有：离子交换法、溶剂热法、沉淀法、浸渍法等。其中，离子交换法制备磷酸银具备工艺简单、对设备要求较低、成本低等优点。
作为绿色工艺的电化学废水处理技术在有机废水的处理方面具有独特的优势，因而近年来备受国内外研究者的青睐。在电化学反应体系中，电极处于“心脏”地位，是实现电化学反应及提高电流效率，降低能耗的关键因素。电极材料是实现电催化过程极为重要的支配因素，而电化学反应通常在电极/溶液界面的电极表面上发生。目前已知电催化电极表面材料主要涉及过渡金属及半导体化合物；基础电极一般采用贵金属电极(如Ti)和碳电极(如石墨、玻碳等)；常用的电催化电极载体多为聚合物膜和些无机物膜。电化学氧化技术以无二次污染、环境友好等优点在处理生物难降解有机废水领域受到广泛关注。
水凝胶是由交联的聚合物链通过共价键、氢键、范德华力相互作用或分子链相互缠结形成的。由于其独特的性能，水凝胶可以应用在药物释放系统、生物医学和组织工程等领域，是制备组织工程支架的理想材料。此外，绝大部分的电催化材料载体不能生物降解，用后废弃对环境容易造成污染，而海藻酸盐作为天然高分子产物，可完全被生物降解，不会造成环境危害。海藻酸盐水凝胶成膜性好，具有一定的柔韧性，方便使用。
本发明公开了一种含磷酸银/磷酸钙的水凝胶电催化电极的制备方法。首先将过量可溶性磷酸盐与硝酸银反应，生成磷酸银和可溶性磷酸盐的混合物水溶液，然后在该混合物水溶液中溶解海藻酸钠，得到铸膜液。将铸膜液涂覆到经过氨基硅烷处理的碳电极表面，在含过量的可溶性钙盐水溶液中充分交联，在生成海藻酸钙水凝胶的同时，在水凝胶中生成磷酸钙盐，且磷酸钙将磷酸银包裹起来避免了其在水凝胶中的流失。磷酸银赋予海藻酸钙水凝胶良好的抗菌性能。本发明制备的一种含磷酸银/磷酸钙的水凝胶电催化电极具有制备简单、成本低、制备过程绿色环保、操作方便、可多次使用等优点，在电催化降解领域有广阔应用前景。
发明内容
针对现有技术的不足，本发明拟解决的技术问题是磷酸银易流失、稳定性差、难以重复使用等问题。
本发明解决所述磷酸银易流失、稳定性差、难以重复使用等问题的技术方案是提供一种含磷酸银/磷酸钙的水凝胶电催化电极的制备方法。
本发明提供了一种含磷酸银/磷酸钙的水凝胶电催化电极的制备方法，其特征是包括以下步骤：
a)配制质量百分比浓度0.1-10％的可溶性磷酸盐水溶液；
b)配制质量百分比浓度0.1-10％的硝酸银水溶液；
c)将步骤a)得到的可溶性磷酸盐水溶液滴加到步骤b)得到的硝酸银水溶液中直至可溶性磷酸盐过量，获得磷酸银和可溶性磷酸盐的混合物溶液，在此混合物溶液中溶解质量百分比浓度0.2-5％的海藻酸钠，静置脱泡得到铸膜液；
d)配制质量百分比浓度0.2-10％的可溶性钙盐水溶液，作为凝固浴；
e)将步骤c)得到的铸膜液涂覆到经过氨基硅烷处理的碳电极表面，在过量的可溶性钙盐水溶液中充分交联，可溶性钙盐与海藻酸钠反应生成海藻酸钙水凝胶的同时，在海藻酸钙水凝胶中可溶性钙盐与可溶性磷酸盐生成磷酸钙，且磷酸钙将磷酸银包裹起来避免了磷酸银在海藻酸钙水凝胶中的流失；磷酸钙盐与海藻酸盐通过钙离子交联生成有机无机杂化结构，再加上其物理增强作用，从而提高了海藻酸钙水凝胶的机械强度，降低了其溶胀性能；最后用去离子水浸泡洗涤除去水凝胶中残留的无机盐，得到含磷酸银/磷酸钙的水凝胶电催化电极，该水凝胶电催化电极使用10次后还保持初始电催化降解性能的85-95％；
本发明所述的可溶性磷酸盐为磷酸氢二铵、磷酸氢二钠、磷酸氢二钾、磷酸三钾、磷酸三钠中的任意一种或两种及以上混合物；所述的可溶性钙盐为氯化钙、硝酸钙、磷酸二氢钙、葡萄糖酸钙中的任意一种或两种及以上混合物；所述的氨基硅烷为3-氨基丙基三乙氧基硅烷、3-氨基丙基三甲氧基硅烷、双(二乙基氨基)硅烷、苯氨基甲基三乙氧基硅烷中的任意一种或两种及以上混合物。
本发明制备简单、成本低、制备过程绿色环保、操作方便，由于催化剂磷酸银被固定在水凝胶及磷酸钙中，得到的电极可重复使用；本发明的电极在染料、抗生素、内分泌干扰物等有机物的电催化降解领域具有广阔的应用前景。
具体实施方式
下面介绍本发明的具体实施例，但本发明不受实施例的限制。
实施例1.
a)配制质量百分比浓度5％的磷酸氢二铵水溶液；
b)配制质量百分比浓度2％的硝酸银水溶液；
c)将步骤a)得到的磷酸氢二铵水溶液滴加到步骤b)得到的硝酸银水溶液中直至磷酸氢二铵过量，获得磷酸银和磷酸氢二铵的混合物溶液，在此混合物溶液中溶解质量百分比浓度2％的海藻酸钠，静置脱泡得到铸膜液；
d)配制质量百分比浓度3％的氯化钙水溶液，作为凝固浴；
将步骤c)得到的铸膜液涂覆到经过3-氨基丙基三乙氧基硅烷处理的碳电极表面，在过量的氯化钙水溶液中充分交联，氯化钙与海藻酸钠反应生成海藻酸钙水凝胶的同时，在海藻酸钙水凝胶中氯化钙与磷酸氢二铵生成磷酸钙，且磷酸钙将磷酸银包裹起来避免了磷酸银在海藻酸钙水凝胶中的流失；磷酸钙盐与海藻酸盐通过钙离子交联生成有机无机杂化结构，再加上其物理增强作用，从而提高了海藻酸钙水凝胶的机械强度，降低了其溶胀性能；最后用去离子水浸泡洗涤除去水凝胶中残留的无机盐，得到含磷酸银/磷酸钙的水凝胶电催化电极；该水凝胶电催化电极使用10次后还保持初始电催化降解性能的95％。
实施例2.
a)配制质量百分比浓度4％的磷酸氢二钾水溶液；
b)配制质量百分比浓度1％的硝酸银水溶液；
c)将步骤a)得到的磷酸氢二钠/磷酸氢二钾水溶液滴加到步骤b)得到的硝酸银水溶液中直至磷酸氢二钠/磷酸氢二钾过量，获得磷酸银和磷酸氢二钠/磷酸氢二钾的混合物溶液，在此混合物溶液中溶解质量百分比浓度2％的海藻酸钠，静置脱泡得到铸膜液；
d)配制质量百分比浓度4％的氯化钙和硝酸钙混合水溶液，作为凝固浴；
将步骤c)得到的铸膜液涂覆到经过3-氨基丙基三甲氧基硅烷处理的碳电极表面，在过量的氯化钙/硝酸钙水溶液中充分交联，氯化钙/硝酸钙与海藻酸钠反应生成海藻酸钙水凝胶的同时，在海藻酸钙水凝胶中氯化钙/硝酸钙与磷酸氢二钠/磷酸氢二钾生成磷酸钙，且磷酸钙将磷酸银包裹起来避免了磷酸银在海藻酸钙水凝胶中的流失；磷酸钙盐与海藻酸盐通过钙离子交联生成有机无机杂化结构，再加上其物理增强作用，从而提高了海藻酸钙水凝胶的机械强度，降低了其溶胀性能；最后用去离子水浸泡洗涤除去水凝胶中残留的无机盐，得到含磷酸银/磷酸钙的水凝胶电催化电极；该水凝胶电催化电极使用10次后还保持初始电催化降解性能的85％。
实施例3.
a)配制质量百分比浓度6％的磷酸氢二钠和磷酸三钾的混合水溶液；
b)配制质量百分比浓度3％的硝酸银水溶液；
c)将步骤a)得到的磷酸氢二钠/磷酸三钾水溶液滴加到步骤b)得到的硝酸银水溶液中直至磷酸氢二钠/磷酸三钾过量，获得磷酸银和磷酸氢二钠/磷酸三钾的混合物溶液，在此混合物溶液中溶解质量百分比浓度5％的海藻酸钠，静置脱泡得到铸膜液；
d)配制质量百分比浓度6％的磷酸二氢钙水溶液，作为凝固浴；
将步骤c)得到的铸膜液涂覆到经过双(二乙基氨基)硅烷处理的碳电极表面，在过量的硝酸钙/磷酸二氢钙水溶液中充分交联，硝酸钙/磷酸二氢钙与海藻酸钠反应生成海藻酸钙水凝胶的同时，在海藻酸钙水凝胶中硝酸钙/磷酸二氢钙与磷酸氢二钠/磷酸三钾生成磷酸钙，且磷酸钙将磷酸银包裹起来避免了磷酸银在海藻酸钙水凝胶中的流失；磷酸钙盐与海藻酸盐通过钙离子交联生成有机无机杂化结构，再加上其物理增强作用，从而提高了海藻酸钙水凝胶的机械强度，降低了其溶胀性能；最后用去离子水浸泡洗涤除去水凝胶中残留的无机盐，得到含磷酸银/磷酸钙的水凝胶电催化电极，该水凝胶电催化电极使用10次后还保持初始电催化降解性能的94％。
实施例4.
a)配制质量百分比浓度5％的磷酸氢二铵水溶液；
b)配制质量百分比浓度2.5％的硝酸银水溶液；
c)将步骤a)得到的磷酸氢二铵/磷酸三钾水溶液滴加到步骤b)得到的硝酸银水溶液中直至磷酸氢二铵/磷酸三钾过量，获得磷酸银和磷酸氢二铵/磷酸三钾的混合物溶液，在此混合物溶液中溶解质量百分比浓度3％的海藻酸钠，静置脱泡得到铸膜液；
d)配制质量百分比浓度5％的葡萄糖酸钙水溶液，作为凝固浴；
将步骤c)得到的铸膜液涂覆到经过苯氨基甲基三乙氧基硅烷处理的碳电极表面，在过量的硝酸钙/葡萄糖酸钙水溶液中充分交联，硝酸钙/葡萄糖酸钙与海藻酸钠反应生成海藻酸钙水凝胶的同时，在海藻酸钙水凝胶中硝酸钙/葡萄糖酸钙与磷酸氢二铵/磷酸三钾生成磷酸钙，且磷酸钙将磷酸银包裹起来避免了磷酸银在海藻酸钙水凝胶中的流失；磷酸钙盐与海藻酸盐通过钙离子交联生成有机无机杂化结构，再加上其物理增强作用，从而提高了海藻酸钙水凝胶的机械强度，降低了其溶胀性能；最后用去离子水浸泡洗涤除去水凝胶中残留的无机盐，得到含磷酸银/磷酸钙的水凝胶电催化电极，该水凝胶电催化电极使用10次后还保持初始电催化降解性能的92％。
Claims (4)
1.一种含磷酸银/磷酸钙的水凝胶电催化电极的制备方法，其特征是包括以下步骤：
a)配制质量百分比浓度0.1-10％的可溶性磷酸盐水溶液；
b)配制质量百分比浓度0.1-10％的硝酸银水溶液；
c)将步骤a)得到的可溶性磷酸盐水溶液滴加到步骤b)得到的硝酸银水溶液中直至可溶性磷酸盐过量，获得磷酸银和可溶性磷酸盐的混合物溶液，在此混合物溶液中溶解质量百分比浓度0.2-5％的海藻酸钠，静置脱泡得到铸膜液；
d)配制质量百分比浓度0.2-10％的可溶性钙盐水溶液，作为凝固浴；
e)将步骤c)得到的铸膜液涂覆到经过氨基硅烷处理的碳电极表面，在过量的可溶性钙盐水溶液中充分交联，可溶性钙盐与海藻酸钠反应生成海藻酸钙水凝胶的同时，在海藻酸钙水凝胶中可溶性钙盐与可溶性磷酸盐生成磷酸钙，且磷酸钙将磷酸银包裹起来避免了磷酸银在海藻酸钙水凝胶中的流失；磷酸钙盐与海藻酸盐通过钙离子交联生成有机无机杂化结构，再加上其物理增强作用，从而提高了海藻酸钙水凝胶的机械强度，降低了其溶胀性能；最后用去离子水浸泡洗涤除去水凝胶中残留的无机盐，得到含磷酸银/磷酸钙的水凝胶电催化电极。
2.如权利要求1所述一种含磷酸银/磷酸钙的水凝胶电催化电极的制备方法，其特征是所述的可溶性磷酸盐为磷酸氢二铵、磷酸氢二钠、磷酸氢二钾、磷酸三钾、磷酸三钠中的任意一种或两种及以上混合物。
3.如权利要求1所述一种含磷酸银/磷酸钙的水凝胶电催化电极的制备方法，其特征是所述的可溶性钙盐为氯化钙、硝酸钙、磷酸二氢钙、葡萄糖酸钙中的任意一种或两种及以上混合物。
4.如权利要求1所述一种含磷酸银/磷酸钙的水凝胶电催化电极的制备方法，其特征是所述的氨基硅烷为3-氨基丙基三乙氧基硅烷、3-氨基丙基三甲氧基硅烷、双(二乙基氨基)硅烷、苯胺基甲基三乙氧基硅烷中的任意一种或两种及以上混合物。
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